EUR23003 EN - 2007

Project HORIZONTAL Validation Reporton polybrominated diphenylethers

Validation of a horizontal standard for the determination ofselected polybrominated diphenylethers (PBDE) by gas-chromatography method with mass selective detection (GC-MS) in a European Intercomparison Exercise

E Sobiecka H van der Sloot D Barcelo B M Gawlik

The mission of the Institute for Environment and Sustainability is to provide scientific-technical support to the European Unionrsquos Policies for the protection and sustainable development of the European and global environment European Commission Joint Research Centre Institute for Environment and Sustainability Contact information Address Via Enrico Fermi 2749 21027 Ispra (VA) Italy E-mail berndgawlikjrcit Tel +39 0332 789487 Fax +39 0332 789158 httpiesjrceceuropaeu httpwwwjrceceuropaeu Legal Notice Neither the European Commission nor any person acting on behalf of the Commission is responsible for the use which might be made of this publication A great deal of additional information on the European Union is available on the Internet It can be accessed through the Europa server httpeuropaeu JRC 40184 EUR 23003 EN ISBN 978-92-79-07403-5 ISSN 1018-5593 DOI 1027884502 Luxembourg Office for Official Publications of the European Communities copy European Communities 2007 Reproduction is authorised provided the source is acknowledged Printed in Luxemburg

Project HORIZONTAL Validation Report

Validation of a horizontal standard for the determination of selected polybrominated diphenylethers (PBDE) by gas-chromatography method with mass selective detection (GC-MS) in a European Intercomparison Exercise E Sobiecka H Van der Sloot D Barcelo B M Gawlik Elzbieta Sobiecka Bernd Manfred Gawlik European Commission Joint Research Centre Institute for Environment and Sustainability Via Enrico Fermi 21020 Ispra - Italy

Hans van der Sloot ECN Emission Characterisation and Reduction Westerduinweg 3 PO Box 1 1755 ZG Petten The Netherlands

Damia Barcelo Consejo Superior de Investigaciones Cientificas (CSIC) IIQAB Jordi Girona 18 E-08034 BARCELONA Spain

to whom correspondence should be sent

by email to berndgawlikjrcit

Summary Project HORIZONTAL is interdisciplinary aiming at a harmonisation and horizontal standardisation of test procedures in particular for sludge soils and biowastes In the context of this standardization project a series of draft technical specification were designed upon an extensive desk study fine-tuned after expert consultations and finally validated in international intercomparisons exercise This report summarises the work performed within the validation study of the draft standard for the determination of polybrominated diphenylethers (PBDE) in soils sludge and treated bio-waste using gas-chromatography method with mass selective detection (GC-MS) It further explains the underlying statistical concept for the calculation of reproducibility and repeatability from intercomparisons data In addition all single values results of the statistical evaluation as well as background information on the validation materials used are described and explained

Abbreviations Throughout this report the following abbreviations are used ANOVA Analysis of variances

CAS Chemical Abstracts System

CEN Comitteeacute Europeacuteen de Normalisation

DG Directorate General

ECD Electron Capture Detector

ECN Energy Research Centre for the Netherlands

EU European Union

IES Institute for Environment and Sustainability

IT Information Technology

ISO International Organization for Standardisation

JRC Joint Research Centre

GC Gas Chromatography

MILC Measure Interlaboratory Comparison

MS Mass Spectroscopy

p Number of labs

PBDE Polybrominated Diphenylethers

r Repeatability limit

R Reproducibility limit

sr Repeatability standard deviation

sR Reproducibility standard deviation

TC Technical Committee

4

Table of Contents Summary 2 Abbreviations 3 Table of Contents 4

Introduction to the validation project 5 11 Statistical concept underlying the validation 6

111 Introduction to the statistical model 6 112 Requirements for precision experiment 7 113 Statistical analysis 8

12 Validation exercise for PBDE 8 121 Compounds to be measured 8 122 Samples dispatched for the validation of PBDE 8 123 Draft standards to be followed 8 124 Analytical programm 8 125 Timing and Submission of data 9 126 Participants 10

13 Summary results and derived performance characteristics 11 14 Annexes 15

5

Introduction to the validation project Project HORIZONTAL is interdisciplinary aiming at a harmonisation and horizontal standardisation of test procedures in particular for sludges soils and biowastes It was created as in response to the European Commission Mandate M 330 given to CEN asking for the development and validation of those standards in support of forthcoming EU Directives such as

o The revision of the Sewage Sludge Directive 86278EEC o The Directive on the biological treatment of biodegradable waste o The initiative on a legal framework for soil monitoring in Europe

This mandate explicitly considers standards for the entire analytical procedure (ie sampling pre-treatment and analytical measurement methods for inorganic organic hygiene and biological parameters) These are grouped into classes according to their physicalchemical properties which in turn determine the methods needed to quantify the potential impact on human and animal health plant uptake soil function and groundwater quality As the materials generally feature a mixture of different types of contaminants it is important to provide an integrated answer covering evaluation of all relevant pollutants In order to fulfil the requirements of the aforementioned mandate the European Commissions Joint Research Centre (JRC) and its Directorate-General for Environment (DG ENV) together with the Technical Committees of the European Standardisation Committee (CEN TCs) concerned designed a pre-normative research initiative called Project HORIZONTAL and presented it to the Commission and the Environmental Authorities in the Member States After an extensive literature research and careful evaluation of the feasibility of a given horizontal standard the standards were drafted and finally validated in an European laboratory intercomparison The underlying statistical concept information about the materials used details about the participants measurement results obtained as well as the derived performance characteristics obtained for the determination of polybrominated diphenylethers (PBDE) are described hereafter

6

11 Statistical concept underlying the validation According to the requirements of the work package concerning data handling amp interpretation of the project HORIZONTAL-ORG the respective validation intercomparisons have to be evaluated according to the principles laid down in ISO standard 5725-21994 In particular repeatability and reproducibility of the draft standard methods have to be determined The determination of trueness would require the availability of independent reference values for the materials investigated This however is not possible and was not requested in the frame of this work In the following the approach chosen is explained

111 Introduction to the statistical model The statistical model used in ISO 5725 for estimation of accuracy of a measurement method assumes that every test result is the sum of three components

eBmy ++= y test result m general mean B laboratory component of bias under repeatability conditions e random error occurring in every measurement under repeatability conditions

In the workprogram the quantification of term e is explicitly asked for (ie repeatability and reproducibility) The repeatability variance is measured directly as the variance of the error term e but the reproducibility depends on the sum of the repeatability variance and the between-laboratory variance

( )er var=σ 22rLR σσσ += with ( )BL var=σ

However soil biowaste and sludge are multi-phase materials ie they contain two or more distinct types of particles which are fundamentally different in their properties and composition As a consequence this introduces an important source of variation for the intercomparison exercise which needs to be considered ie the inherent heterogeneity of the materials Thus a contribution of variation between samples H is introduced to the general statistical model

HeBmy +++= Using ANOVA techniques the different variances are calculated and separated for the evaluation

7

112 Requirements for precision experiment

Layout of the experiment A suite of 10 to 12 different materials (soil sludge and biowaste) has been made available for the intercomparison exercise For each parameter investigated at least 10 to laboratories should be nominated to participate The same laboratories should be used for different parameters as far as possible Due to the complexity of analysis and the respective workload to the laboratories it was decided to propose three materials for the validation of the PBDE draft standard Each laboratory received two bottles of each material and was be requested to perform 4 independent analyses per material1 (2 per bottle) using the respective draft standard methods The 4 analysis per material should be carried out under repeatability conditions (ie same operator2 same equipment within a short period of time) As far as possible also the different materials should be measured under repeatability conditions however changes of eg operator or equipment are permitted but must be reported Likewise different materials can be analysed on different days if necessary Equipment used in the experiment needed to be checked prior to the experiment according to the requirements of the draft standard The results of these checks have to be documented Similarly date and time of each measurement had to be recorded for verification of repeatability conditions An appropriate timeframe for the entire exercise has been set and was to be respected

Recruitment of the laboratories Each sub-workpackage leader of HORIZONTAL was asked to select the laboratories using the information from section 52 of ISO 5725-21994 and provide the signed questionnaires (see also Annex 1) The workpackage leaders were responsible for providing the laboratories with the draft standard method and explaining the context of this exercise

Preparation and use of the materials Materials used for the exercise were prepared according to the general requirements for reference materials as laid down in ISO Guide 34 Materials were accompanied by instructions for use

Reporting of results Online submissions of results using an internet-based IT platform as well as XLS-Spreadsheets were used In case of online data submission the participating laboratories received a unique and confidential login and password in due time enabling them to

1 Independent analysis means analysis of independent test portions applying the entire analytical scheme to this test portion from eg extraction to quantification For instance it does not mean replicate injections of aliquots into a GC-MS instrument 2 Operator in this context may also consist of a fixed team of persons eg one person performing extraction one clean-up one quantification

8

enter their data in a structured form For authentication purposes a signed printout had to be submitted by mail The online data submission included a detailed questionnaire for additional information on the measurements

113 Statistical analysis Statistical analysis of data followed the requirements of ISO 5725-21994 and ISO 5725-51998 Appropriate tests for the homogeneity of variance detection of outliers and normal distribution were applied Statistical evaluation was done using an Excel Macro developed tested and successfully applied in other occasion by ECN Evaluation was executed jointly by JRC and ECN

12 Validation exercise for PBDE

121 Compounds to be measured The following compound were selected for the validation exercise Tetra-BDE-47 Penta-BDE-100 Penta-BDE-99 Hexa-BDE-154 Hexa-BDE-153 Hepta-BDE-183 Octa-BDE-196 Octa-BDE-197 Octa-BDE-203 Deca-BDE-209

122 Samples dispatched for the validation of PBDE After a preliminary rough screening the following materials were used for the validation round of PBDE

bull Compost 1 A pollutant loaded compost material from Vienna bull Sewage Sludge 1 A mixed sewage sludge from Essen bull Soil 3 A sludge amended soil from Barcelona

A more detailed description of background concentrations can be found in Annex 2 to this report The samples were dispatched simultaneously to all participants using a private courier service

123 Draft standards to be followed The draft standards to be followed could be downloaded following this link which is situated on the website of the Project HORIZONTAL httpwwwecnnldocssocietyhorizontalBFR_Standard_for_validationpdf

124 Analytical programm Of each of the three materials 2 bottles had to be analysed and each bottle had to analysed independently twice As mentioned above analyses were to be done under repeatability conditions Results were to be reported referring to DRY MATTER content The choice how to apply dm correction was free for each participant

9

125 Timing and Submission of data Dispatch of samples was done on the 18th of October 2006 For users of the Online data submission system (MILC) User Registration was possible from 14th of November 2006 with opening of the MILC Data Submission on 1st of December 2006 The deadline for submission of results has been set for PBDE to the 12th of January 2007 but was extended to the end of the same months After that no further submission was possible Alternatively the participants were allowed to submit data electronically as Excel sheet using simply Email All data were treated in a confidential way Any presentation hereafter will refer only to numerical data and it will not be possible to identify the originating laboratory Lab Codes displayed are NOT related to the order of laboratories hereafter In addition to the information provide an Helpdesk was implemented in order to give quick and individual response to the participants during and immediately after the validation study In case of doubt and suspected transcription errors further enquires were conducted by JRC

10

126 Participants The following table lists the participating organisations and entities in the validation exercise for the horizontal PBDE standard

bull Austria o Umweltbundesamt

bull Czech Republic o Povodi Labe statni podnik - OVHL Laboratory

bull France o CIRSEE o CTC Environnement o INERIS

bull Germany o Federal Environmental Agency Section III 34 Laboratory Methods for

the Surveillance of Waste and Wastewater (UBA) bull Italy

o European Commission DG JRC IES bull Spain

o Consejo Superior de Investigaciones Cientificas (CSIC)

bull Sweden o ALCONTROL AB

11

13 Summary results and derived performance characteristics The result of the various statistical evaluation including outlier tests calculation of repeatability and reproducibility standard deviation for the congeners of interest can be found in Annex 3 of this report In addition all data submitted by the participants as well as those considered for the calculation of the performance characteristics are listed in Annex 3 to this report Based on these calculations the following results were obtained in the validation round upon statistical evaluation according to ISO 5725-2 The average values the repeatability standard deviation (sr) and the reproducibility standard deviation (sR) were obtained (Table1) The repeatability is determined as an interval around a measurement result (ie repeatability limit) This interval corresponds to the maximum difference that can be expected (with a 95 statistical confidence) between one test result and another both test results being obtained under the following conditions The tests are performed in accordance with all the requirements of the present standard by the same laboratory using its own facilities and testing laboratory samples obtained from the same primary field sample and prepared under identical procedures The repeatability limit was calculated using the relationship r test = f radic2 s rtest with the critical range factor f = 2 The reproducibility like repeatability is also determined as an interval around a measurement result (ie reproducibility limit) This interval corresponds to the maximum difference that can be expected (with a 95 statistical confidence) between one test result and another test result obtained by another laboratory both test results being obtained under the following conditions The tests are performed in accordance with all the requirements of the present standard by two different laboratories using their own facilities and testing laboratory samples obtained from the same primary field sample and prepared under identical procedures The reproducibility limit was calculated using the relationship R = f radic2 sR with the critical range factor f = 2

12

Table 1 - Results of the interlaboratory comparison studies of the determination of selected polybrominated diphenyl ethers (PBDE) by gaschromatography with mass spectrometric detection (GC-MS) in soil sludge and treated biowaste All concentrations are expressed in mgkg dm

Matrix Parameter Mean sr sR r R p Outliers Used No of data

No of data reported below

detection

Total no of data

Sludge 1 PBD 47 00181 461 4 15 5 20 Compost 1 00039 94 3 12 0 12 Soil 3 00010 50 50 00014 00014 4 0 13 10 23 Sludge 1 PBD 99 00239 64 28 00043 00186 5 1 19 0 23 Compost 1 00029 31 35 00025 00028 5 0 17 4 21 Soil 3 00013 499 4 16 8 24 Sludge 1 PBD 100 00049 51 17 00007 00024 5 1 18 2 24 Compost 1 00009 25 29 00006 00007 4 0 14 7 21 Soil 3 61103 211 3 10 15 25 Sludge 1 PBD 153 00038 33 38 00034 0004 5 0 18 0 18 Compost 1 00019 116 3 11 3 14 Soil 3 00011 177 2 10 10 20 Sludge 1 PBD 154 00023 234 4 15 2 17 Compost 1 00008 1118 3 9 5 14

13

Matrix Parameter Mean sr sR r R p Outliers Used No of data

No of data reported below

detection

Total no of data

Soil 3 00002 1049 4 13 6 19 Sludge 1 PBD 183 00048 1217 3 12 2 14 Compost 1 00009 1048 2 8 5 13 Soil 3 00011 1395 3 12 6 18 Sludge 1 PBD 196 00037 470 2 8 7 15 Compost 1 00004 950 2 6 4 10 Soil 3 00023 519 3 12 2 14 Sludge 1 PBD 197 00062 834 2 6 8 14 Compost 1 00009 1001 2 7 7 14 Soil 3 00032 904 2 8 6 14 Sludge 1 PBD 203 00037 461 2 8 4 12 Compost 1 00004 978 2 5 3 8 Soil 3 00022 598 3 12 0 12 Sludge 1 PBD 209 02493 170 39 01186 02689 5 0 16 2 18 Compost 1 00273 104 3 10 5 15 Soil 3 02582 1115 51 00806 03676 6 0 22 0 22

14

Matrix Parameter Mean sr sR r R p Outliers Used No of data

No of data reported below

detection

Total no of data

Sludge 1 Sum PBD 0256 155 548 0111 0392 6 1 22 Compost 1 0009 331 637 0008 0016 5 1 18 Soil 3 0227 116 717 0074 0455 7 1 26 Abbreviations sr Repeatability standard deviation SR Reproducibility standard deviation r Repeatability limit (comparing two measurements) R Reproducibility limit (comparing two measurements) p Number of labs determination not possible

15

14 Annexes Annex 1 Model questionnaire to be filled by the participating laboratories Annex 3 Report on the validation materials used Annex 2 Statistical calculations Annex 3 Data submitted

16

Annex 1

Model questionnaire to be filled by the participating laboratories

Model questionnaire to be filled by the participating laboratories Name of laboratory Contact person Contact details email Phone Fax Mail address of lab Dispatch address of lab for shipment of samples (no PO boxes) Title of measurement method (copy attached) Our laboratory is willing to participate in the precision experiment for this draft standard method

Yes No As participant we understand that

bull All essential apparatus chemicals and other requirements specified in the method must be available in our laboratory when the programme begins

bull Specified timing requirements such as starting and finishing date of the programme must be rigidly met

bull The method must be strictly adhered to bull Samples must be handled in accordance with instructions bull A qualified operator must perform the measurements

Having studied the method and having made a fair appraisal of our capabilities and facilities we feel that we will be adequately prepared for cooperative testing of this method Comments helliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphellip Signature Date

17

Annex 2

Report on the validation materials used

VI

Abstract This report gives an overview on the available analytical information on the following raw materials to be used for the production of validation materials of the so-called Project HORIZONTAL

bull Four sludge materials from Duumlsseldorf Germany

bull An agricultural soil material from Reading United Kingdom

bull A compost material from Vienna Austria

bull A compost material from Korschenbroich Germany

bull A sludge-amended agricultural soil from Pavia Province Italy

bull A sludge-amended soil from Barcelona Spain

bull A sludge-amended soil from Essen Germany

bull A long-term sludge exposed soil from Hohenheim Germany

VII

List of Abbreviations Throughout this report the following abbreviations are used

AOX absorbable organic halogens

Corg organic carbon content

Ctotal total carbon content

CAT cation exchangeable

CDD chlorinated dibenzodioxin

CDF chlorinated dibenzofuran

DEHP di(2-ethylhexyl)phthalate

DM dry matter

EPA Environment Protection Agency

EU European Union

FM fresh matter

Hp hepta

Hx hexa

IES Institute for Environment and Sustainability

IRMM Institute for Reference Materials and Measurements

JRC Joint Research Centre

LAS linear alkylsulfonates

LoD limit of detection

LUA Landesumweltamt

Ntotal total nitrogen content

NH4-N Ammonium nitrogen

NO3-N Nitrate nitrogen

NP nonylphenol

NRW North Rhine Westphalia

O octa

P poly

PAH polycyclic aromatic hydrocarbon

PCB polychlorinated biphenyl

Pe penta

T tetra

TEQ toxicity equivalent

UBA Umweltbundesamt

WHO World Health Organization

WWTP waste water treatment plant

6

1 Introduction This report gives an overview on the available analytical information on the following raw materials to be used for the production of validation materials of the so-called Project HORIZONTAL

bull Four sludge materials from Duumlsseldorf Germany

bull An agricultural soil material from Reading United Kingdom

bull A compost material from Vienna Austria

bull A compost material from Korschenbroich Germany

bull A sludge-amended agricultural soil from Pavia Province Italy

bull A sludge-amended soil from Barcelona Spain

bull A sludge-amended soil from Essen Germany

bull A long-term sludge exposed soil from Hohenheim Germany

The following analytical information was gathered partly before and during the sampling of the raw materials to be used for the production of the HORIZONTAL validation materials The material were sampled by IES and shipped to IRMM in the course of the year 2005 The information gathered was then completed by various analytical screenings for PAHs and PCBs done by the Institute for Reference Materials and Measurements Geel Belgium for phthalates done by UBA Berlin Germany for PBDE done by IIQAB-CSIC Barcelona Spain for trace elements and some selected major and minor elements by the Institute for Environment and Sustainability Ispra Italy

The work compiled hereafter is based on the numerous additional efforts of the scientists working at various members of the consortium Project HORIZONTAL-Org and contributing organisations

This work is gratefully acknowledged

2 Overview on property values

21 Sludge materials from Duumlsseldorf Germany

The various sewage sludge materials originate from various installations in the North Rhine Westphalia and were produced and sampled by staff from the Landesumweltamt (LUA) NRW under the responsibility from Dr K Furtmann

In total four sludge materials (Sludge A and D from a major municipal WWTP Sludge B from a municipal WWTP with industrial input and Sludge C from a municipal WWTP with high PCB-Content) were obtained and will be blended to two final materials Before sampling the following analytical data for a typical sample were received

7

Table 1 ndash Analytical data obtained on an average sludge sample in LUA NRW (with courtesy of K Furtmann LUA Duumlsseldorf)

Parameter Concentration PCB 120 ugkg DEHP 110 mgkg PAH 5 mgkg (EPA) PCDDF 15 ng TEkg PBDE 400 ugkg NP 40 mgkg LAS 3 gkg AOX 300 mgkg

Subsequent screening led to the information displayed hereafter It should be stressed that the data were obtained as SCREENING information on the UNTREATED or partially treated raw materials Therefore the final target values which are relevant for the validation intercomparison can be different

Table 2 ndash Analytical data obtained on a first screening on the sludge samples from LUA NRW

Sewage sludge A

Dusseldorf

sewage sludge D

Dusseldorf PCB (ngg) 28 62 35 52 101 65 101 31 38 118 49 40 153 30 33 105 24 11 138 46 38 156 lt1 lt1 180 34 23 170 23 19 PAH (ngg) Naphtalene 34 381 Acenaphtylene 15 43 Acenaphthene 81 108 Fluorene 94 1167 Phenantrene 3440 Anthracene 22 344 Flouranthene 316 4817 Pyrene 235 3011 Benz(a)anthracene 473 791 Chrysene 691 1078 Benz(b)fluoranthene 538 1688 Benz(k)fluoranthene 228 635 Benz(a)pyrene 383 1114 Indeno(123-cd)pyrene 92 229 Dibenzo(ah)anthracene 71 70 Benzo(ghi)perylene 80 185

8

Table 3 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Sludge D (1) 0135 41474 385 Sludge B (2) 0538 0034 30634 547 Sludge A (3) 0184 0037 31399 146 Sludge C (4) 0354 1528 6678 229

Table 4 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Sludge 2

(B)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

554

959

694

591

772

509

nq

nq

970

2216

2379

Table 5 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena IES Ispra Spain) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Sludge 1 (D) 265 290 533 359 1231 338 784 438 lt 005 232 786 Sludge 2 (B) 119 311 626 202 278 299 722 251 lt 005 118 625 Sludge 3 (A) 168 360 621 332 847 416 119 451 lt 005 116 1237 Sludge 4 (C) 563 198 116 273 726 511 473 618 lt 005 444 2015

Table 6 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Sludge 1 (D) 2154 58 844 099 103 101 4367 lt15 50448 Sludge 2 (B) 1067 366 692 046 1491 077 5217 lt15 57633 Sludge 3 (A) 731 663 684 035 1287 068 3733 lt15 60369 Sludge 4 (C) 4379 965 527 163 522 107 5628 lt15 23945

Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM)Sludge 1 (D) 03 2403 101 1002 350 15 1944 132Sludge 2 (B) 031 315 97 879 172 12 514 180Sludge 3 (A) 031 1281 153 1567 265 16 1440 168Sludge 4 (C) 055 231 628 2625 371 81 1101 244

9

22 Agricultural soil material from Reading United Kingdom

The material was proposed by the University of Reading (S Nortcliff) and was sampled from a site called ldquoFrogmore Farmrdquo which was featured in the ldquoMetalsrdquo Report for HORIZONTAL This site is close to Reading with soils developed on flintyloamy periglacial materials over Chalk has a long and well documented history of sludge application The focus of the work of Nortcliff et al undertook at this site and the monitoring and control at the site (by Thames Water and the subsequent subsidiary bodies dealing with sludge application to soil) was on metals (and metal loads) with no analysis or indeed any form of investigation in to organics in the broadest sense

The analytical information produced in the context of the screening of the raw material is displayed below

Table 7 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 3

(Reading) 0032 0119 669

Table 8 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 3 (Reading) 015 706 279 138 152 901 267 300 lt 005 258 931

Table 9 ndash Analytical data obtained on a first screening on the sludge-amended soil from Reading (courtesy of IRMM)

Parameter Concentration

PCB ngg 28 lt1 52 lt1 101 lt1 118 lt1 153 lt1 105 lt1 138 lt1 156 lt1 180 lt1 170 lt1 PAH ngg Naphtalene lt10 Acenaphtylene 21 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene lt10 Flouranthene 818 Pyrene 776 Benz(a)anthracene 565

10

Parameter Concentration

Chrysene 608 Benz(b)fluoranthene 824 Benz(k)fluoranthene 329 Benz(a)pyrene 799 Indeno(123-cd)pyrene

779

Dibenzo(ah)anthracene 118 Benzo(ghi)perylene 394

Table 10 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 3

(Reading)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

103

003

nq

nq

nq

nd

nd

272

273

Table 11 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 3 (Reading) 015 706 279 138 152 901 267 300 lt 005 258 931

Table 12 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 3 (Reading) 7936 477 112 096 194 017 4107 443 2102 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 3 (Reading) 042 13 45 69 69 69 216 92

Table 13 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 3 (Reading) 012

11

23 Compost from Vienna Austria

The fresh compost material was obtained from the Austrian Federal Environment Agency (UBA Vienna) which had used a sub-batch of the raw material for national intercomparson The remainder of the material was stored at 4degC until shipment to IRMM for further processing The following analytical information was provided by UBA Austria and completed with various screenings

Table 14 ndash Analytical data on compost material received from UBA Austria Inorganic and sum parameters

Parameter Unit Sample fraction used Observed mean B CAT mgl FM Fresh sample lt10mm 61 K CAT mgl FM Fresh sample lt10mm 2624 Mg CAT mgl FM Fresh sample lt10mm 242 P CAT mgl FM Fresh sample lt10mm 49 B CAT DM Fresh sample lt10mm 00017 K CAT DM Fresh sample lt10mm 072 Mg CAT DM Fresh sample lt10mm 007 P CAT DM Fresh sample lt10mm 001 NO3-N mgkg FM Fresh sample lt10mm 35 NH4-N mgkg FM Fresh sample lt10mm 230 Ctotal DM lt45degdry milled 29 Corg DM lt45degdry milled 27 Ntotal DM lt45degdry milled 17 P mgkg DM lt45degdry milled 2596 K mgkg DM lt45degdry milled 11019 K DM lt45degdry milled 110 B mgkg DM lt45degdry milled 60 Cd mgkg DM lt45degdry milled 046 Cr mgkg DM lt45degdry milled 25 Cu mgkg DM lt45degdry milled 46 Hg mgkg DM lt45degdry milled 020 Ni mgkg DM lt45degdry milled 18 Pb mgkg DM lt45degdry milled 45 Zn mgkg DM lt45degdry milled 198 Ca mgkg DM lt45degdry milled 68776 Ca DM lt45degdry milled 69 Mo mgkg DM lt45degdry milled 08 S mgkg DM lt45degdry milled 2137 Fe mgkg DM lt45degdry milled 9959 Mn mgkg DM lt45degdry milled 418 Na mgkg DM lt45degdry milled 742 Co mgkg DM lt45degdry milled 41 AOX mgkg DM lt30deg dry milled 62

Table 15 ndash Analytical data on compost material received from UBA Austria Polycyclic aromatic hydrocarbons

PAH Unit Result Naphthaline microgkg DM 93 Acenaphthylene microgkg DM 86 Acenaphthene microgkg DM 5 Fluorene microgkg DM 80 Phenanthrene microgkg DM 89 Anthracene microgkg DM 27 Fluoranthene microgkg DM 487 Pyrene microgkg DM 380

12

PAH Unit Result Benzo(a)anthracene microgkg DM 278 Chrysene microgkg DM 317 Benzo(b)fluoranthene microgkg DM 365 Benzo(k)fluoranthene microgkg DM 193 Benz(a)pyrene microgkg DM 320 Indeno(123-cd)pyrene microgkg DM 233 Dibenz(ah)anthracene microgkg DM 67 Benzo(ghi)perylene microgkg DM 225 Sum EPA microgkg DM 3013 Sum EPA mgkg DM 30

Table 16 ndash Analytical data on compost material received from UBA Austria Sum PCDDs and PCBs

Parameter

Dioxine TEQ (ITEF) ngkg DM 73 TEQ (WHO) ngkg DM 35 PCB Σ Ballschmiter mgkg DM 005

Table 17 ndash Analytical data on compost material obtained by screening in IRMM

Parameter Result in ngg

PCB 28 2 52 2 101 4 118 3 153 10 105 1 138 8 156 1 180 5 170 lt1 PAH Naphtalene lt10 Acenaphtylene lt10 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene 26 Fluoranthene 611 Pyrene 510 Benz(a)anthracene 888 Chrysene 957 Benz(b)fluoranthene 1531 Benz(k)fluoranthene 547 Benz(a)pyrene 1101 Indeno(123-cd)pyrene 416 Dibenzo(ah)anthracene 81 Benzo(ghi)perylene 295

13

Table 18 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Compost 1

(Vienna)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

402

019

259

nq

023

004

nq

nq

144

174

259

Table 19 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Compost 1

(Vienna) 0058 1426 557

Table 20 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Compost 1 (Vienna) 039 736 319 410 365 127 495 004 079 013 208

Table 21 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Compost 1 (Vienna) 2063 431 617 426 199 249 1602 lt15 10521

Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Compost 1 (Vienna) 035 3496 81 375 79 55 653 60

Table 22 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Compost 1 (Vienna) 017

14

24 Agricultural soil sludge amended soil from Pavia Italy

This sludge-amended soil material was obtained during a monitoring campaign which aimed at a generic description of the over-all soil quality in Pavia Province Italy The material which was collected from the upper horizon originates from a small farm called ldquoCascina Novellordquo During the characterisation of the site the following analytical information was obtained on a pooled sample of a sub-area of the farm of 20 X 20 m2

Table 23 ndash Analytical data on Pavia soil

Parameter Result Al 713 Wgt As 224 mgkg Cd 079 mgkg Cr 59 mgkg Cu 308 mgkg Hg 008 mgkg Ni 344 mgkg Pb 246 mgkg Zn 95 mgkg C 091 Wgt 2378-TCDD 0047 pgg 12378-PeCDD 015 pgg 123478-HxCDD 019 pgg 123678-HxCDD 15 pgg 123789-HxCDD 074 pgg 1234678-HpCDD 26 pgg OCDD 382 pgg 2378-TCDF 068 pgg 12378-PeCDF 053 pgg 23478-PeCDF 071 pgg 123478-HxDF 100 pgg 123678-HxDF 066 pgg 234678-HxDF 16 pgg 123789-HxDF 027 pgg 1234678-HpDF 12 pgg 1234789-HpDF 068 pgg OCDF 33 pgg I-TEQ 20 pgg WHO-TEQ 17 pgg

In addition the screening performed at IRMM did not reveal significant quantities of PCBs and PAHs which were all below the LoDs (1 ngg for PCBs and 10 ngg for PAHs respectively)

Table 24 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 5 (Pavia) 0005 0011 154

15

Table 25 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 5

(Pavia)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

039

nq

nq

008

nq

nd

nd

670

671

Table 26 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 5 (Pavia) 033 184 573 225 426 305 206 200 lt 005 381 878

Table 27 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 5 (Pavia) 6939 129 145 224 425 116 6118 255 1789 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 5 (Pavia) 184 62 38 108 55 66 597 110

Table 28 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 5 (Pavia) 006

16

25 Sludge-amended-soil from Barcelona Spain

The sludge-amended soil material from Barcelona sampled upon indication from the Barcelorsquo- Group in Barcelona

Table 29 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 2 (Lleida T) 0015 0183 1138

Table 30 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 2

(Lleida T)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

159

045

nq

048

160

nq

nq

1000

1004

Table 31 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 2 (Lleida T) 059 141 327 536 405 186 184 224 lt 005 318 111

Table 32 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 2 (Lleida T) 4443 1067 1429 253 344 204 4116 780 3396 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 2 (Lleida T) 064 65 26 125 59 17 547 65

Table 33 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 2 (Lleida T) 010

17

26 Sludge amended soil from Essen Germany

The German sludge-amended soil from Essen which was provided as the three sludge materials by LUA NRW did not feature significant concentrations of the PCB congeners 28 52 101 118 153 105 138 156 180 170 but had detectable amounts of some PAHs

Table 34 ndash Analytical screening data on the German sludge-amended soil

Parameter Concentration(ngg)

Naphtalene lt10 Acenaphtylene lt10 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene lt10 Fluoranthene 28 Pyrene 20 Benz(a)anthracene 24 Chrysene 47 Benz(b)fluoranthene 76 Benz(k)fluoranthene 20 Benz(a)pyrene 35 Indeno(123-cd)pyrene 35 Dibenzo(ah)anthracene 10 Benzo(ghi)perylene 26

Table 35 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 4 (Essen) 0011 0302 055

Table 36 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 4

(Essen)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

nq

nq

nq

nq

nq

nq

128

191

203

18

Table 37 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 4 (Essen) 052 545 261 805 320 403 273 273 lt 005 295 781

Table 38 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 4 (Essen) 7947 442 085 06 086 007 2163 189 2019 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 4 (Essen) 045 19 42 87 683 60 462 61

Table 39 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 4 (Essen) 004

27 Long-term sludge exposed soil from Hohenheim-Stuttgart Germany

Similarly an additional sludge exposed soil was sampled at the University of Hohenheim Stuttgart were a test soil was long-term exposed to elevated concentrations of sewage sludge

Table 40 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 1 (Stuttgart) 0045 0263 1765

Table 41 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 1

(Stuttgart)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

230

006

004

004

nq

nd

nd

498

500

19

Table 42 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 1 (Stuttgart) 069 127 361 262 504 183 252 262 lt 005 266 142

Table 43 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 1 (Stuttgart) 7194 1006 133 186 366 088 7874 275 3571 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 1 (Stuttgart) 123 50 47 212 85 69 991 129

Table 44 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 1 (Stuttgart) 177

18

Annex 3

Statistical calculations

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 47)Mandels h statistics(Sludge 1 - PBD 47)

Sample Sludge 1 NUM

Element PBD 47

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00213 0001 3 -021 005 - - 10L - - NUM46L 00273 0002 4 016 021 - - 46L - - NUM64L 00059 0000 4 -116 002 NUM - 64L - - NUM12L 00188 0000 4 -036 002 - - 12L - - NUM26L 00499 0024 2 157 223 Fail - - 26L - - NUM

Totgem 0025 0005 mgkg 1-level 172 (185) NUM (10L46L64L12L26L) -1Totstd= 0016 0010 5-level 157 (162) 5

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 5 Labs rejected (10L46L64L12L26L)

000 050 100 150 200 250

k-values

10L

46L

64L

12L

26L

Mandels k statistics(Sludge 1 - PBD 47)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

10L

46L

64L

12L

26L

Labo

rato

ries

NUM

-200 -100 000 100 200

h-values

10L

46L

64L

12L

26L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 47)

Sludge 1-PBD 47

Unit mgkg

Mandels k statistics(Soil 3 - PBD 47)Mandels h statistics(Soil 3 - PBD 47)

Sample Soil 3 Soil 3 - PBD 47 -- Mean PARM = 0001 [mgkg]

Element PBD 47

General calcparmT1= 134814E-02T2= 142830E-05T3= 13T4= 45T5= 22767E-06

n= variabelp= 4

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean26L 00007 0000 2 -143 001 00007 00000 2 1 00046L 00010 0001 4 010 181 00010 00008 4 3 00010L 00011 0000 3 049 023 00011 00001 3 2 00012L 00012 0000 4 084 081 00012 00004 4 3 000

Totgem 0001 0000 mgkg 1-level 149 (177) 4 00010 () 4 3Totstd= 0000 0000 5-level 142 (159)

RESULTS Mean = 000100 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000050 --gt 5031 r = 00014Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000050 --gt 5031 R = 00014Remarks none

000 050 100 150 200

k-values

26L

46L

10L

12L

Mandels k statistics(Soil 3 - PBD 47)

00 00 00 00 00 00 00 00 00 00 00

Deviation from Mean

26L

46L

10L

12L

Labo

rato

ries

Soil 3 - PBD 47 -- Mean PARM = 0001 [mgkg]

-200 -100 000 100

h-values

26L

46L

10L

12L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 47)

Soil 3-PBD 47

Unit mgkg

Mandels k statistics(Compost 1 - PBD 99)Mandels h statistics(Compost 1 - PBD 99)

Sample Compost 1 Compost 1 - PBD 99 -- Mean PARM = 0003 [mgkg]

Element PBD 99

General calcparmT1= 492124E-02T2= 148747E-04T3= 17T4= 61T5= 93196E-06

n= variabelp= 5

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00020 0000 4 -137 053 00020 00004 4 3 000

26L 00025 0000 2 -058 024 00025 00002 2 1 00010L 00029 0000 3 012 032 00029 00003 3 2 00046L 00033 0001 4 069 161 00033 00013 4 3 00012L 00036 0001 4 114 140 00036 00011 4 3 000

Totgem 0003 0001 mgkg 1-level 172 (185) 5 00029 () 5 4Totstd= 0001 0001 5-level 157 (162)

RESULTS Mean = 000286 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000088 --gt 3086 r = 00025Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000101 --gt 3525 R = 00028Remarks none

000 050 100 150 200

k-values

4L

26L

10L

46L

12L

Mandels k statistics(Compost 1 - PBD 99)

00 00 00 00 00 00 00 00 00 00

Deviation from Mean

4L

26L

10L

46L

12L

Labo

rato

ries

Compost 1 - PBD 99 -- Mean PARM = 0003 [mgkg]

-200 -100 000 100 200

h-values

4L

26L

10L

46L

12L

Labo

rato

ries

Mandels h statistics(Compost 1 - PBD 99)

Compost 1-PBD 99

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 99)Mandels h statistics(Sludge 1 - PBD 99)

Sample Sludge 1 Sludge 1 - PBD 99 -- Mean PARM = 0024 [mgkg]

Element PBD 99

General calcparmT1= 448050E-01T2= 112113E-02T3= 19T4= 73T5= 32972E-05

n= variabelp= 5

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean64L 00173 0002 4 -118 041 Fail 00173 00019 4 3 -0014L 00183 0002 4 -104 032 00183 00015 4 3 -001

12L 00227 0001 4 -038 022 00227 00010 4 3 00010L 00290 0001 3 055 021 00290 00010 3 2 00146L 00320 0002 4 100 039 00320 00018 4 3 00126L 00323 0011 2 105 234 - - 26L - - 001

Totgem 0025 0003 mgkg 1-level 187 (177) 5 00239 (26L) 5 4Totstd= 0007 0004 5-level 166 (154) 1

RESULTS Mean = 002385 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000153 --gt 643 r = 00043Between lab variance S2L = 000004Reproducibility var S2R = 000004Reproducibility std SR = 000666 --gt 2791 R = 00186Remarks 1 Lab rejected (26L)

000 050 100 150 200 250

k-values

64L

4L

12L

10L

46L

26L

Mandels k statistics(Sludge 1 - PBD 99)

00 00 00 00 00 00 00 00 00 00

Deviation from Mean

64L

4L

12L

10L

46L

26L

Labo

rato

ries

Sludge 1 - PBD 99 -- Mean PARM = 0024 [mgkg]

-200 -100 000 100 200

h-values

64L

4L

12L

10L

46L

26L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 99)

Sludge 1-PBD 99

Unit mgkg

Mandels k statistics(Soil 3 - PBD 99)Mandels h statistics(Soil 3 - PBD 99)

Sample Soil 3 NUM

Element PBD 99

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00017 0000 4 091 068 - - 10L - - NUM46L 00017 0001 4 100 211 - - 46L - - NUM64L 00005 0000 4 -106 023 NUM - 64L - - NUM12L 00012 0000 4 015 014 - - 12L - - NUM26L 00006 0000 2 -101 012 - - 26L - - NUM

Totgem 0001 0000 mgkg 1-level 172 (173) NUM (10L46L64L12L26L) -1Totstd= 0001 0000 5-level 157 (153) 5

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 5 Labs rejected (10L46L64L12L26L)

000 050 100 150 200 250

k-values

10L

46L

64L

12L

26L

Mandels k statistics(Soil 3 - PBD 99)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

10L

46L

64L

12L

26L

Labo

rato

ries

NUM

-200 -100 000 100 200

h-values

10L

46L

64L

12L

26L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 99)

Soil 3-PBD 99

Unit mgkg

Mandels k statistics(Compost 1 - PBD 100)Mandels h statistics(Compost 1 - PBD 100)

Sample Compost 1 Compost 1 - PBD 100 -- Mean PARM = 0001 [mgkg]

Element PBD 100

General calcparmT1= 124272E-02T2= 113129E-05T3= 14T4= 52T5= 46584E-07

n= variabelp= 4

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean26L 00006 0000 2 -131 037 Fail 00006 00001 2 1 00010L 00009 0000 4 003 083 00009 00002 4 3 00046L 00009 0000 4 016 115 00009 00002 4 3 00012L 00011 0000 4 112 136 Fail 00011 00003 4 3 000

Totgem 0001 0000 mgkg 1-level 149 (167) 4 00009 () 4 3Totstd= 0000 0000 5-level 142 (15)

RESULTS Mean = 000085 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000022 --gt 2531 r = 00006Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000025 --gt 2882 R = 00007Remarks none

000 050 100 150

k-values

26L

10L

46L

12L

Mandels k statistics(Compost 1 - PBD 100)

00 00 00 00 00 00 00 00 00 00 00

Deviation from Mean

26L

10L

46L

12L

Labo

rato

ries

Compost 1 - PBD 100 -- Mean PARM = 0001 [mgkg]

-200 -100 000 100 200

h-values

26L

10L

46L

12L

Labo

rato

ries

Mandels h statistics(Compost 1 - PBD 100)

Compost 1-PBD 100

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 100)Mandels h statistics(Sludge 1 - PBD 100)

Sample Sludge 1 Sludge 1 - PBD 100 -- Mean PARM = 0005 [mgkg]

Element PBD 100

General calcparmT1= 852065E-02T2= 412762E-04T3= 18T4= 68T5= 78914E-07

n= variabelp= 5

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00039 0000 4 -042 007 Fail 00039 00002 4 3 000

12L 00044 0000 4 -041 005 Fail 00044 00001 4 3 00010L 00046 0000 4 -041 013 Fail 00046 00003 4 3 00046L 00056 0000 4 -040 012 Fail 00056 00003 4 3 00026L 00059 0000 2 -040 013 Fail 00059 00003 2 1 00038L 02168 0006 4 204 244 Fail - - 38L - - 021

Totgem 0040 0001 mgkg 1-level 187 (177) 5 00049 (38L) 5 4Totstd= 0087 0002 5-level 166 (154) 1

RESULTS Mean = 000486 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000025 --gt 507 r = 00007Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000084 --gt 1731 R = 00024Remarks 1 Lab rejected (38L)

000 050 100 150 200 250

k-values

4L

12L

10L

46L

26L

38L

Mandels k statistics(Sludge 1 - PBD 100)

-01 00 01 01 02 02 03

Deviation from Mean

4L

12L

10L

46L

26L

38L

Labo

rato

ries

Sludge 1 - PBD 100 -- Mean PARM = 0005 [mgkg]

-100 000 100 200 300

h-values

4L

12L

10L

46L

26L

38L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 100)

Sludge 1-PBD 100

Unit mgkg

Mandels k statistics(Soil 3 - PBD 100)Mandels h statistics(Soil 3 - PBD 100)

Sample Soil 3 NUM

Element PBD 100

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00003 0000 4 -050 000 Fail - - 10L - - NUM46L 00003 0000 4 -050 000 Fail NUM - 46L - - NUM3L 305500 2051 2 150 200 Fail - - 3L - - NUM

26L 00005 0000 2 -050 000 Fail - - 26L - - NUM

Totgem 7638 0513 mgkg 1-level 149 (177) NUM (10L46L3L26L) -1Totstd= 15275 1025 5-level 142 (159) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (10L46L3L26L)

000 050 100 150 200

k-values

10L

46L

3L

26L

Mandels k statistics(Soil 3 - PBD 100)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

10L

46L

3L

26L

Labo

rato

ries

NUM

-100 000 100 200

h-values

10L

46L

3L

26L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 100)

Soil 3-PBD 100

Unit mgkg

Mandels k statistics(Compost 1 - PBD 153)Mandels h statistics(Compost 1 - PBD 153)

Sample Compost 1 NUM

Element PBD 153

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean44L 00053 0001 3 150 157 Fail - - 44L - - NUM46L 00007 0000 4 -044 111 Fail - - 46L - - NUM12L 00005 0000 4 -051 055 Fail - - 12L - - NUM26L 00005 0000 2 -054 001 Fail NUM - 26L - - NUM

Totgem 0002 0000 mgkg 1-level 149 (177) NUM (44L46L12L26L) -1Totstd= 0002 0000 5-level 142 (159) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (44L46L12L26L)

000 050 100 150 200

k-values

44L

46L

12L

26L

Mandels k statistics(Compost 1 - PBD 153)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

44L

46L

12L

26L

Labo

rato

ries

NUM

-100 000 100 200

h-values

44L

46L

12L

26L

Labo

rato

ries

Mandels h statistics(Compost 1 - PBD 153)

Compost 1-PBD 153

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 153)Mandels h statistics(Sludge 1 - PBD 153)

Sample Sludge 1 Sludge 1 - PBD 153 -- Mean PARM = 0004 [mgkg]

Element PBD 153

General calcparmT1= 676738E-02T2= 267609E-04T3= 18T4= 68T5= 19626E-05

n= variabelp= 5

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00024 0000 4 -157 017 00024 00002 4 3 000

12L 00038 0002 4 006 154 00038 00018 4 3 00046L 00039 0000 4 011 026 00039 00003 4 3 00026L 00039 0000 2 018 004 00039 00000 2 1 00064L 00049 0002 4 122 159 00049 00018 4 3 000

Totgem 0004 0001 mgkg 1-level 172 (173) 5 00038 () 5 4Totstd= 0001 0001 5-level 157 (153)

RESULTS Mean = 000378 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000123 --gt 3252 r = 00034Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000142 --gt 3754 R = 00040Remarks none

000 050 100 150 200

k-values

4L

12L

46L

26L

64L

Mandels k statistics(Sludge 1 - PBD 153)

00 00 00 00 00 00 00

Deviation from Mean

4L

12L

46L

26L

64L

Labo

rato

ries

Sludge 1 - PBD 153 -- Mean PARM = 0004 [mgkg]

-200 -100 000 100 200

h-values

4L

12L

46L

26L

64L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 153)

Sludge 1-PBD 153

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 154)Mandels h statistics(Sludge 1 - PBD 154)

Sample Sludge 1 NA

Element PBD 154

General calcparmT1= NAT2= NAT3=T4=T5=

n= variabelp=

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00021 0000 3 -100 021 NA - 4L - - NA

46L 00025 0000 4 115 018 NA - 46L - - NA64L 00021 0001 4 -066 179 - - 64L - - NA12L 00023 0000 4 050 085 - - 12L - - NA

Totgem 0002 0000 mgkg 1-level 149 (167) NA (4L46L64L12L) -1Totstd= 0000 0000 5-level 142 (15) 4

RESULTS Mean = NA mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NAReproducibility var S2R = NAReproducibility std SR = NA --gt NA R = NARemarks 4 Labs rejected (4L46L64L12L)

000 050 100 150 200

k-values

4L

46L

64L

12L

Mandels k statistics(Sludge 1 - PBD 154)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

4L

46L

64L

12L

Labo

rato

ries

NA

-100 000 100 200

h-values

4L

46L

64L

12L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 154)

Sludge 1-PBD 154

Unit mgkg

Mandels k statistics(Soil 3 - PBD 154)Mandels h statistics(Soil 3 - PBD 154)

Sample Soil 3 NUM

Element PBD 154

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

4L 00010 - 1 150 Fail - - 4L - - NUM46L 00001 0000 4 -053 096 Fail - - 46L - - NUM64L 00001 0000 4 -056 105 Fail NUM - 64L - - NUM12L 00002 0000 4 -040 099 Fail - - 12L - - NUM

Totgem 000037 0000 mgkg 1-level 149 (164) NUM (4L46L64L12L) -1Totstd= 000042 0000 5-level 142 (153) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (4L46L64L12L)

000 050 100 150

k-values

4L

46L

64L

12L

Mandels k statistics(Soil 3 - PBD 154)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

4L

46L

64L

12L

Labo

rato

ries

NUM

-100 000 100 200

h-values

4L

46L

64L

12L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 154)

Soil 3-PBD 154

Unit mgkg

Mandels k statistics(Compost 1 - PBD 209)Mandels h statistics(Compost 1 - PBD 209)

Sample Compost 1 NUM

Element PBD 209

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00065 0003 2 -049 032 - - 4L - - NUM

44L 00573 0021 4 150 197 Fail - - 44L - - NUM12L 00078 0001 4 -045 011 - - 12L - - NUM26L 00049 0000 2 -056 000 NUM - 26L - - NUM

Totgem 0019 0006 mgkg 1-level 149 (177) NUM (4L44L12L26L) -1Totstd= 0025 0010 5-level 142 (159) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (4L44L12L26L)

000 050 100 150 200

k-values

4L

44L

12L

26L

Mandels k statistics(Compost 1 - PBD 209)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

4L

44L

12L

26L

Labo

rato

ries

NUM

-100 000 100 200

h-values

4L

44L

12L

26L

Labo

rato

ries

Mandels h statistics(Compost 1 - PBD 209)

Compost 1-PBD 209

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 209)Mandels h statistics(Sludge 1 - PBD 209)

Sample Sludge 1 Sludge 1 - PBD 209 -- Mean PARM = 0249 [mgkg]

Element PBD 209

General calcparmT1= 394542E+00T2= 107296E+00T3= 16T4= 56T5= 19723E-02

n= variabelp= 5

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 01550 0055 4 -112 148 Fail 01550 00551 4 3 -009

46L 02050 0007 2 -053 019 02050 00071 2 1 -00412L 02137 0058 4 -042 155 02137 00576 4 3 -00426L 03149 0021 2 078 057 Fail 03149 00210 2 1 00764L 03577 0007 4 129 020 Fail 03577 00074 4 3 011

Totgem 0249 0030 mgkg 1-level 172 (185) 5 02493 () 5 4Totstd= 0084 0025 5-level 157 (162)

RESULTS Mean = 024926 mgkg

Repeatability variance S2r = 000179Repeatability std Sr = 004234 --gt 1699 r = 01186Between lab variance S2L = 000743Reproducibility var S2R = 000922Reproducibility std SR = 009604 --gt 3853 R = 02689Remarks none

000 050 100 150 200

k-values

4L

46L

12L

26L

64L

Mandels k statistics(Sludge 1 - PBD 209)

-01 -01 00 01 01 02

Deviation from Mean

4L

46L

12L

26L

64L

Labo

rato

ries

Sludge 1 - PBD 209 -- Mean PARM = 0249 [mgkg]

-200 -100 000 100 200

h-values

4L

46L

12L

26L

64L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 209)

Sludge 1-PBD 209

Unit mgkg

Mandels k statistics(Soil 3 - PBD 209)Mandels h statistics(Soil 3 - PBD 209)

Sample Soil 3 Soil 3 - PBD 209 -- Mean PARM = 0258 [mgkg]

Element PBD 209

General calcparmT1= 596398E+00T2= 191917E+00T3= 22T4= 84T5= 13249E-02

n= variabelp= 6

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean26L 01162 0021 2 -108 074 Fail 01162 00207 2 1 -0144L 01303 0031 4 -097 111 Fail 01303 00312 4 3 -013

46L 01975 0036 4 -046 128 Fail 01975 00359 4 3 -00644L 02898 0035 4 024 124 Fail 02898 00346 4 3 00312L 03895 0018 4 100 065 Fail 03895 00181 4 3 01364L 04260 0022 4 127 078 Fail 04260 00219 4 3 017

Totgem 0258 0027 mgkg 1-level 187 (177) 6 02582 () 6 5Totstd= 0132 0008 5-level 166 (154)

RESULTS Mean = 025818 mgkg

Repeatability variance S2r = 000083Repeatability std Sr = 002878 --gt 1115 r = 00806Between lab variance S2L = 001640Reproducibility var S2R = 001723Reproducibility std SR = 013127 --gt 5084 R = 03676Remarks none

000 050 100 150

k-values

26L

4L

46L

44L

12L

64L

Mandels k statistics(Soil 3 - PBD 209)

-02 -01 -01 00 01 01 02 02

Deviation from Mean

26L

4L

46L

44L

12L

64L

Labo

rato

ries

Soil 3 - PBD 209 -- Mean PARM = 0258 [mgkg]

-200 -100 000 100 200

h-values

26L

4L

46L

44L

12L

64L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 209)

Soil 3-PBD 209

Unit mgkg

Mandels k statistics(Compost 1 - Sum PBD)Mandels h statistics(Compost 1 - Sum PBD)

Sample Compost 1 Compost 1 - Sum PBD -- Mean PARM = 0009 [mgkg]

Element Sum PBD

General calcparmT1= 154064E-01T2= 169065E-03T3= 18T4= 68T5= 11354E-04

n= variabelp= 5

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00031 0002 4 -067 016 00031 00016 4 3 -0014L 00055 0005 4 -056 048 00055 00047 4 3 000

46L 00085 0003 4 -042 031 00085 00030 4 3 00026L 00123 0000 2 -024 003 00123 00002 2 1 00012L 00154 0002 4 -011 021 00154 00021 4 3 00144L 00613 0023 4 200 237 Fail - - 44L - - 005

Totgem 0018 0006 mgkg 1-level 187 (177) 5 00089 (44L) 5 4Totstd= 0022 0009 5-level 166 (154) 1

RESULTS Mean = 000893 mgkg

Repeatability variance S2r = 000001Repeatability std Sr = 000296 --gt 3308 r = 00083Between lab variance S2L = 000002Reproducibility var S2R = 000003Reproducibility std SR = 000570 --gt 6374 R = 00159Remarks 1 Lab rejected (44L)

000 050 100 150 200 250

k-values

10L

4L

46L

26L

12L

44L

Mandels k statistics(Compost 1 - Sum PBD)

00 00 00 00 00 00 01 01

Deviation from Mean

10L

4L

46L

26L

12L

44L

Labo

rato

ries

Compost 1 - Sum PBD -- Mean PARM = 0009 [mgkg]

-100 000 100 200

h-values

10L

4L

46L

26L

12L

44L

Labo

rato

ries

Mandels h statistics(Compost 1 - Sum PBD)

Compost 1-Sum PBD

Unit mgkg

Mandels k statistics(Sludge 1 - Sum PBD)Mandels h statistics(Sludge 1 - Sum PBD)

Sample Sludge 1 Sludge 1 - Sum PBD -- Mean PARM = 0256 [mgkg]

Element Sum PBD

General calcparmT1= 531806E+00T2= 162188E+00T3= 22T4= 84T5= 25223E-02

n= variabelp= 6

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00423 0025 4 -156 044 Fail 00423 00252 4 3 -02146L 01808 0118 4 -049 205 - - 46L - - -0074L 01810 0056 4 -049 097 01810 00558 4 3 -007

38L 02168 0006 4 -022 010 02168 00059 4 3 -00412L 02890 0065 4 034 113 02890 00647 4 3 00364L 03958 0008 4 116 014 Fail 03958 00079 4 3 01426L 04094 0034 2 126 059 Fail 04094 00337 2 1 015

Totgem 0245 0044 mgkg 1-level 198 (179) 6 02557 (46L) 6 5Totstd= 0130 0039 5-level 171 (155) 1

RESULTS Mean = 025570 mgkg

Repeatability variance S2r = 000158Repeatability std Sr = 003970 --gt 1553 r = 01112Between lab variance S2L = 001807Reproducibility var S2R = 001964Reproducibility std SR = 014015 --gt 5481 R = 03924Remarks 1 Lab rejected (46L)

000 050 100 150 200 250

k-values

10L

46L

4L

38L

12L

64L

26L

Mandels k statistics(Sludge 1 - Sum PBD)

-03 -02 -02 -01 -01 00 01 01 02 02

Deviation from Mean

10L

46L

4L

38L

12L

64L

26L

Labo

rato

ries

Sludge 1 - Sum PBD -- Mean PARM = 0256 [mgkg]

-200 -100 000 100 200

h-values

10L

46L

4L

38L

12L

64L

26L

Labo

rato

ries

Mandels h statistics(Sludge 1 - Sum PBD)

Sludge 1-Sum PBD

Unit mgkg

Mandels k statistics(Soil 3 - Sum PBD)Mandels h statistics(Soil 3 - Sum PBD)

Sample Soil 3 Soil 3 - Sum PBD -- Mean PARM = 0227 [mgkg]

Element Sum PBD

General calcparmT1= 610980E+00T2= 200876E+00T3= 26T4= 100T5= 13106E-02

n= variabelp= 7

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00028 0001 4 -037 000 Fail 00028 00005 4 3 -02226L 01179 0021 2 -036 003 Fail 01179 00208 2 1 -0114L 01305 0031 4 -036 004 Fail 01305 00308 4 3 -010

46L 02065 0035 4 -036 005 Fail 02065 00350 4 3 -00244L 02923 0037 4 -035 005 Fail 02923 00365 4 3 00712L 04051 0015 4 -034 002 Fail 04051 00149 4 3 01864L 04314 0022 4 -033 003 Fail 04314 00223 4 3 0203L 305500 2051 2 247 283 Fail - - 3L - - 3032

Totgem 4017 0276 mgkg 1-level 206 (181) 7 02266 (3L) 7 6Totstd= 10722 0717 5-level 175 (156) 1

RESULTS Mean = 022663 mgkg

Repeatability variance S2r = 000069Repeatability std Sr = 002626 --gt 1159 r = 00735Between lab variance S2L = 002568Reproducibility var S2R = 002637Reproducibility std SR = 016238 --gt 7165 R = 04547Remarks 1 Lab rejected (3L)

000 050 100 150 200 250 300

k-values

10L

26L

4L

46L

44L

12L

64L

3L

Mandels k statistics(Soil 3 - Sum PBD)

-50 00 50 100 150 200 250 300 350

Deviation from Mean

10L

26L

4L

46L

44L

12L

64L

3L

Labo

rato

ries

Soil 3 - Sum PBD -- Mean PARM = 0227 [mgkg]

-100 000 100 200 300

h-values

10L

26L

4L

46L

44L

12L

64L

3L

Labo

rato

ries

Mandels h statistics(Soil 3 - Sum PBD)

Soil 3-Sum PBD

19

Annex 4

Raw data submitted

Sample Compost1 Sample Compost 1 Sample Compost 1Element PBD 99 Element PBD 100 Element PBD 153

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]4L 00021 10L 00008 44L 000504L 00024 10L 00008 44L 000604L 00014 10L 00007 44L 000504L 00020 10L 00011 46L 00004

10L 00029 46L 00007 46L 0001210L 00027 46L 00012 46L 0000410L 00032 46L 00009 46L 0000946L 00025 46L 00007 12L 0000446L 00052 12L 00008 12L 0000846L 00029 12L 00012 12L 0000446L 00026 12L 00008 12L 0000712L 00026 12L 00014 26L 0000512L 00043 26L 00007 26L 0000512L 00026 26L 0000612L 0004726L 0002626L 00024

Sample Compost 1 Sample Compost 1 Sample Compost 1Element PBD 154 Element PBD 183 Element PBD 196

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]4L 00010 46L 00002 46L 00011

46L 00003 46L 00024 46L 0000846L 00007 46L 00021 12L 0000246L 00003 46L 00003 12L 0000346L 00004 12L 00003 12L 0000112L 00003 12L 00011 12L 0000212L 00005 12L 0000312L 00031 12L 0000312L 00006

Sample Compost 1 Sample Compost 1 Sample Compost 1Element PBD 197 Element PBD 203 Element PBD 209

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00002 46L 00010 4L 0004146L 00023 12L 00002 4L 0008946L 00022 12L 00003 44L 0041012L 00004 12L 00002 44L 0084012L 00006 12L 00002 44L 0064012L 00003 44L 0040012L 00004 12L 00079

12L 0007312L 0006512L 0009326L 0004926L 00049

Sample Compost 1Element PBD 47

LAB PARM [mgkg]26L 0003826L 00039

Element PBD 99 Element PBD 47 Element PBD 209LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]

4L 00170 10L 00210 4L 010004L 00200 10L 00220 4L 018004L 00170 10L 00210 4L 012004L 00190 46L 00300 4L 0220010L 00280 46L 00280 46L 0210010L 00300 46L 00250 46L 0200010L 00290 46L 00260 64L 0351846L 00340 64L 00059 64L 0363846L 00330 64L 00057 64L 0364546L 00300 64L 00062 64L 0350846L 00310 64L 00060 12L 0220964L 00194 12L 00191 12L 0177164L 00154 12L 00187 12L 0292264L 00185 12L 00190 12L 0164664L 00159 12L 00186 26L 0329712L 00242 26L 00666 26L 0300012L 00223 26L 0033212L 0022112L 0022226L 0024626L 00400

Element PBD 203 Element PBD 197 Element PBD 196LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00022 46L 00027 46L 0002446L 00014 46L 00024 46L 0002264L 00036 12L 00161 64L 0005864L 00058 12L 00060 64L 0006512L 00063 12L 00061 12L 0004812L 00034 12L 00036 12L 0002512L 00038 12L 0003212L 00027 12L 00022

Element PBD 183 Element PBD 154 Element PBD 153LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00049 4L 00020 4L 0002246L 00035 4L 00022 4L 0002446L 00036 4L 00020 4L 0002246L 00034 46L 00025 4L 0002664L 00027 46L 00025 46L 0004064L 00023 46L 00025 46L 0004264L 00024 46L 00023 46L 0003564L 00020 64L 00034 46L 0003812L 00230 64L 00023 64L 0007412L 00032 64L 00017 64L 0004712L 00031 64L 00011 64L 0004612L 00030 12L 00030 64L 0003026L 00007 12L 00021 12L 0006526L 00008 12L 00021 12L 00029

12L 00021 12L 0003226L 00015 12L 0002926L 00019 26L 00039

26L 00040

Element PBD 100LAB PARM [mgkg]

4L 000384L 000414L 000374L 00038

38L 0219038L 0220038L 0208038L 0220010L 0004410L 0005010L 0004310L 0004646L 0005746L 0005946L 0005346L 0005312L 0004312L 0004512L 0004312L 0004326L 0006226L 00057

Sample Soil 3 Sample Soil 3 Sample Soil 3Element PBD 99 Element PBD 47 Element PBD 100

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]10L 00016 10L 00011 10L 0000310L 00019 10L 00010 10L 0000410L 00013 10L 00012 10L 0000410L 00019 46L 00007 10L 0000246L 00025 46L 00022 46L 0000246L 00025 46L 00005 46L 0000646L 00008 46L 00007 46L 0000246L 00011 12L 00010 46L 0000264L 00005 12L 00017 3L 29100064L 00005 12L 00010 3L 32000064L 00006 12L 00009 26L 0000564L 00007 26L 00007 26L 0000512L 00012 26L 0000712L 0001312L 0001312L 0001226L 0000526L 00006

Sample Soil 3 Sample Soil 3 Sample Soil 3Element PBD 153 Element PBD 154 Element PBD 196

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]44L 00050 4L 00010 46L 0000744L 00050 46L 00001 46L 0001146L 00002 46L 00002 46L 0000846L 00003 46L 00001 46L 0001146L 00002 46L 00002 64L 0002646L 00002 64L 00001 64L 0002664L 00001 64L 00001 64L 0002964L 00001 64L 00001 64L 0003464L 00001 64L 00002 12L 0004564L 00002 12L 00003 12L 00032

12L 00002 12L 0002212L 00002 12L 0002112L 00002

Sample Soil 3 Sample Soil 3 Sample Soil 3Element PBD 197 Element PBD 203 Element PBD 209

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00006 46L 00011 4L 0091046L 00013 46L 00017 4L 0150046L 00011 46L 00015 4L 0120046L 00013 46L 00018 4L 0160012L 00090 64L 00013 44L 0337012L 00056 64L 00014 44L 0281012L 00033 64L 00016 44L 0287012L 00032 64L 00015 44L 02540

12L 00055 46L 0230012L 00041 46L 0220012L 00027 46L 0150012L 00026 46L 01900

64L 0438164L 0401664L 0414464L 0449812L 0367112L 0397812L 0409112L 03838

Sample Soil 3 26L 0102Element PBD 183 26L 0131

LAB PARM [mgkg]46L 0000746L 0000846L 0005846L 0000764L 0000264L 0000364L 0000364L 0000312L 0001512L 0001112L 0000712L 00007

European Commission EUR 23003 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on polybrominated diphenylethers Author(s) E Sobiecka H van der Sloot D Barcelo B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 68 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07403-5 Abstract Project HORIZONTAL is interdisciplinary aiming at a harmonisation and horizontal standardisation of test procedures in particular for sludge soils and biowastes In the context of this standardization project a series of draft technical specification were designed upon an extensive desk study fine-tuned after expert consultations and finally validated in international intercomparisons exercise This report summarises the work performed within the validation study of the draft standard for the determination of polybrominated diphenylethers (PBDE) in soils sludge and treated bio-waste using gas-chromatography method with mass selective detection (GC-MS) It further explains the underlying statistical concept for the calculation of reproducibility and repeatability from intercomparisons data In addition all single values results of the statistical evaluation as well as background information on the validation materials used are described and explained

The mission of the JRC is to provide customer-driven scientific and technical support for the conception development implementation and monitoring of EU policies As a service of the European Commission the JRC functions as a reference centre of science and technology for the Union Close to the policy-making process it serves the common interest of the Member States while being independent of special interests whether private or national

LB

-NA

-23003-EN

-C

The mission of the Institute for Environment and Sustainability is to provide scientific-technical support to the European Unionrsquos Policies for the protection and sustainable development of the European and global environment European Commission Joint Research Centre Institute for Environment and Sustainability Contact information Address Via Enrico Fermi 2749 21027 Ispra (VA) Italy E-mail berndgawlikjrcit Tel +39 0332 789487 Fax +39 0332 789158 httpiesjrceceuropaeu httpwwwjrceceuropaeu Legal Notice Neither the European Commission nor any person acting on behalf of the Commission is responsible for the use which might be made of this publication A great deal of additional information on the European Union is available on the Internet It can be accessed through the Europa server httpeuropaeu JRC 40184 EUR 23003 EN ISBN 978-92-79-07403-5 ISSN 1018-5593 DOI 1027884502 Luxembourg Office for Official Publications of the European Communities copy European Communities 2007 Reproduction is authorised provided the source is acknowledged Printed in Luxemburg

Project HORIZONTAL Validation Report

Validation of a horizontal standard for the determination of selected polybrominated diphenylethers (PBDE) by gas-chromatography method with mass selective detection (GC-MS) in a European Intercomparison Exercise E Sobiecka H Van der Sloot D Barcelo B M Gawlik Elzbieta Sobiecka Bernd Manfred Gawlik European Commission Joint Research Centre Institute for Environment and Sustainability Via Enrico Fermi 21020 Ispra - Italy

Hans van der Sloot ECN Emission Characterisation and Reduction Westerduinweg 3 PO Box 1 1755 ZG Petten The Netherlands

Damia Barcelo Consejo Superior de Investigaciones Cientificas (CSIC) IIQAB Jordi Girona 18 E-08034 BARCELONA Spain

to whom correspondence should be sent

by email to berndgawlikjrcit

Summary Project HORIZONTAL is interdisciplinary aiming at a harmonisation and horizontal standardisation of test procedures in particular for sludge soils and biowastes In the context of this standardization project a series of draft technical specification were designed upon an extensive desk study fine-tuned after expert consultations and finally validated in international intercomparisons exercise This report summarises the work performed within the validation study of the draft standard for the determination of polybrominated diphenylethers (PBDE) in soils sludge and treated bio-waste using gas-chromatography method with mass selective detection (GC-MS) It further explains the underlying statistical concept for the calculation of reproducibility and repeatability from intercomparisons data In addition all single values results of the statistical evaluation as well as background information on the validation materials used are described and explained

Abbreviations Throughout this report the following abbreviations are used ANOVA Analysis of variances

CAS Chemical Abstracts System

CEN Comitteeacute Europeacuteen de Normalisation

DG Directorate General

ECD Electron Capture Detector

ECN Energy Research Centre for the Netherlands

EU European Union

IES Institute for Environment and Sustainability

IT Information Technology

ISO International Organization for Standardisation

JRC Joint Research Centre

GC Gas Chromatography

MILC Measure Interlaboratory Comparison

MS Mass Spectroscopy

p Number of labs

PBDE Polybrominated Diphenylethers

r Repeatability limit

R Reproducibility limit

sr Repeatability standard deviation

sR Reproducibility standard deviation

TC Technical Committee

4

Table of Contents Summary 2 Abbreviations 3 Table of Contents 4

Introduction to the validation project 5 11 Statistical concept underlying the validation 6

111 Introduction to the statistical model 6 112 Requirements for precision experiment 7 113 Statistical analysis 8

12 Validation exercise for PBDE 8 121 Compounds to be measured 8 122 Samples dispatched for the validation of PBDE 8 123 Draft standards to be followed 8 124 Analytical programm 8 125 Timing and Submission of data 9 126 Participants 10

13 Summary results and derived performance characteristics 11 14 Annexes 15

5

Introduction to the validation project Project HORIZONTAL is interdisciplinary aiming at a harmonisation and horizontal standardisation of test procedures in particular for sludges soils and biowastes It was created as in response to the European Commission Mandate M 330 given to CEN asking for the development and validation of those standards in support of forthcoming EU Directives such as

o The revision of the Sewage Sludge Directive 86278EEC o The Directive on the biological treatment of biodegradable waste o The initiative on a legal framework for soil monitoring in Europe

This mandate explicitly considers standards for the entire analytical procedure (ie sampling pre-treatment and analytical measurement methods for inorganic organic hygiene and biological parameters) These are grouped into classes according to their physicalchemical properties which in turn determine the methods needed to quantify the potential impact on human and animal health plant uptake soil function and groundwater quality As the materials generally feature a mixture of different types of contaminants it is important to provide an integrated answer covering evaluation of all relevant pollutants In order to fulfil the requirements of the aforementioned mandate the European Commissions Joint Research Centre (JRC) and its Directorate-General for Environment (DG ENV) together with the Technical Committees of the European Standardisation Committee (CEN TCs) concerned designed a pre-normative research initiative called Project HORIZONTAL and presented it to the Commission and the Environmental Authorities in the Member States After an extensive literature research and careful evaluation of the feasibility of a given horizontal standard the standards were drafted and finally validated in an European laboratory intercomparison The underlying statistical concept information about the materials used details about the participants measurement results obtained as well as the derived performance characteristics obtained for the determination of polybrominated diphenylethers (PBDE) are described hereafter

6

11 Statistical concept underlying the validation According to the requirements of the work package concerning data handling amp interpretation of the project HORIZONTAL-ORG the respective validation intercomparisons have to be evaluated according to the principles laid down in ISO standard 5725-21994 In particular repeatability and reproducibility of the draft standard methods have to be determined The determination of trueness would require the availability of independent reference values for the materials investigated This however is not possible and was not requested in the frame of this work In the following the approach chosen is explained

111 Introduction to the statistical model The statistical model used in ISO 5725 for estimation of accuracy of a measurement method assumes that every test result is the sum of three components

eBmy ++= y test result m general mean B laboratory component of bias under repeatability conditions e random error occurring in every measurement under repeatability conditions

In the workprogram the quantification of term e is explicitly asked for (ie repeatability and reproducibility) The repeatability variance is measured directly as the variance of the error term e but the reproducibility depends on the sum of the repeatability variance and the between-laboratory variance

( )er var=σ 22rLR σσσ += with ( )BL var=σ

However soil biowaste and sludge are multi-phase materials ie they contain two or more distinct types of particles which are fundamentally different in their properties and composition As a consequence this introduces an important source of variation for the intercomparison exercise which needs to be considered ie the inherent heterogeneity of the materials Thus a contribution of variation between samples H is introduced to the general statistical model

HeBmy +++= Using ANOVA techniques the different variances are calculated and separated for the evaluation

7

112 Requirements for precision experiment

Layout of the experiment A suite of 10 to 12 different materials (soil sludge and biowaste) has been made available for the intercomparison exercise For each parameter investigated at least 10 to laboratories should be nominated to participate The same laboratories should be used for different parameters as far as possible Due to the complexity of analysis and the respective workload to the laboratories it was decided to propose three materials for the validation of the PBDE draft standard Each laboratory received two bottles of each material and was be requested to perform 4 independent analyses per material1 (2 per bottle) using the respective draft standard methods The 4 analysis per material should be carried out under repeatability conditions (ie same operator2 same equipment within a short period of time) As far as possible also the different materials should be measured under repeatability conditions however changes of eg operator or equipment are permitted but must be reported Likewise different materials can be analysed on different days if necessary Equipment used in the experiment needed to be checked prior to the experiment according to the requirements of the draft standard The results of these checks have to be documented Similarly date and time of each measurement had to be recorded for verification of repeatability conditions An appropriate timeframe for the entire exercise has been set and was to be respected

Recruitment of the laboratories Each sub-workpackage leader of HORIZONTAL was asked to select the laboratories using the information from section 52 of ISO 5725-21994 and provide the signed questionnaires (see also Annex 1) The workpackage leaders were responsible for providing the laboratories with the draft standard method and explaining the context of this exercise

Preparation and use of the materials Materials used for the exercise were prepared according to the general requirements for reference materials as laid down in ISO Guide 34 Materials were accompanied by instructions for use

Reporting of results Online submissions of results using an internet-based IT platform as well as XLS-Spreadsheets were used In case of online data submission the participating laboratories received a unique and confidential login and password in due time enabling them to

1 Independent analysis means analysis of independent test portions applying the entire analytical scheme to this test portion from eg extraction to quantification For instance it does not mean replicate injections of aliquots into a GC-MS instrument 2 Operator in this context may also consist of a fixed team of persons eg one person performing extraction one clean-up one quantification

8

enter their data in a structured form For authentication purposes a signed printout had to be submitted by mail The online data submission included a detailed questionnaire for additional information on the measurements

113 Statistical analysis Statistical analysis of data followed the requirements of ISO 5725-21994 and ISO 5725-51998 Appropriate tests for the homogeneity of variance detection of outliers and normal distribution were applied Statistical evaluation was done using an Excel Macro developed tested and successfully applied in other occasion by ECN Evaluation was executed jointly by JRC and ECN

12 Validation exercise for PBDE

121 Compounds to be measured The following compound were selected for the validation exercise Tetra-BDE-47 Penta-BDE-100 Penta-BDE-99 Hexa-BDE-154 Hexa-BDE-153 Hepta-BDE-183 Octa-BDE-196 Octa-BDE-197 Octa-BDE-203 Deca-BDE-209

122 Samples dispatched for the validation of PBDE After a preliminary rough screening the following materials were used for the validation round of PBDE

bull Compost 1 A pollutant loaded compost material from Vienna bull Sewage Sludge 1 A mixed sewage sludge from Essen bull Soil 3 A sludge amended soil from Barcelona

A more detailed description of background concentrations can be found in Annex 2 to this report The samples were dispatched simultaneously to all participants using a private courier service

123 Draft standards to be followed The draft standards to be followed could be downloaded following this link which is situated on the website of the Project HORIZONTAL httpwwwecnnldocssocietyhorizontalBFR_Standard_for_validationpdf

124 Analytical programm Of each of the three materials 2 bottles had to be analysed and each bottle had to analysed independently twice As mentioned above analyses were to be done under repeatability conditions Results were to be reported referring to DRY MATTER content The choice how to apply dm correction was free for each participant

9

125 Timing and Submission of data Dispatch of samples was done on the 18th of October 2006 For users of the Online data submission system (MILC) User Registration was possible from 14th of November 2006 with opening of the MILC Data Submission on 1st of December 2006 The deadline for submission of results has been set for PBDE to the 12th of January 2007 but was extended to the end of the same months After that no further submission was possible Alternatively the participants were allowed to submit data electronically as Excel sheet using simply Email All data were treated in a confidential way Any presentation hereafter will refer only to numerical data and it will not be possible to identify the originating laboratory Lab Codes displayed are NOT related to the order of laboratories hereafter In addition to the information provide an Helpdesk was implemented in order to give quick and individual response to the participants during and immediately after the validation study In case of doubt and suspected transcription errors further enquires were conducted by JRC

10

126 Participants The following table lists the participating organisations and entities in the validation exercise for the horizontal PBDE standard

bull Austria o Umweltbundesamt

bull Czech Republic o Povodi Labe statni podnik - OVHL Laboratory

bull France o CIRSEE o CTC Environnement o INERIS

bull Germany o Federal Environmental Agency Section III 34 Laboratory Methods for

the Surveillance of Waste and Wastewater (UBA) bull Italy

o European Commission DG JRC IES bull Spain

o Consejo Superior de Investigaciones Cientificas (CSIC)

bull Sweden o ALCONTROL AB

11

13 Summary results and derived performance characteristics The result of the various statistical evaluation including outlier tests calculation of repeatability and reproducibility standard deviation for the congeners of interest can be found in Annex 3 of this report In addition all data submitted by the participants as well as those considered for the calculation of the performance characteristics are listed in Annex 3 to this report Based on these calculations the following results were obtained in the validation round upon statistical evaluation according to ISO 5725-2 The average values the repeatability standard deviation (sr) and the reproducibility standard deviation (sR) were obtained (Table1) The repeatability is determined as an interval around a measurement result (ie repeatability limit) This interval corresponds to the maximum difference that can be expected (with a 95 statistical confidence) between one test result and another both test results being obtained under the following conditions The tests are performed in accordance with all the requirements of the present standard by the same laboratory using its own facilities and testing laboratory samples obtained from the same primary field sample and prepared under identical procedures The repeatability limit was calculated using the relationship r test = f radic2 s rtest with the critical range factor f = 2 The reproducibility like repeatability is also determined as an interval around a measurement result (ie reproducibility limit) This interval corresponds to the maximum difference that can be expected (with a 95 statistical confidence) between one test result and another test result obtained by another laboratory both test results being obtained under the following conditions The tests are performed in accordance with all the requirements of the present standard by two different laboratories using their own facilities and testing laboratory samples obtained from the same primary field sample and prepared under identical procedures The reproducibility limit was calculated using the relationship R = f radic2 sR with the critical range factor f = 2

12

Table 1 - Results of the interlaboratory comparison studies of the determination of selected polybrominated diphenyl ethers (PBDE) by gaschromatography with mass spectrometric detection (GC-MS) in soil sludge and treated biowaste All concentrations are expressed in mgkg dm

Matrix Parameter Mean sr sR r R p Outliers Used No of data

No of data reported below

detection

Total no of data

Sludge 1 PBD 47 00181 461 4 15 5 20 Compost 1 00039 94 3 12 0 12 Soil 3 00010 50 50 00014 00014 4 0 13 10 23 Sludge 1 PBD 99 00239 64 28 00043 00186 5 1 19 0 23 Compost 1 00029 31 35 00025 00028 5 0 17 4 21 Soil 3 00013 499 4 16 8 24 Sludge 1 PBD 100 00049 51 17 00007 00024 5 1 18 2 24 Compost 1 00009 25 29 00006 00007 4 0 14 7 21 Soil 3 61103 211 3 10 15 25 Sludge 1 PBD 153 00038 33 38 00034 0004 5 0 18 0 18 Compost 1 00019 116 3 11 3 14 Soil 3 00011 177 2 10 10 20 Sludge 1 PBD 154 00023 234 4 15 2 17 Compost 1 00008 1118 3 9 5 14

13

Matrix Parameter Mean sr sR r R p Outliers Used No of data

No of data reported below

detection

Total no of data

Soil 3 00002 1049 4 13 6 19 Sludge 1 PBD 183 00048 1217 3 12 2 14 Compost 1 00009 1048 2 8 5 13 Soil 3 00011 1395 3 12 6 18 Sludge 1 PBD 196 00037 470 2 8 7 15 Compost 1 00004 950 2 6 4 10 Soil 3 00023 519 3 12 2 14 Sludge 1 PBD 197 00062 834 2 6 8 14 Compost 1 00009 1001 2 7 7 14 Soil 3 00032 904 2 8 6 14 Sludge 1 PBD 203 00037 461 2 8 4 12 Compost 1 00004 978 2 5 3 8 Soil 3 00022 598 3 12 0 12 Sludge 1 PBD 209 02493 170 39 01186 02689 5 0 16 2 18 Compost 1 00273 104 3 10 5 15 Soil 3 02582 1115 51 00806 03676 6 0 22 0 22

14

Matrix Parameter Mean sr sR r R p Outliers Used No of data

No of data reported below

detection

Total no of data

Sludge 1 Sum PBD 0256 155 548 0111 0392 6 1 22 Compost 1 0009 331 637 0008 0016 5 1 18 Soil 3 0227 116 717 0074 0455 7 1 26 Abbreviations sr Repeatability standard deviation SR Reproducibility standard deviation r Repeatability limit (comparing two measurements) R Reproducibility limit (comparing two measurements) p Number of labs determination not possible

15

14 Annexes Annex 1 Model questionnaire to be filled by the participating laboratories Annex 3 Report on the validation materials used Annex 2 Statistical calculations Annex 3 Data submitted

16

Annex 1

Model questionnaire to be filled by the participating laboratories

Model questionnaire to be filled by the participating laboratories Name of laboratory Contact person Contact details email Phone Fax Mail address of lab Dispatch address of lab for shipment of samples (no PO boxes) Title of measurement method (copy attached) Our laboratory is willing to participate in the precision experiment for this draft standard method

Yes No As participant we understand that

bull All essential apparatus chemicals and other requirements specified in the method must be available in our laboratory when the programme begins

bull Specified timing requirements such as starting and finishing date of the programme must be rigidly met

bull The method must be strictly adhered to bull Samples must be handled in accordance with instructions bull A qualified operator must perform the measurements

Having studied the method and having made a fair appraisal of our capabilities and facilities we feel that we will be adequately prepared for cooperative testing of this method Comments helliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphellip Signature Date

17

Annex 2

Report on the validation materials used

VI

Abstract This report gives an overview on the available analytical information on the following raw materials to be used for the production of validation materials of the so-called Project HORIZONTAL

bull Four sludge materials from Duumlsseldorf Germany

bull An agricultural soil material from Reading United Kingdom

bull A compost material from Vienna Austria

bull A compost material from Korschenbroich Germany

bull A sludge-amended agricultural soil from Pavia Province Italy

bull A sludge-amended soil from Barcelona Spain

bull A sludge-amended soil from Essen Germany

bull A long-term sludge exposed soil from Hohenheim Germany

VII

List of Abbreviations Throughout this report the following abbreviations are used

AOX absorbable organic halogens

Corg organic carbon content

Ctotal total carbon content

CAT cation exchangeable

CDD chlorinated dibenzodioxin

CDF chlorinated dibenzofuran

DEHP di(2-ethylhexyl)phthalate

DM dry matter

EPA Environment Protection Agency

EU European Union

FM fresh matter

Hp hepta

Hx hexa

IES Institute for Environment and Sustainability

IRMM Institute for Reference Materials and Measurements

JRC Joint Research Centre

LAS linear alkylsulfonates

LoD limit of detection

LUA Landesumweltamt

Ntotal total nitrogen content

NH4-N Ammonium nitrogen

NO3-N Nitrate nitrogen

NP nonylphenol

NRW North Rhine Westphalia

O octa

P poly

PAH polycyclic aromatic hydrocarbon

PCB polychlorinated biphenyl

Pe penta

T tetra

TEQ toxicity equivalent

UBA Umweltbundesamt

WHO World Health Organization

WWTP waste water treatment plant

6

1 Introduction This report gives an overview on the available analytical information on the following raw materials to be used for the production of validation materials of the so-called Project HORIZONTAL

bull Four sludge materials from Duumlsseldorf Germany

bull An agricultural soil material from Reading United Kingdom

bull A compost material from Vienna Austria

bull A compost material from Korschenbroich Germany

bull A sludge-amended agricultural soil from Pavia Province Italy

bull A sludge-amended soil from Barcelona Spain

bull A sludge-amended soil from Essen Germany

bull A long-term sludge exposed soil from Hohenheim Germany

The following analytical information was gathered partly before and during the sampling of the raw materials to be used for the production of the HORIZONTAL validation materials The material were sampled by IES and shipped to IRMM in the course of the year 2005 The information gathered was then completed by various analytical screenings for PAHs and PCBs done by the Institute for Reference Materials and Measurements Geel Belgium for phthalates done by UBA Berlin Germany for PBDE done by IIQAB-CSIC Barcelona Spain for trace elements and some selected major and minor elements by the Institute for Environment and Sustainability Ispra Italy

The work compiled hereafter is based on the numerous additional efforts of the scientists working at various members of the consortium Project HORIZONTAL-Org and contributing organisations

This work is gratefully acknowledged

2 Overview on property values

21 Sludge materials from Duumlsseldorf Germany

The various sewage sludge materials originate from various installations in the North Rhine Westphalia and were produced and sampled by staff from the Landesumweltamt (LUA) NRW under the responsibility from Dr K Furtmann

In total four sludge materials (Sludge A and D from a major municipal WWTP Sludge B from a municipal WWTP with industrial input and Sludge C from a municipal WWTP with high PCB-Content) were obtained and will be blended to two final materials Before sampling the following analytical data for a typical sample were received

7

Table 1 ndash Analytical data obtained on an average sludge sample in LUA NRW (with courtesy of K Furtmann LUA Duumlsseldorf)

Parameter Concentration PCB 120 ugkg DEHP 110 mgkg PAH 5 mgkg (EPA) PCDDF 15 ng TEkg PBDE 400 ugkg NP 40 mgkg LAS 3 gkg AOX 300 mgkg

Subsequent screening led to the information displayed hereafter It should be stressed that the data were obtained as SCREENING information on the UNTREATED or partially treated raw materials Therefore the final target values which are relevant for the validation intercomparison can be different

Table 2 ndash Analytical data obtained on a first screening on the sludge samples from LUA NRW

Sewage sludge A

Dusseldorf

sewage sludge D

Dusseldorf PCB (ngg) 28 62 35 52 101 65 101 31 38 118 49 40 153 30 33 105 24 11 138 46 38 156 lt1 lt1 180 34 23 170 23 19 PAH (ngg) Naphtalene 34 381 Acenaphtylene 15 43 Acenaphthene 81 108 Fluorene 94 1167 Phenantrene 3440 Anthracene 22 344 Flouranthene 316 4817 Pyrene 235 3011 Benz(a)anthracene 473 791 Chrysene 691 1078 Benz(b)fluoranthene 538 1688 Benz(k)fluoranthene 228 635 Benz(a)pyrene 383 1114 Indeno(123-cd)pyrene 92 229 Dibenzo(ah)anthracene 71 70 Benzo(ghi)perylene 80 185

8

Table 3 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Sludge D (1) 0135 41474 385 Sludge B (2) 0538 0034 30634 547 Sludge A (3) 0184 0037 31399 146 Sludge C (4) 0354 1528 6678 229

Table 4 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Sludge 2

(B)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

554

959

694

591

772

509

nq

nq

970

2216

2379

Table 5 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena IES Ispra Spain) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Sludge 1 (D) 265 290 533 359 1231 338 784 438 lt 005 232 786 Sludge 2 (B) 119 311 626 202 278 299 722 251 lt 005 118 625 Sludge 3 (A) 168 360 621 332 847 416 119 451 lt 005 116 1237 Sludge 4 (C) 563 198 116 273 726 511 473 618 lt 005 444 2015

Table 6 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Sludge 1 (D) 2154 58 844 099 103 101 4367 lt15 50448 Sludge 2 (B) 1067 366 692 046 1491 077 5217 lt15 57633 Sludge 3 (A) 731 663 684 035 1287 068 3733 lt15 60369 Sludge 4 (C) 4379 965 527 163 522 107 5628 lt15 23945

Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM)Sludge 1 (D) 03 2403 101 1002 350 15 1944 132Sludge 2 (B) 031 315 97 879 172 12 514 180Sludge 3 (A) 031 1281 153 1567 265 16 1440 168Sludge 4 (C) 055 231 628 2625 371 81 1101 244

9

22 Agricultural soil material from Reading United Kingdom

The material was proposed by the University of Reading (S Nortcliff) and was sampled from a site called ldquoFrogmore Farmrdquo which was featured in the ldquoMetalsrdquo Report for HORIZONTAL This site is close to Reading with soils developed on flintyloamy periglacial materials over Chalk has a long and well documented history of sludge application The focus of the work of Nortcliff et al undertook at this site and the monitoring and control at the site (by Thames Water and the subsequent subsidiary bodies dealing with sludge application to soil) was on metals (and metal loads) with no analysis or indeed any form of investigation in to organics in the broadest sense

The analytical information produced in the context of the screening of the raw material is displayed below

Table 7 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 3

(Reading) 0032 0119 669

Table 8 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 3 (Reading) 015 706 279 138 152 901 267 300 lt 005 258 931

Table 9 ndash Analytical data obtained on a first screening on the sludge-amended soil from Reading (courtesy of IRMM)

Parameter Concentration

PCB ngg 28 lt1 52 lt1 101 lt1 118 lt1 153 lt1 105 lt1 138 lt1 156 lt1 180 lt1 170 lt1 PAH ngg Naphtalene lt10 Acenaphtylene 21 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene lt10 Flouranthene 818 Pyrene 776 Benz(a)anthracene 565

10

Parameter Concentration

Chrysene 608 Benz(b)fluoranthene 824 Benz(k)fluoranthene 329 Benz(a)pyrene 799 Indeno(123-cd)pyrene

779

Dibenzo(ah)anthracene 118 Benzo(ghi)perylene 394

Table 10 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 3

(Reading)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

103

003

nq

nq

nq

nd

nd

272

273

Table 11 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 3 (Reading) 015 706 279 138 152 901 267 300 lt 005 258 931

Table 12 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 3 (Reading) 7936 477 112 096 194 017 4107 443 2102 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 3 (Reading) 042 13 45 69 69 69 216 92

Table 13 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 3 (Reading) 012

11

23 Compost from Vienna Austria

The fresh compost material was obtained from the Austrian Federal Environment Agency (UBA Vienna) which had used a sub-batch of the raw material for national intercomparson The remainder of the material was stored at 4degC until shipment to IRMM for further processing The following analytical information was provided by UBA Austria and completed with various screenings

Table 14 ndash Analytical data on compost material received from UBA Austria Inorganic and sum parameters

Parameter Unit Sample fraction used Observed mean B CAT mgl FM Fresh sample lt10mm 61 K CAT mgl FM Fresh sample lt10mm 2624 Mg CAT mgl FM Fresh sample lt10mm 242 P CAT mgl FM Fresh sample lt10mm 49 B CAT DM Fresh sample lt10mm 00017 K CAT DM Fresh sample lt10mm 072 Mg CAT DM Fresh sample lt10mm 007 P CAT DM Fresh sample lt10mm 001 NO3-N mgkg FM Fresh sample lt10mm 35 NH4-N mgkg FM Fresh sample lt10mm 230 Ctotal DM lt45degdry milled 29 Corg DM lt45degdry milled 27 Ntotal DM lt45degdry milled 17 P mgkg DM lt45degdry milled 2596 K mgkg DM lt45degdry milled 11019 K DM lt45degdry milled 110 B mgkg DM lt45degdry milled 60 Cd mgkg DM lt45degdry milled 046 Cr mgkg DM lt45degdry milled 25 Cu mgkg DM lt45degdry milled 46 Hg mgkg DM lt45degdry milled 020 Ni mgkg DM lt45degdry milled 18 Pb mgkg DM lt45degdry milled 45 Zn mgkg DM lt45degdry milled 198 Ca mgkg DM lt45degdry milled 68776 Ca DM lt45degdry milled 69 Mo mgkg DM lt45degdry milled 08 S mgkg DM lt45degdry milled 2137 Fe mgkg DM lt45degdry milled 9959 Mn mgkg DM lt45degdry milled 418 Na mgkg DM lt45degdry milled 742 Co mgkg DM lt45degdry milled 41 AOX mgkg DM lt30deg dry milled 62

Table 15 ndash Analytical data on compost material received from UBA Austria Polycyclic aromatic hydrocarbons

PAH Unit Result Naphthaline microgkg DM 93 Acenaphthylene microgkg DM 86 Acenaphthene microgkg DM 5 Fluorene microgkg DM 80 Phenanthrene microgkg DM 89 Anthracene microgkg DM 27 Fluoranthene microgkg DM 487 Pyrene microgkg DM 380

12

PAH Unit Result Benzo(a)anthracene microgkg DM 278 Chrysene microgkg DM 317 Benzo(b)fluoranthene microgkg DM 365 Benzo(k)fluoranthene microgkg DM 193 Benz(a)pyrene microgkg DM 320 Indeno(123-cd)pyrene microgkg DM 233 Dibenz(ah)anthracene microgkg DM 67 Benzo(ghi)perylene microgkg DM 225 Sum EPA microgkg DM 3013 Sum EPA mgkg DM 30

Table 16 ndash Analytical data on compost material received from UBA Austria Sum PCDDs and PCBs

Parameter

Dioxine TEQ (ITEF) ngkg DM 73 TEQ (WHO) ngkg DM 35 PCB Σ Ballschmiter mgkg DM 005

Table 17 ndash Analytical data on compost material obtained by screening in IRMM

Parameter Result in ngg

PCB 28 2 52 2 101 4 118 3 153 10 105 1 138 8 156 1 180 5 170 lt1 PAH Naphtalene lt10 Acenaphtylene lt10 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene 26 Fluoranthene 611 Pyrene 510 Benz(a)anthracene 888 Chrysene 957 Benz(b)fluoranthene 1531 Benz(k)fluoranthene 547 Benz(a)pyrene 1101 Indeno(123-cd)pyrene 416 Dibenzo(ah)anthracene 81 Benzo(ghi)perylene 295

13

Table 18 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Compost 1

(Vienna)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

402

019

259

nq

023

004

nq

nq

144

174

259

Table 19 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Compost 1

(Vienna) 0058 1426 557

Table 20 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Compost 1 (Vienna) 039 736 319 410 365 127 495 004 079 013 208

Table 21 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Compost 1 (Vienna) 2063 431 617 426 199 249 1602 lt15 10521

Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Compost 1 (Vienna) 035 3496 81 375 79 55 653 60

Table 22 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Compost 1 (Vienna) 017

14

24 Agricultural soil sludge amended soil from Pavia Italy

This sludge-amended soil material was obtained during a monitoring campaign which aimed at a generic description of the over-all soil quality in Pavia Province Italy The material which was collected from the upper horizon originates from a small farm called ldquoCascina Novellordquo During the characterisation of the site the following analytical information was obtained on a pooled sample of a sub-area of the farm of 20 X 20 m2

Table 23 ndash Analytical data on Pavia soil

Parameter Result Al 713 Wgt As 224 mgkg Cd 079 mgkg Cr 59 mgkg Cu 308 mgkg Hg 008 mgkg Ni 344 mgkg Pb 246 mgkg Zn 95 mgkg C 091 Wgt 2378-TCDD 0047 pgg 12378-PeCDD 015 pgg 123478-HxCDD 019 pgg 123678-HxCDD 15 pgg 123789-HxCDD 074 pgg 1234678-HpCDD 26 pgg OCDD 382 pgg 2378-TCDF 068 pgg 12378-PeCDF 053 pgg 23478-PeCDF 071 pgg 123478-HxDF 100 pgg 123678-HxDF 066 pgg 234678-HxDF 16 pgg 123789-HxDF 027 pgg 1234678-HpDF 12 pgg 1234789-HpDF 068 pgg OCDF 33 pgg I-TEQ 20 pgg WHO-TEQ 17 pgg

In addition the screening performed at IRMM did not reveal significant quantities of PCBs and PAHs which were all below the LoDs (1 ngg for PCBs and 10 ngg for PAHs respectively)

Table 24 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 5 (Pavia) 0005 0011 154

15

Table 25 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 5

(Pavia)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

039

nq

nq

008

nq

nd

nd

670

671

Table 26 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 5 (Pavia) 033 184 573 225 426 305 206 200 lt 005 381 878

Table 27 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 5 (Pavia) 6939 129 145 224 425 116 6118 255 1789 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 5 (Pavia) 184 62 38 108 55 66 597 110

Table 28 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 5 (Pavia) 006

16

25 Sludge-amended-soil from Barcelona Spain

The sludge-amended soil material from Barcelona sampled upon indication from the Barcelorsquo- Group in Barcelona

Table 29 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 2 (Lleida T) 0015 0183 1138

Table 30 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 2

(Lleida T)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

159

045

nq

048

160

nq

nq

1000

1004

Table 31 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 2 (Lleida T) 059 141 327 536 405 186 184 224 lt 005 318 111

Table 32 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 2 (Lleida T) 4443 1067 1429 253 344 204 4116 780 3396 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 2 (Lleida T) 064 65 26 125 59 17 547 65

Table 33 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 2 (Lleida T) 010

17

26 Sludge amended soil from Essen Germany

The German sludge-amended soil from Essen which was provided as the three sludge materials by LUA NRW did not feature significant concentrations of the PCB congeners 28 52 101 118 153 105 138 156 180 170 but had detectable amounts of some PAHs

Table 34 ndash Analytical screening data on the German sludge-amended soil

Parameter Concentration(ngg)

Naphtalene lt10 Acenaphtylene lt10 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene lt10 Fluoranthene 28 Pyrene 20 Benz(a)anthracene 24 Chrysene 47 Benz(b)fluoranthene 76 Benz(k)fluoranthene 20 Benz(a)pyrene 35 Indeno(123-cd)pyrene 35 Dibenzo(ah)anthracene 10 Benzo(ghi)perylene 26

Table 35 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 4 (Essen) 0011 0302 055

Table 36 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 4

(Essen)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

nq

nq

nq

nq

nq

nq

128

191

203

18

Table 37 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 4 (Essen) 052 545 261 805 320 403 273 273 lt 005 295 781

Table 38 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 4 (Essen) 7947 442 085 06 086 007 2163 189 2019 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 4 (Essen) 045 19 42 87 683 60 462 61

Table 39 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 4 (Essen) 004

27 Long-term sludge exposed soil from Hohenheim-Stuttgart Germany

Similarly an additional sludge exposed soil was sampled at the University of Hohenheim Stuttgart were a test soil was long-term exposed to elevated concentrations of sewage sludge

Table 40 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 1 (Stuttgart) 0045 0263 1765

Table 41 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 1

(Stuttgart)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

230

006

004

004

nq

nd

nd

498

500

19

Table 42 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 1 (Stuttgart) 069 127 361 262 504 183 252 262 lt 005 266 142

Table 43 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 1 (Stuttgart) 7194 1006 133 186 366 088 7874 275 3571 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 1 (Stuttgart) 123 50 47 212 85 69 991 129

Table 44 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 1 (Stuttgart) 177

18

Annex 3

Statistical calculations

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 47)Mandels h statistics(Sludge 1 - PBD 47)

Sample Sludge 1 NUM

Element PBD 47

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00213 0001 3 -021 005 - - 10L - - NUM46L 00273 0002 4 016 021 - - 46L - - NUM64L 00059 0000 4 -116 002 NUM - 64L - - NUM12L 00188 0000 4 -036 002 - - 12L - - NUM26L 00499 0024 2 157 223 Fail - - 26L - - NUM

Totgem 0025 0005 mgkg 1-level 172 (185) NUM (10L46L64L12L26L) -1Totstd= 0016 0010 5-level 157 (162) 5

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 5 Labs rejected (10L46L64L12L26L)

000 050 100 150 200 250

k-values

10L

46L

64L

12L

26L

Mandels k statistics(Sludge 1 - PBD 47)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

10L

46L

64L

12L

26L

Labo

rato

ries

NUM

-200 -100 000 100 200

h-values

10L

46L

64L

12L

26L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 47)

Sludge 1-PBD 47

Unit mgkg

Mandels k statistics(Soil 3 - PBD 47)Mandels h statistics(Soil 3 - PBD 47)

Sample Soil 3 Soil 3 - PBD 47 -- Mean PARM = 0001 [mgkg]

Element PBD 47

General calcparmT1= 134814E-02T2= 142830E-05T3= 13T4= 45T5= 22767E-06

n= variabelp= 4

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean26L 00007 0000 2 -143 001 00007 00000 2 1 00046L 00010 0001 4 010 181 00010 00008 4 3 00010L 00011 0000 3 049 023 00011 00001 3 2 00012L 00012 0000 4 084 081 00012 00004 4 3 000

Totgem 0001 0000 mgkg 1-level 149 (177) 4 00010 () 4 3Totstd= 0000 0000 5-level 142 (159)

RESULTS Mean = 000100 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000050 --gt 5031 r = 00014Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000050 --gt 5031 R = 00014Remarks none

000 050 100 150 200

k-values

26L

46L

10L

12L

Mandels k statistics(Soil 3 - PBD 47)

00 00 00 00 00 00 00 00 00 00 00

Deviation from Mean

26L

46L

10L

12L

Labo

rato

ries

Soil 3 - PBD 47 -- Mean PARM = 0001 [mgkg]

-200 -100 000 100

h-values

26L

46L

10L

12L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 47)

Soil 3-PBD 47

Unit mgkg

Mandels k statistics(Compost 1 - PBD 99)Mandels h statistics(Compost 1 - PBD 99)

Sample Compost 1 Compost 1 - PBD 99 -- Mean PARM = 0003 [mgkg]

Element PBD 99

General calcparmT1= 492124E-02T2= 148747E-04T3= 17T4= 61T5= 93196E-06

n= variabelp= 5

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00020 0000 4 -137 053 00020 00004 4 3 000

26L 00025 0000 2 -058 024 00025 00002 2 1 00010L 00029 0000 3 012 032 00029 00003 3 2 00046L 00033 0001 4 069 161 00033 00013 4 3 00012L 00036 0001 4 114 140 00036 00011 4 3 000

Totgem 0003 0001 mgkg 1-level 172 (185) 5 00029 () 5 4Totstd= 0001 0001 5-level 157 (162)

RESULTS Mean = 000286 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000088 --gt 3086 r = 00025Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000101 --gt 3525 R = 00028Remarks none

000 050 100 150 200

k-values

4L

26L

10L

46L

12L

Mandels k statistics(Compost 1 - PBD 99)

00 00 00 00 00 00 00 00 00 00

Deviation from Mean

4L

26L

10L

46L

12L

Labo

rato

ries

Compost 1 - PBD 99 -- Mean PARM = 0003 [mgkg]

-200 -100 000 100 200

h-values

4L

26L

10L

46L

12L

Labo

rato

ries

Mandels h statistics(Compost 1 - PBD 99)

Compost 1-PBD 99

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 99)Mandels h statistics(Sludge 1 - PBD 99)

Sample Sludge 1 Sludge 1 - PBD 99 -- Mean PARM = 0024 [mgkg]

Element PBD 99

General calcparmT1= 448050E-01T2= 112113E-02T3= 19T4= 73T5= 32972E-05

n= variabelp= 5

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean64L 00173 0002 4 -118 041 Fail 00173 00019 4 3 -0014L 00183 0002 4 -104 032 00183 00015 4 3 -001

12L 00227 0001 4 -038 022 00227 00010 4 3 00010L 00290 0001 3 055 021 00290 00010 3 2 00146L 00320 0002 4 100 039 00320 00018 4 3 00126L 00323 0011 2 105 234 - - 26L - - 001

Totgem 0025 0003 mgkg 1-level 187 (177) 5 00239 (26L) 5 4Totstd= 0007 0004 5-level 166 (154) 1

RESULTS Mean = 002385 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000153 --gt 643 r = 00043Between lab variance S2L = 000004Reproducibility var S2R = 000004Reproducibility std SR = 000666 --gt 2791 R = 00186Remarks 1 Lab rejected (26L)

000 050 100 150 200 250

k-values

64L

4L

12L

10L

46L

26L

Mandels k statistics(Sludge 1 - PBD 99)

00 00 00 00 00 00 00 00 00 00

Deviation from Mean

64L

4L

12L

10L

46L

26L

Labo

rato

ries

Sludge 1 - PBD 99 -- Mean PARM = 0024 [mgkg]

-200 -100 000 100 200

h-values

64L

4L

12L

10L

46L

26L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 99)

Sludge 1-PBD 99

Unit mgkg

Mandels k statistics(Soil 3 - PBD 99)Mandels h statistics(Soil 3 - PBD 99)

Sample Soil 3 NUM

Element PBD 99

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00017 0000 4 091 068 - - 10L - - NUM46L 00017 0001 4 100 211 - - 46L - - NUM64L 00005 0000 4 -106 023 NUM - 64L - - NUM12L 00012 0000 4 015 014 - - 12L - - NUM26L 00006 0000 2 -101 012 - - 26L - - NUM

Totgem 0001 0000 mgkg 1-level 172 (173) NUM (10L46L64L12L26L) -1Totstd= 0001 0000 5-level 157 (153) 5

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 5 Labs rejected (10L46L64L12L26L)

000 050 100 150 200 250

k-values

10L

46L

64L

12L

26L

Mandels k statistics(Soil 3 - PBD 99)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

10L

46L

64L

12L

26L

Labo

rato

ries

NUM

-200 -100 000 100 200

h-values

10L

46L

64L

12L

26L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 99)

Soil 3-PBD 99

Unit mgkg

Mandels k statistics(Compost 1 - PBD 100)Mandels h statistics(Compost 1 - PBD 100)

Sample Compost 1 Compost 1 - PBD 100 -- Mean PARM = 0001 [mgkg]

Element PBD 100

General calcparmT1= 124272E-02T2= 113129E-05T3= 14T4= 52T5= 46584E-07

n= variabelp= 4

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean26L 00006 0000 2 -131 037 Fail 00006 00001 2 1 00010L 00009 0000 4 003 083 00009 00002 4 3 00046L 00009 0000 4 016 115 00009 00002 4 3 00012L 00011 0000 4 112 136 Fail 00011 00003 4 3 000

Totgem 0001 0000 mgkg 1-level 149 (167) 4 00009 () 4 3Totstd= 0000 0000 5-level 142 (15)

RESULTS Mean = 000085 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000022 --gt 2531 r = 00006Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000025 --gt 2882 R = 00007Remarks none

000 050 100 150

k-values

26L

10L

46L

12L

Mandels k statistics(Compost 1 - PBD 100)

00 00 00 00 00 00 00 00 00 00 00

Deviation from Mean

26L

10L

46L

12L

Labo

rato

ries

Compost 1 - PBD 100 -- Mean PARM = 0001 [mgkg]

-200 -100 000 100 200

h-values

26L

10L

46L

12L

Labo

rato

ries

Mandels h statistics(Compost 1 - PBD 100)

Compost 1-PBD 100

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 100)Mandels h statistics(Sludge 1 - PBD 100)

Sample Sludge 1 Sludge 1 - PBD 100 -- Mean PARM = 0005 [mgkg]

Element PBD 100

General calcparmT1= 852065E-02T2= 412762E-04T3= 18T4= 68T5= 78914E-07

n= variabelp= 5

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00039 0000 4 -042 007 Fail 00039 00002 4 3 000

12L 00044 0000 4 -041 005 Fail 00044 00001 4 3 00010L 00046 0000 4 -041 013 Fail 00046 00003 4 3 00046L 00056 0000 4 -040 012 Fail 00056 00003 4 3 00026L 00059 0000 2 -040 013 Fail 00059 00003 2 1 00038L 02168 0006 4 204 244 Fail - - 38L - - 021

Totgem 0040 0001 mgkg 1-level 187 (177) 5 00049 (38L) 5 4Totstd= 0087 0002 5-level 166 (154) 1

RESULTS Mean = 000486 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000025 --gt 507 r = 00007Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000084 --gt 1731 R = 00024Remarks 1 Lab rejected (38L)

000 050 100 150 200 250

k-values

4L

12L

10L

46L

26L

38L

Mandels k statistics(Sludge 1 - PBD 100)

-01 00 01 01 02 02 03

Deviation from Mean

4L

12L

10L

46L

26L

38L

Labo

rato

ries

Sludge 1 - PBD 100 -- Mean PARM = 0005 [mgkg]

-100 000 100 200 300

h-values

4L

12L

10L

46L

26L

38L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 100)

Sludge 1-PBD 100

Unit mgkg

Mandels k statistics(Soil 3 - PBD 100)Mandels h statistics(Soil 3 - PBD 100)

Sample Soil 3 NUM

Element PBD 100

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00003 0000 4 -050 000 Fail - - 10L - - NUM46L 00003 0000 4 -050 000 Fail NUM - 46L - - NUM3L 305500 2051 2 150 200 Fail - - 3L - - NUM

26L 00005 0000 2 -050 000 Fail - - 26L - - NUM

Totgem 7638 0513 mgkg 1-level 149 (177) NUM (10L46L3L26L) -1Totstd= 15275 1025 5-level 142 (159) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (10L46L3L26L)

000 050 100 150 200

k-values

10L

46L

3L

26L

Mandels k statistics(Soil 3 - PBD 100)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

10L

46L

3L

26L

Labo

rato

ries

NUM

-100 000 100 200

h-values

10L

46L

3L

26L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 100)

Soil 3-PBD 100

Unit mgkg

Mandels k statistics(Compost 1 - PBD 153)Mandels h statistics(Compost 1 - PBD 153)

Sample Compost 1 NUM

Element PBD 153

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean44L 00053 0001 3 150 157 Fail - - 44L - - NUM46L 00007 0000 4 -044 111 Fail - - 46L - - NUM12L 00005 0000 4 -051 055 Fail - - 12L - - NUM26L 00005 0000 2 -054 001 Fail NUM - 26L - - NUM

Totgem 0002 0000 mgkg 1-level 149 (177) NUM (44L46L12L26L) -1Totstd= 0002 0000 5-level 142 (159) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (44L46L12L26L)

000 050 100 150 200

k-values

44L

46L

12L

26L

Mandels k statistics(Compost 1 - PBD 153)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

44L

46L

12L

26L

Labo

rato

ries

NUM

-100 000 100 200

h-values

44L

46L

12L

26L

Labo

rato

ries

Mandels h statistics(Compost 1 - PBD 153)

Compost 1-PBD 153

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 153)Mandels h statistics(Sludge 1 - PBD 153)

Sample Sludge 1 Sludge 1 - PBD 153 -- Mean PARM = 0004 [mgkg]

Element PBD 153

General calcparmT1= 676738E-02T2= 267609E-04T3= 18T4= 68T5= 19626E-05

n= variabelp= 5

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00024 0000 4 -157 017 00024 00002 4 3 000

12L 00038 0002 4 006 154 00038 00018 4 3 00046L 00039 0000 4 011 026 00039 00003 4 3 00026L 00039 0000 2 018 004 00039 00000 2 1 00064L 00049 0002 4 122 159 00049 00018 4 3 000

Totgem 0004 0001 mgkg 1-level 172 (173) 5 00038 () 5 4Totstd= 0001 0001 5-level 157 (153)

RESULTS Mean = 000378 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000123 --gt 3252 r = 00034Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000142 --gt 3754 R = 00040Remarks none

000 050 100 150 200

k-values

4L

12L

46L

26L

64L

Mandels k statistics(Sludge 1 - PBD 153)

00 00 00 00 00 00 00

Deviation from Mean

4L

12L

46L

26L

64L

Labo

rato

ries

Sludge 1 - PBD 153 -- Mean PARM = 0004 [mgkg]

-200 -100 000 100 200

h-values

4L

12L

46L

26L

64L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 153)

Sludge 1-PBD 153

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 154)Mandels h statistics(Sludge 1 - PBD 154)

Sample Sludge 1 NA

Element PBD 154

General calcparmT1= NAT2= NAT3=T4=T5=

n= variabelp=

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00021 0000 3 -100 021 NA - 4L - - NA

46L 00025 0000 4 115 018 NA - 46L - - NA64L 00021 0001 4 -066 179 - - 64L - - NA12L 00023 0000 4 050 085 - - 12L - - NA

Totgem 0002 0000 mgkg 1-level 149 (167) NA (4L46L64L12L) -1Totstd= 0000 0000 5-level 142 (15) 4

RESULTS Mean = NA mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NAReproducibility var S2R = NAReproducibility std SR = NA --gt NA R = NARemarks 4 Labs rejected (4L46L64L12L)

000 050 100 150 200

k-values

4L

46L

64L

12L

Mandels k statistics(Sludge 1 - PBD 154)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

4L

46L

64L

12L

Labo

rato

ries

NA

-100 000 100 200

h-values

4L

46L

64L

12L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 154)

Sludge 1-PBD 154

Unit mgkg

Mandels k statistics(Soil 3 - PBD 154)Mandels h statistics(Soil 3 - PBD 154)

Sample Soil 3 NUM

Element PBD 154

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

4L 00010 - 1 150 Fail - - 4L - - NUM46L 00001 0000 4 -053 096 Fail - - 46L - - NUM64L 00001 0000 4 -056 105 Fail NUM - 64L - - NUM12L 00002 0000 4 -040 099 Fail - - 12L - - NUM

Totgem 000037 0000 mgkg 1-level 149 (164) NUM (4L46L64L12L) -1Totstd= 000042 0000 5-level 142 (153) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (4L46L64L12L)

000 050 100 150

k-values

4L

46L

64L

12L

Mandels k statistics(Soil 3 - PBD 154)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

4L

46L

64L

12L

Labo

rato

ries

NUM

-100 000 100 200

h-values

4L

46L

64L

12L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 154)

Soil 3-PBD 154

Unit mgkg

Mandels k statistics(Compost 1 - PBD 209)Mandels h statistics(Compost 1 - PBD 209)

Sample Compost 1 NUM

Element PBD 209

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00065 0003 2 -049 032 - - 4L - - NUM

44L 00573 0021 4 150 197 Fail - - 44L - - NUM12L 00078 0001 4 -045 011 - - 12L - - NUM26L 00049 0000 2 -056 000 NUM - 26L - - NUM

Totgem 0019 0006 mgkg 1-level 149 (177) NUM (4L44L12L26L) -1Totstd= 0025 0010 5-level 142 (159) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (4L44L12L26L)

000 050 100 150 200

k-values

4L

44L

12L

26L

Mandels k statistics(Compost 1 - PBD 209)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

4L

44L

12L

26L

Labo

rato

ries

NUM

-100 000 100 200

h-values

4L

44L

12L

26L

Labo

rato

ries

Mandels h statistics(Compost 1 - PBD 209)

Compost 1-PBD 209

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 209)Mandels h statistics(Sludge 1 - PBD 209)

Sample Sludge 1 Sludge 1 - PBD 209 -- Mean PARM = 0249 [mgkg]

Element PBD 209

General calcparmT1= 394542E+00T2= 107296E+00T3= 16T4= 56T5= 19723E-02

n= variabelp= 5

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 01550 0055 4 -112 148 Fail 01550 00551 4 3 -009

46L 02050 0007 2 -053 019 02050 00071 2 1 -00412L 02137 0058 4 -042 155 02137 00576 4 3 -00426L 03149 0021 2 078 057 Fail 03149 00210 2 1 00764L 03577 0007 4 129 020 Fail 03577 00074 4 3 011

Totgem 0249 0030 mgkg 1-level 172 (185) 5 02493 () 5 4Totstd= 0084 0025 5-level 157 (162)

RESULTS Mean = 024926 mgkg

Repeatability variance S2r = 000179Repeatability std Sr = 004234 --gt 1699 r = 01186Between lab variance S2L = 000743Reproducibility var S2R = 000922Reproducibility std SR = 009604 --gt 3853 R = 02689Remarks none

000 050 100 150 200

k-values

4L

46L

12L

26L

64L

Mandels k statistics(Sludge 1 - PBD 209)

-01 -01 00 01 01 02

Deviation from Mean

4L

46L

12L

26L

64L

Labo

rato

ries

Sludge 1 - PBD 209 -- Mean PARM = 0249 [mgkg]

-200 -100 000 100 200

h-values

4L

46L

12L

26L

64L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 209)

Sludge 1-PBD 209

Unit mgkg

Mandels k statistics(Soil 3 - PBD 209)Mandels h statistics(Soil 3 - PBD 209)

Sample Soil 3 Soil 3 - PBD 209 -- Mean PARM = 0258 [mgkg]

Element PBD 209

General calcparmT1= 596398E+00T2= 191917E+00T3= 22T4= 84T5= 13249E-02

n= variabelp= 6

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean26L 01162 0021 2 -108 074 Fail 01162 00207 2 1 -0144L 01303 0031 4 -097 111 Fail 01303 00312 4 3 -013

46L 01975 0036 4 -046 128 Fail 01975 00359 4 3 -00644L 02898 0035 4 024 124 Fail 02898 00346 4 3 00312L 03895 0018 4 100 065 Fail 03895 00181 4 3 01364L 04260 0022 4 127 078 Fail 04260 00219 4 3 017

Totgem 0258 0027 mgkg 1-level 187 (177) 6 02582 () 6 5Totstd= 0132 0008 5-level 166 (154)

RESULTS Mean = 025818 mgkg

Repeatability variance S2r = 000083Repeatability std Sr = 002878 --gt 1115 r = 00806Between lab variance S2L = 001640Reproducibility var S2R = 001723Reproducibility std SR = 013127 --gt 5084 R = 03676Remarks none

000 050 100 150

k-values

26L

4L

46L

44L

12L

64L

Mandels k statistics(Soil 3 - PBD 209)

-02 -01 -01 00 01 01 02 02

Deviation from Mean

26L

4L

46L

44L

12L

64L

Labo

rato

ries

Soil 3 - PBD 209 -- Mean PARM = 0258 [mgkg]

-200 -100 000 100 200

h-values

26L

4L

46L

44L

12L

64L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 209)

Soil 3-PBD 209

Unit mgkg

Mandels k statistics(Compost 1 - Sum PBD)Mandels h statistics(Compost 1 - Sum PBD)

Sample Compost 1 Compost 1 - Sum PBD -- Mean PARM = 0009 [mgkg]

Element Sum PBD

General calcparmT1= 154064E-01T2= 169065E-03T3= 18T4= 68T5= 11354E-04

n= variabelp= 5

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00031 0002 4 -067 016 00031 00016 4 3 -0014L 00055 0005 4 -056 048 00055 00047 4 3 000

46L 00085 0003 4 -042 031 00085 00030 4 3 00026L 00123 0000 2 -024 003 00123 00002 2 1 00012L 00154 0002 4 -011 021 00154 00021 4 3 00144L 00613 0023 4 200 237 Fail - - 44L - - 005

Totgem 0018 0006 mgkg 1-level 187 (177) 5 00089 (44L) 5 4Totstd= 0022 0009 5-level 166 (154) 1

RESULTS Mean = 000893 mgkg

Repeatability variance S2r = 000001Repeatability std Sr = 000296 --gt 3308 r = 00083Between lab variance S2L = 000002Reproducibility var S2R = 000003Reproducibility std SR = 000570 --gt 6374 R = 00159Remarks 1 Lab rejected (44L)

000 050 100 150 200 250

k-values

10L

4L

46L

26L

12L

44L

Mandels k statistics(Compost 1 - Sum PBD)

00 00 00 00 00 00 01 01

Deviation from Mean

10L

4L

46L

26L

12L

44L

Labo

rato

ries

Compost 1 - Sum PBD -- Mean PARM = 0009 [mgkg]

-100 000 100 200

h-values

10L

4L

46L

26L

12L

44L

Labo

rato

ries

Mandels h statistics(Compost 1 - Sum PBD)

Compost 1-Sum PBD

Unit mgkg

Mandels k statistics(Sludge 1 - Sum PBD)Mandels h statistics(Sludge 1 - Sum PBD)

Sample Sludge 1 Sludge 1 - Sum PBD -- Mean PARM = 0256 [mgkg]

Element Sum PBD

General calcparmT1= 531806E+00T2= 162188E+00T3= 22T4= 84T5= 25223E-02

n= variabelp= 6

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00423 0025 4 -156 044 Fail 00423 00252 4 3 -02146L 01808 0118 4 -049 205 - - 46L - - -0074L 01810 0056 4 -049 097 01810 00558 4 3 -007

38L 02168 0006 4 -022 010 02168 00059 4 3 -00412L 02890 0065 4 034 113 02890 00647 4 3 00364L 03958 0008 4 116 014 Fail 03958 00079 4 3 01426L 04094 0034 2 126 059 Fail 04094 00337 2 1 015

Totgem 0245 0044 mgkg 1-level 198 (179) 6 02557 (46L) 6 5Totstd= 0130 0039 5-level 171 (155) 1

RESULTS Mean = 025570 mgkg

Repeatability variance S2r = 000158Repeatability std Sr = 003970 --gt 1553 r = 01112Between lab variance S2L = 001807Reproducibility var S2R = 001964Reproducibility std SR = 014015 --gt 5481 R = 03924Remarks 1 Lab rejected (46L)

000 050 100 150 200 250

k-values

10L

46L

4L

38L

12L

64L

26L

Mandels k statistics(Sludge 1 - Sum PBD)

-03 -02 -02 -01 -01 00 01 01 02 02

Deviation from Mean

10L

46L

4L

38L

12L

64L

26L

Labo

rato

ries

Sludge 1 - Sum PBD -- Mean PARM = 0256 [mgkg]

-200 -100 000 100 200

h-values

10L

46L

4L

38L

12L

64L

26L

Labo

rato

ries

Mandels h statistics(Sludge 1 - Sum PBD)

Sludge 1-Sum PBD

Unit mgkg

Mandels k statistics(Soil 3 - Sum PBD)Mandels h statistics(Soil 3 - Sum PBD)

Sample Soil 3 Soil 3 - Sum PBD -- Mean PARM = 0227 [mgkg]

Element Sum PBD

General calcparmT1= 610980E+00T2= 200876E+00T3= 26T4= 100T5= 13106E-02

n= variabelp= 7

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00028 0001 4 -037 000 Fail 00028 00005 4 3 -02226L 01179 0021 2 -036 003 Fail 01179 00208 2 1 -0114L 01305 0031 4 -036 004 Fail 01305 00308 4 3 -010

46L 02065 0035 4 -036 005 Fail 02065 00350 4 3 -00244L 02923 0037 4 -035 005 Fail 02923 00365 4 3 00712L 04051 0015 4 -034 002 Fail 04051 00149 4 3 01864L 04314 0022 4 -033 003 Fail 04314 00223 4 3 0203L 305500 2051 2 247 283 Fail - - 3L - - 3032

Totgem 4017 0276 mgkg 1-level 206 (181) 7 02266 (3L) 7 6Totstd= 10722 0717 5-level 175 (156) 1

RESULTS Mean = 022663 mgkg

Repeatability variance S2r = 000069Repeatability std Sr = 002626 --gt 1159 r = 00735Between lab variance S2L = 002568Reproducibility var S2R = 002637Reproducibility std SR = 016238 --gt 7165 R = 04547Remarks 1 Lab rejected (3L)

000 050 100 150 200 250 300

k-values

10L

26L

4L

46L

44L

12L

64L

3L

Mandels k statistics(Soil 3 - Sum PBD)

-50 00 50 100 150 200 250 300 350

Deviation from Mean

10L

26L

4L

46L

44L

12L

64L

3L

Labo

rato

ries

Soil 3 - Sum PBD -- Mean PARM = 0227 [mgkg]

-100 000 100 200 300

h-values

10L

26L

4L

46L

44L

12L

64L

3L

Labo

rato

ries

Mandels h statistics(Soil 3 - Sum PBD)

Soil 3-Sum PBD

19

Annex 4

Raw data submitted

Sample Compost1 Sample Compost 1 Sample Compost 1Element PBD 99 Element PBD 100 Element PBD 153

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]4L 00021 10L 00008 44L 000504L 00024 10L 00008 44L 000604L 00014 10L 00007 44L 000504L 00020 10L 00011 46L 00004

10L 00029 46L 00007 46L 0001210L 00027 46L 00012 46L 0000410L 00032 46L 00009 46L 0000946L 00025 46L 00007 12L 0000446L 00052 12L 00008 12L 0000846L 00029 12L 00012 12L 0000446L 00026 12L 00008 12L 0000712L 00026 12L 00014 26L 0000512L 00043 26L 00007 26L 0000512L 00026 26L 0000612L 0004726L 0002626L 00024

Sample Compost 1 Sample Compost 1 Sample Compost 1Element PBD 154 Element PBD 183 Element PBD 196

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]4L 00010 46L 00002 46L 00011

46L 00003 46L 00024 46L 0000846L 00007 46L 00021 12L 0000246L 00003 46L 00003 12L 0000346L 00004 12L 00003 12L 0000112L 00003 12L 00011 12L 0000212L 00005 12L 0000312L 00031 12L 0000312L 00006

Sample Compost 1 Sample Compost 1 Sample Compost 1Element PBD 197 Element PBD 203 Element PBD 209

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00002 46L 00010 4L 0004146L 00023 12L 00002 4L 0008946L 00022 12L 00003 44L 0041012L 00004 12L 00002 44L 0084012L 00006 12L 00002 44L 0064012L 00003 44L 0040012L 00004 12L 00079

12L 0007312L 0006512L 0009326L 0004926L 00049

Sample Compost 1Element PBD 47

LAB PARM [mgkg]26L 0003826L 00039

Element PBD 99 Element PBD 47 Element PBD 209LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]

4L 00170 10L 00210 4L 010004L 00200 10L 00220 4L 018004L 00170 10L 00210 4L 012004L 00190 46L 00300 4L 0220010L 00280 46L 00280 46L 0210010L 00300 46L 00250 46L 0200010L 00290 46L 00260 64L 0351846L 00340 64L 00059 64L 0363846L 00330 64L 00057 64L 0364546L 00300 64L 00062 64L 0350846L 00310 64L 00060 12L 0220964L 00194 12L 00191 12L 0177164L 00154 12L 00187 12L 0292264L 00185 12L 00190 12L 0164664L 00159 12L 00186 26L 0329712L 00242 26L 00666 26L 0300012L 00223 26L 0033212L 0022112L 0022226L 0024626L 00400

Element PBD 203 Element PBD 197 Element PBD 196LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00022 46L 00027 46L 0002446L 00014 46L 00024 46L 0002264L 00036 12L 00161 64L 0005864L 00058 12L 00060 64L 0006512L 00063 12L 00061 12L 0004812L 00034 12L 00036 12L 0002512L 00038 12L 0003212L 00027 12L 00022

Element PBD 183 Element PBD 154 Element PBD 153LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00049 4L 00020 4L 0002246L 00035 4L 00022 4L 0002446L 00036 4L 00020 4L 0002246L 00034 46L 00025 4L 0002664L 00027 46L 00025 46L 0004064L 00023 46L 00025 46L 0004264L 00024 46L 00023 46L 0003564L 00020 64L 00034 46L 0003812L 00230 64L 00023 64L 0007412L 00032 64L 00017 64L 0004712L 00031 64L 00011 64L 0004612L 00030 12L 00030 64L 0003026L 00007 12L 00021 12L 0006526L 00008 12L 00021 12L 00029

12L 00021 12L 0003226L 00015 12L 0002926L 00019 26L 00039

26L 00040

Element PBD 100LAB PARM [mgkg]

4L 000384L 000414L 000374L 00038

38L 0219038L 0220038L 0208038L 0220010L 0004410L 0005010L 0004310L 0004646L 0005746L 0005946L 0005346L 0005312L 0004312L 0004512L 0004312L 0004326L 0006226L 00057

Sample Soil 3 Sample Soil 3 Sample Soil 3Element PBD 99 Element PBD 47 Element PBD 100

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]10L 00016 10L 00011 10L 0000310L 00019 10L 00010 10L 0000410L 00013 10L 00012 10L 0000410L 00019 46L 00007 10L 0000246L 00025 46L 00022 46L 0000246L 00025 46L 00005 46L 0000646L 00008 46L 00007 46L 0000246L 00011 12L 00010 46L 0000264L 00005 12L 00017 3L 29100064L 00005 12L 00010 3L 32000064L 00006 12L 00009 26L 0000564L 00007 26L 00007 26L 0000512L 00012 26L 0000712L 0001312L 0001312L 0001226L 0000526L 00006

Sample Soil 3 Sample Soil 3 Sample Soil 3Element PBD 153 Element PBD 154 Element PBD 196

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]44L 00050 4L 00010 46L 0000744L 00050 46L 00001 46L 0001146L 00002 46L 00002 46L 0000846L 00003 46L 00001 46L 0001146L 00002 46L 00002 64L 0002646L 00002 64L 00001 64L 0002664L 00001 64L 00001 64L 0002964L 00001 64L 00001 64L 0003464L 00001 64L 00002 12L 0004564L 00002 12L 00003 12L 00032

12L 00002 12L 0002212L 00002 12L 0002112L 00002

Sample Soil 3 Sample Soil 3 Sample Soil 3Element PBD 197 Element PBD 203 Element PBD 209

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00006 46L 00011 4L 0091046L 00013 46L 00017 4L 0150046L 00011 46L 00015 4L 0120046L 00013 46L 00018 4L 0160012L 00090 64L 00013 44L 0337012L 00056 64L 00014 44L 0281012L 00033 64L 00016 44L 0287012L 00032 64L 00015 44L 02540

12L 00055 46L 0230012L 00041 46L 0220012L 00027 46L 0150012L 00026 46L 01900

64L 0438164L 0401664L 0414464L 0449812L 0367112L 0397812L 0409112L 03838

Sample Soil 3 26L 0102Element PBD 183 26L 0131

LAB PARM [mgkg]46L 0000746L 0000846L 0005846L 0000764L 0000264L 0000364L 0000364L 0000312L 0001512L 0001112L 0000712L 00007

European Commission EUR 23003 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on polybrominated diphenylethers Author(s) E Sobiecka H van der Sloot D Barcelo B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 68 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07403-5 Abstract Project HORIZONTAL is interdisciplinary aiming at a harmonisation and horizontal standardisation of test procedures in particular for sludge soils and biowastes In the context of this standardization project a series of draft technical specification were designed upon an extensive desk study fine-tuned after expert consultations and finally validated in international intercomparisons exercise This report summarises the work performed within the validation study of the draft standard for the determination of polybrominated diphenylethers (PBDE) in soils sludge and treated bio-waste using gas-chromatography method with mass selective detection (GC-MS) It further explains the underlying statistical concept for the calculation of reproducibility and repeatability from intercomparisons data In addition all single values results of the statistical evaluation as well as background information on the validation materials used are described and explained

The mission of the JRC is to provide customer-driven scientific and technical support for the conception development implementation and monitoring of EU policies As a service of the European Commission the JRC functions as a reference centre of science and technology for the Union Close to the policy-making process it serves the common interest of the Member States while being independent of special interests whether private or national

LB

-NA

-23003-EN

-C

Project HORIZONTAL Validation Report

Validation of a horizontal standard for the determination of selected polybrominated diphenylethers (PBDE) by gas-chromatography method with mass selective detection (GC-MS) in a European Intercomparison Exercise E Sobiecka H Van der Sloot D Barcelo B M Gawlik Elzbieta Sobiecka Bernd Manfred Gawlik European Commission Joint Research Centre Institute for Environment and Sustainability Via Enrico Fermi 21020 Ispra - Italy

Hans van der Sloot ECN Emission Characterisation and Reduction Westerduinweg 3 PO Box 1 1755 ZG Petten The Netherlands

Damia Barcelo Consejo Superior de Investigaciones Cientificas (CSIC) IIQAB Jordi Girona 18 E-08034 BARCELONA Spain

to whom correspondence should be sent

by email to berndgawlikjrcit

Summary Project HORIZONTAL is interdisciplinary aiming at a harmonisation and horizontal standardisation of test procedures in particular for sludge soils and biowastes In the context of this standardization project a series of draft technical specification were designed upon an extensive desk study fine-tuned after expert consultations and finally validated in international intercomparisons exercise This report summarises the work performed within the validation study of the draft standard for the determination of polybrominated diphenylethers (PBDE) in soils sludge and treated bio-waste using gas-chromatography method with mass selective detection (GC-MS) It further explains the underlying statistical concept for the calculation of reproducibility and repeatability from intercomparisons data In addition all single values results of the statistical evaluation as well as background information on the validation materials used are described and explained

Abbreviations Throughout this report the following abbreviations are used ANOVA Analysis of variances

CAS Chemical Abstracts System

CEN Comitteeacute Europeacuteen de Normalisation

DG Directorate General

ECD Electron Capture Detector

ECN Energy Research Centre for the Netherlands

EU European Union

IES Institute for Environment and Sustainability

IT Information Technology

ISO International Organization for Standardisation

JRC Joint Research Centre

GC Gas Chromatography

MILC Measure Interlaboratory Comparison

MS Mass Spectroscopy

p Number of labs

PBDE Polybrominated Diphenylethers

r Repeatability limit

R Reproducibility limit

sr Repeatability standard deviation

sR Reproducibility standard deviation

TC Technical Committee

4

Table of Contents Summary 2 Abbreviations 3 Table of Contents 4

Introduction to the validation project 5 11 Statistical concept underlying the validation 6

111 Introduction to the statistical model 6 112 Requirements for precision experiment 7 113 Statistical analysis 8

12 Validation exercise for PBDE 8 121 Compounds to be measured 8 122 Samples dispatched for the validation of PBDE 8 123 Draft standards to be followed 8 124 Analytical programm 8 125 Timing and Submission of data 9 126 Participants 10

13 Summary results and derived performance characteristics 11 14 Annexes 15

5

Introduction to the validation project Project HORIZONTAL is interdisciplinary aiming at a harmonisation and horizontal standardisation of test procedures in particular for sludges soils and biowastes It was created as in response to the European Commission Mandate M 330 given to CEN asking for the development and validation of those standards in support of forthcoming EU Directives such as

o The revision of the Sewage Sludge Directive 86278EEC o The Directive on the biological treatment of biodegradable waste o The initiative on a legal framework for soil monitoring in Europe

This mandate explicitly considers standards for the entire analytical procedure (ie sampling pre-treatment and analytical measurement methods for inorganic organic hygiene and biological parameters) These are grouped into classes according to their physicalchemical properties which in turn determine the methods needed to quantify the potential impact on human and animal health plant uptake soil function and groundwater quality As the materials generally feature a mixture of different types of contaminants it is important to provide an integrated answer covering evaluation of all relevant pollutants In order to fulfil the requirements of the aforementioned mandate the European Commissions Joint Research Centre (JRC) and its Directorate-General for Environment (DG ENV) together with the Technical Committees of the European Standardisation Committee (CEN TCs) concerned designed a pre-normative research initiative called Project HORIZONTAL and presented it to the Commission and the Environmental Authorities in the Member States After an extensive literature research and careful evaluation of the feasibility of a given horizontal standard the standards were drafted and finally validated in an European laboratory intercomparison The underlying statistical concept information about the materials used details about the participants measurement results obtained as well as the derived performance characteristics obtained for the determination of polybrominated diphenylethers (PBDE) are described hereafter

6

11 Statistical concept underlying the validation According to the requirements of the work package concerning data handling amp interpretation of the project HORIZONTAL-ORG the respective validation intercomparisons have to be evaluated according to the principles laid down in ISO standard 5725-21994 In particular repeatability and reproducibility of the draft standard methods have to be determined The determination of trueness would require the availability of independent reference values for the materials investigated This however is not possible and was not requested in the frame of this work In the following the approach chosen is explained

111 Introduction to the statistical model The statistical model used in ISO 5725 for estimation of accuracy of a measurement method assumes that every test result is the sum of three components

eBmy ++= y test result m general mean B laboratory component of bias under repeatability conditions e random error occurring in every measurement under repeatability conditions

In the workprogram the quantification of term e is explicitly asked for (ie repeatability and reproducibility) The repeatability variance is measured directly as the variance of the error term e but the reproducibility depends on the sum of the repeatability variance and the between-laboratory variance

( )er var=σ 22rLR σσσ += with ( )BL var=σ

However soil biowaste and sludge are multi-phase materials ie they contain two or more distinct types of particles which are fundamentally different in their properties and composition As a consequence this introduces an important source of variation for the intercomparison exercise which needs to be considered ie the inherent heterogeneity of the materials Thus a contribution of variation between samples H is introduced to the general statistical model

HeBmy +++= Using ANOVA techniques the different variances are calculated and separated for the evaluation

7

112 Requirements for precision experiment

Layout of the experiment A suite of 10 to 12 different materials (soil sludge and biowaste) has been made available for the intercomparison exercise For each parameter investigated at least 10 to laboratories should be nominated to participate The same laboratories should be used for different parameters as far as possible Due to the complexity of analysis and the respective workload to the laboratories it was decided to propose three materials for the validation of the PBDE draft standard Each laboratory received two bottles of each material and was be requested to perform 4 independent analyses per material1 (2 per bottle) using the respective draft standard methods The 4 analysis per material should be carried out under repeatability conditions (ie same operator2 same equipment within a short period of time) As far as possible also the different materials should be measured under repeatability conditions however changes of eg operator or equipment are permitted but must be reported Likewise different materials can be analysed on different days if necessary Equipment used in the experiment needed to be checked prior to the experiment according to the requirements of the draft standard The results of these checks have to be documented Similarly date and time of each measurement had to be recorded for verification of repeatability conditions An appropriate timeframe for the entire exercise has been set and was to be respected

Recruitment of the laboratories Each sub-workpackage leader of HORIZONTAL was asked to select the laboratories using the information from section 52 of ISO 5725-21994 and provide the signed questionnaires (see also Annex 1) The workpackage leaders were responsible for providing the laboratories with the draft standard method and explaining the context of this exercise

Preparation and use of the materials Materials used for the exercise were prepared according to the general requirements for reference materials as laid down in ISO Guide 34 Materials were accompanied by instructions for use

Reporting of results Online submissions of results using an internet-based IT platform as well as XLS-Spreadsheets were used In case of online data submission the participating laboratories received a unique and confidential login and password in due time enabling them to

1 Independent analysis means analysis of independent test portions applying the entire analytical scheme to this test portion from eg extraction to quantification For instance it does not mean replicate injections of aliquots into a GC-MS instrument 2 Operator in this context may also consist of a fixed team of persons eg one person performing extraction one clean-up one quantification

8

enter their data in a structured form For authentication purposes a signed printout had to be submitted by mail The online data submission included a detailed questionnaire for additional information on the measurements

113 Statistical analysis Statistical analysis of data followed the requirements of ISO 5725-21994 and ISO 5725-51998 Appropriate tests for the homogeneity of variance detection of outliers and normal distribution were applied Statistical evaluation was done using an Excel Macro developed tested and successfully applied in other occasion by ECN Evaluation was executed jointly by JRC and ECN

12 Validation exercise for PBDE

121 Compounds to be measured The following compound were selected for the validation exercise Tetra-BDE-47 Penta-BDE-100 Penta-BDE-99 Hexa-BDE-154 Hexa-BDE-153 Hepta-BDE-183 Octa-BDE-196 Octa-BDE-197 Octa-BDE-203 Deca-BDE-209

122 Samples dispatched for the validation of PBDE After a preliminary rough screening the following materials were used for the validation round of PBDE

bull Compost 1 A pollutant loaded compost material from Vienna bull Sewage Sludge 1 A mixed sewage sludge from Essen bull Soil 3 A sludge amended soil from Barcelona

A more detailed description of background concentrations can be found in Annex 2 to this report The samples were dispatched simultaneously to all participants using a private courier service

123 Draft standards to be followed The draft standards to be followed could be downloaded following this link which is situated on the website of the Project HORIZONTAL httpwwwecnnldocssocietyhorizontalBFR_Standard_for_validationpdf

124 Analytical programm Of each of the three materials 2 bottles had to be analysed and each bottle had to analysed independently twice As mentioned above analyses were to be done under repeatability conditions Results were to be reported referring to DRY MATTER content The choice how to apply dm correction was free for each participant

9

125 Timing and Submission of data Dispatch of samples was done on the 18th of October 2006 For users of the Online data submission system (MILC) User Registration was possible from 14th of November 2006 with opening of the MILC Data Submission on 1st of December 2006 The deadline for submission of results has been set for PBDE to the 12th of January 2007 but was extended to the end of the same months After that no further submission was possible Alternatively the participants were allowed to submit data electronically as Excel sheet using simply Email All data were treated in a confidential way Any presentation hereafter will refer only to numerical data and it will not be possible to identify the originating laboratory Lab Codes displayed are NOT related to the order of laboratories hereafter In addition to the information provide an Helpdesk was implemented in order to give quick and individual response to the participants during and immediately after the validation study In case of doubt and suspected transcription errors further enquires were conducted by JRC

10

126 Participants The following table lists the participating organisations and entities in the validation exercise for the horizontal PBDE standard

bull Austria o Umweltbundesamt

bull Czech Republic o Povodi Labe statni podnik - OVHL Laboratory

bull France o CIRSEE o CTC Environnement o INERIS

bull Germany o Federal Environmental Agency Section III 34 Laboratory Methods for

the Surveillance of Waste and Wastewater (UBA) bull Italy

o European Commission DG JRC IES bull Spain

o Consejo Superior de Investigaciones Cientificas (CSIC)

bull Sweden o ALCONTROL AB

11

13 Summary results and derived performance characteristics The result of the various statistical evaluation including outlier tests calculation of repeatability and reproducibility standard deviation for the congeners of interest can be found in Annex 3 of this report In addition all data submitted by the participants as well as those considered for the calculation of the performance characteristics are listed in Annex 3 to this report Based on these calculations the following results were obtained in the validation round upon statistical evaluation according to ISO 5725-2 The average values the repeatability standard deviation (sr) and the reproducibility standard deviation (sR) were obtained (Table1) The repeatability is determined as an interval around a measurement result (ie repeatability limit) This interval corresponds to the maximum difference that can be expected (with a 95 statistical confidence) between one test result and another both test results being obtained under the following conditions The tests are performed in accordance with all the requirements of the present standard by the same laboratory using its own facilities and testing laboratory samples obtained from the same primary field sample and prepared under identical procedures The repeatability limit was calculated using the relationship r test = f radic2 s rtest with the critical range factor f = 2 The reproducibility like repeatability is also determined as an interval around a measurement result (ie reproducibility limit) This interval corresponds to the maximum difference that can be expected (with a 95 statistical confidence) between one test result and another test result obtained by another laboratory both test results being obtained under the following conditions The tests are performed in accordance with all the requirements of the present standard by two different laboratories using their own facilities and testing laboratory samples obtained from the same primary field sample and prepared under identical procedures The reproducibility limit was calculated using the relationship R = f radic2 sR with the critical range factor f = 2

12

Table 1 - Results of the interlaboratory comparison studies of the determination of selected polybrominated diphenyl ethers (PBDE) by gaschromatography with mass spectrometric detection (GC-MS) in soil sludge and treated biowaste All concentrations are expressed in mgkg dm

Matrix Parameter Mean sr sR r R p Outliers Used No of data

No of data reported below

detection

Total no of data

Sludge 1 PBD 47 00181 461 4 15 5 20 Compost 1 00039 94 3 12 0 12 Soil 3 00010 50 50 00014 00014 4 0 13 10 23 Sludge 1 PBD 99 00239 64 28 00043 00186 5 1 19 0 23 Compost 1 00029 31 35 00025 00028 5 0 17 4 21 Soil 3 00013 499 4 16 8 24 Sludge 1 PBD 100 00049 51 17 00007 00024 5 1 18 2 24 Compost 1 00009 25 29 00006 00007 4 0 14 7 21 Soil 3 61103 211 3 10 15 25 Sludge 1 PBD 153 00038 33 38 00034 0004 5 0 18 0 18 Compost 1 00019 116 3 11 3 14 Soil 3 00011 177 2 10 10 20 Sludge 1 PBD 154 00023 234 4 15 2 17 Compost 1 00008 1118 3 9 5 14

13

Matrix Parameter Mean sr sR r R p Outliers Used No of data

No of data reported below

detection

Total no of data

Soil 3 00002 1049 4 13 6 19 Sludge 1 PBD 183 00048 1217 3 12 2 14 Compost 1 00009 1048 2 8 5 13 Soil 3 00011 1395 3 12 6 18 Sludge 1 PBD 196 00037 470 2 8 7 15 Compost 1 00004 950 2 6 4 10 Soil 3 00023 519 3 12 2 14 Sludge 1 PBD 197 00062 834 2 6 8 14 Compost 1 00009 1001 2 7 7 14 Soil 3 00032 904 2 8 6 14 Sludge 1 PBD 203 00037 461 2 8 4 12 Compost 1 00004 978 2 5 3 8 Soil 3 00022 598 3 12 0 12 Sludge 1 PBD 209 02493 170 39 01186 02689 5 0 16 2 18 Compost 1 00273 104 3 10 5 15 Soil 3 02582 1115 51 00806 03676 6 0 22 0 22

14

Matrix Parameter Mean sr sR r R p Outliers Used No of data

No of data reported below

detection

Total no of data

Sludge 1 Sum PBD 0256 155 548 0111 0392 6 1 22 Compost 1 0009 331 637 0008 0016 5 1 18 Soil 3 0227 116 717 0074 0455 7 1 26 Abbreviations sr Repeatability standard deviation SR Reproducibility standard deviation r Repeatability limit (comparing two measurements) R Reproducibility limit (comparing two measurements) p Number of labs determination not possible

15

14 Annexes Annex 1 Model questionnaire to be filled by the participating laboratories Annex 3 Report on the validation materials used Annex 2 Statistical calculations Annex 3 Data submitted

16

Annex 1

Model questionnaire to be filled by the participating laboratories

Model questionnaire to be filled by the participating laboratories Name of laboratory Contact person Contact details email Phone Fax Mail address of lab Dispatch address of lab for shipment of samples (no PO boxes) Title of measurement method (copy attached) Our laboratory is willing to participate in the precision experiment for this draft standard method

Yes No As participant we understand that

bull All essential apparatus chemicals and other requirements specified in the method must be available in our laboratory when the programme begins

bull Specified timing requirements such as starting and finishing date of the programme must be rigidly met

bull The method must be strictly adhered to bull Samples must be handled in accordance with instructions bull A qualified operator must perform the measurements

Having studied the method and having made a fair appraisal of our capabilities and facilities we feel that we will be adequately prepared for cooperative testing of this method Comments helliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphellip Signature Date

17

Annex 2

Report on the validation materials used

VI

Abstract This report gives an overview on the available analytical information on the following raw materials to be used for the production of validation materials of the so-called Project HORIZONTAL

bull Four sludge materials from Duumlsseldorf Germany

bull An agricultural soil material from Reading United Kingdom

bull A compost material from Vienna Austria

bull A compost material from Korschenbroich Germany

bull A sludge-amended agricultural soil from Pavia Province Italy

bull A sludge-amended soil from Barcelona Spain

bull A sludge-amended soil from Essen Germany

bull A long-term sludge exposed soil from Hohenheim Germany

VII

List of Abbreviations Throughout this report the following abbreviations are used

AOX absorbable organic halogens

Corg organic carbon content

Ctotal total carbon content

CAT cation exchangeable

CDD chlorinated dibenzodioxin

CDF chlorinated dibenzofuran

DEHP di(2-ethylhexyl)phthalate

DM dry matter

EPA Environment Protection Agency

EU European Union

FM fresh matter

Hp hepta

Hx hexa

IES Institute for Environment and Sustainability

IRMM Institute for Reference Materials and Measurements

JRC Joint Research Centre

LAS linear alkylsulfonates

LoD limit of detection

LUA Landesumweltamt

Ntotal total nitrogen content

NH4-N Ammonium nitrogen

NO3-N Nitrate nitrogen

NP nonylphenol

NRW North Rhine Westphalia

O octa

P poly

PAH polycyclic aromatic hydrocarbon

PCB polychlorinated biphenyl

Pe penta

T tetra

TEQ toxicity equivalent

UBA Umweltbundesamt

WHO World Health Organization

WWTP waste water treatment plant

6

1 Introduction This report gives an overview on the available analytical information on the following raw materials to be used for the production of validation materials of the so-called Project HORIZONTAL

bull Four sludge materials from Duumlsseldorf Germany

bull An agricultural soil material from Reading United Kingdom

bull A compost material from Vienna Austria

bull A compost material from Korschenbroich Germany

bull A sludge-amended agricultural soil from Pavia Province Italy

bull A sludge-amended soil from Barcelona Spain

bull A sludge-amended soil from Essen Germany

bull A long-term sludge exposed soil from Hohenheim Germany

The following analytical information was gathered partly before and during the sampling of the raw materials to be used for the production of the HORIZONTAL validation materials The material were sampled by IES and shipped to IRMM in the course of the year 2005 The information gathered was then completed by various analytical screenings for PAHs and PCBs done by the Institute for Reference Materials and Measurements Geel Belgium for phthalates done by UBA Berlin Germany for PBDE done by IIQAB-CSIC Barcelona Spain for trace elements and some selected major and minor elements by the Institute for Environment and Sustainability Ispra Italy

The work compiled hereafter is based on the numerous additional efforts of the scientists working at various members of the consortium Project HORIZONTAL-Org and contributing organisations

This work is gratefully acknowledged

2 Overview on property values

21 Sludge materials from Duumlsseldorf Germany

The various sewage sludge materials originate from various installations in the North Rhine Westphalia and were produced and sampled by staff from the Landesumweltamt (LUA) NRW under the responsibility from Dr K Furtmann

In total four sludge materials (Sludge A and D from a major municipal WWTP Sludge B from a municipal WWTP with industrial input and Sludge C from a municipal WWTP with high PCB-Content) were obtained and will be blended to two final materials Before sampling the following analytical data for a typical sample were received

7

Table 1 ndash Analytical data obtained on an average sludge sample in LUA NRW (with courtesy of K Furtmann LUA Duumlsseldorf)

Parameter Concentration PCB 120 ugkg DEHP 110 mgkg PAH 5 mgkg (EPA) PCDDF 15 ng TEkg PBDE 400 ugkg NP 40 mgkg LAS 3 gkg AOX 300 mgkg

Subsequent screening led to the information displayed hereafter It should be stressed that the data were obtained as SCREENING information on the UNTREATED or partially treated raw materials Therefore the final target values which are relevant for the validation intercomparison can be different

Table 2 ndash Analytical data obtained on a first screening on the sludge samples from LUA NRW

Sewage sludge A

Dusseldorf

sewage sludge D

Dusseldorf PCB (ngg) 28 62 35 52 101 65 101 31 38 118 49 40 153 30 33 105 24 11 138 46 38 156 lt1 lt1 180 34 23 170 23 19 PAH (ngg) Naphtalene 34 381 Acenaphtylene 15 43 Acenaphthene 81 108 Fluorene 94 1167 Phenantrene 3440 Anthracene 22 344 Flouranthene 316 4817 Pyrene 235 3011 Benz(a)anthracene 473 791 Chrysene 691 1078 Benz(b)fluoranthene 538 1688 Benz(k)fluoranthene 228 635 Benz(a)pyrene 383 1114 Indeno(123-cd)pyrene 92 229 Dibenzo(ah)anthracene 71 70 Benzo(ghi)perylene 80 185

8

Table 3 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Sludge D (1) 0135 41474 385 Sludge B (2) 0538 0034 30634 547 Sludge A (3) 0184 0037 31399 146 Sludge C (4) 0354 1528 6678 229

Table 4 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Sludge 2

(B)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

554

959

694

591

772

509

nq

nq

970

2216

2379

Table 5 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena IES Ispra Spain) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Sludge 1 (D) 265 290 533 359 1231 338 784 438 lt 005 232 786 Sludge 2 (B) 119 311 626 202 278 299 722 251 lt 005 118 625 Sludge 3 (A) 168 360 621 332 847 416 119 451 lt 005 116 1237 Sludge 4 (C) 563 198 116 273 726 511 473 618 lt 005 444 2015

Table 6 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Sludge 1 (D) 2154 58 844 099 103 101 4367 lt15 50448 Sludge 2 (B) 1067 366 692 046 1491 077 5217 lt15 57633 Sludge 3 (A) 731 663 684 035 1287 068 3733 lt15 60369 Sludge 4 (C) 4379 965 527 163 522 107 5628 lt15 23945

Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM)Sludge 1 (D) 03 2403 101 1002 350 15 1944 132Sludge 2 (B) 031 315 97 879 172 12 514 180Sludge 3 (A) 031 1281 153 1567 265 16 1440 168Sludge 4 (C) 055 231 628 2625 371 81 1101 244

9

22 Agricultural soil material from Reading United Kingdom

The material was proposed by the University of Reading (S Nortcliff) and was sampled from a site called ldquoFrogmore Farmrdquo which was featured in the ldquoMetalsrdquo Report for HORIZONTAL This site is close to Reading with soils developed on flintyloamy periglacial materials over Chalk has a long and well documented history of sludge application The focus of the work of Nortcliff et al undertook at this site and the monitoring and control at the site (by Thames Water and the subsequent subsidiary bodies dealing with sludge application to soil) was on metals (and metal loads) with no analysis or indeed any form of investigation in to organics in the broadest sense

The analytical information produced in the context of the screening of the raw material is displayed below

Table 7 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 3

(Reading) 0032 0119 669

Table 8 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 3 (Reading) 015 706 279 138 152 901 267 300 lt 005 258 931

Table 9 ndash Analytical data obtained on a first screening on the sludge-amended soil from Reading (courtesy of IRMM)

Parameter Concentration

PCB ngg 28 lt1 52 lt1 101 lt1 118 lt1 153 lt1 105 lt1 138 lt1 156 lt1 180 lt1 170 lt1 PAH ngg Naphtalene lt10 Acenaphtylene 21 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene lt10 Flouranthene 818 Pyrene 776 Benz(a)anthracene 565

10

Parameter Concentration

Chrysene 608 Benz(b)fluoranthene 824 Benz(k)fluoranthene 329 Benz(a)pyrene 799 Indeno(123-cd)pyrene

779

Dibenzo(ah)anthracene 118 Benzo(ghi)perylene 394

Table 10 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 3

(Reading)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

103

003

nq

nq

nq

nd

nd

272

273

Table 11 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 3 (Reading) 015 706 279 138 152 901 267 300 lt 005 258 931

Table 12 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 3 (Reading) 7936 477 112 096 194 017 4107 443 2102 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 3 (Reading) 042 13 45 69 69 69 216 92

Table 13 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 3 (Reading) 012

11

23 Compost from Vienna Austria

The fresh compost material was obtained from the Austrian Federal Environment Agency (UBA Vienna) which had used a sub-batch of the raw material for national intercomparson The remainder of the material was stored at 4degC until shipment to IRMM for further processing The following analytical information was provided by UBA Austria and completed with various screenings

Table 14 ndash Analytical data on compost material received from UBA Austria Inorganic and sum parameters

Parameter Unit Sample fraction used Observed mean B CAT mgl FM Fresh sample lt10mm 61 K CAT mgl FM Fresh sample lt10mm 2624 Mg CAT mgl FM Fresh sample lt10mm 242 P CAT mgl FM Fresh sample lt10mm 49 B CAT DM Fresh sample lt10mm 00017 K CAT DM Fresh sample lt10mm 072 Mg CAT DM Fresh sample lt10mm 007 P CAT DM Fresh sample lt10mm 001 NO3-N mgkg FM Fresh sample lt10mm 35 NH4-N mgkg FM Fresh sample lt10mm 230 Ctotal DM lt45degdry milled 29 Corg DM lt45degdry milled 27 Ntotal DM lt45degdry milled 17 P mgkg DM lt45degdry milled 2596 K mgkg DM lt45degdry milled 11019 K DM lt45degdry milled 110 B mgkg DM lt45degdry milled 60 Cd mgkg DM lt45degdry milled 046 Cr mgkg DM lt45degdry milled 25 Cu mgkg DM lt45degdry milled 46 Hg mgkg DM lt45degdry milled 020 Ni mgkg DM lt45degdry milled 18 Pb mgkg DM lt45degdry milled 45 Zn mgkg DM lt45degdry milled 198 Ca mgkg DM lt45degdry milled 68776 Ca DM lt45degdry milled 69 Mo mgkg DM lt45degdry milled 08 S mgkg DM lt45degdry milled 2137 Fe mgkg DM lt45degdry milled 9959 Mn mgkg DM lt45degdry milled 418 Na mgkg DM lt45degdry milled 742 Co mgkg DM lt45degdry milled 41 AOX mgkg DM lt30deg dry milled 62

Table 15 ndash Analytical data on compost material received from UBA Austria Polycyclic aromatic hydrocarbons

PAH Unit Result Naphthaline microgkg DM 93 Acenaphthylene microgkg DM 86 Acenaphthene microgkg DM 5 Fluorene microgkg DM 80 Phenanthrene microgkg DM 89 Anthracene microgkg DM 27 Fluoranthene microgkg DM 487 Pyrene microgkg DM 380

12

PAH Unit Result Benzo(a)anthracene microgkg DM 278 Chrysene microgkg DM 317 Benzo(b)fluoranthene microgkg DM 365 Benzo(k)fluoranthene microgkg DM 193 Benz(a)pyrene microgkg DM 320 Indeno(123-cd)pyrene microgkg DM 233 Dibenz(ah)anthracene microgkg DM 67 Benzo(ghi)perylene microgkg DM 225 Sum EPA microgkg DM 3013 Sum EPA mgkg DM 30

Table 16 ndash Analytical data on compost material received from UBA Austria Sum PCDDs and PCBs

Parameter

Dioxine TEQ (ITEF) ngkg DM 73 TEQ (WHO) ngkg DM 35 PCB Σ Ballschmiter mgkg DM 005

Table 17 ndash Analytical data on compost material obtained by screening in IRMM

Parameter Result in ngg

PCB 28 2 52 2 101 4 118 3 153 10 105 1 138 8 156 1 180 5 170 lt1 PAH Naphtalene lt10 Acenaphtylene lt10 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene 26 Fluoranthene 611 Pyrene 510 Benz(a)anthracene 888 Chrysene 957 Benz(b)fluoranthene 1531 Benz(k)fluoranthene 547 Benz(a)pyrene 1101 Indeno(123-cd)pyrene 416 Dibenzo(ah)anthracene 81 Benzo(ghi)perylene 295

13

Table 18 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Compost 1

(Vienna)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

402

019

259

nq

023

004

nq

nq

144

174

259

Table 19 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Compost 1

(Vienna) 0058 1426 557

Table 20 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Compost 1 (Vienna) 039 736 319 410 365 127 495 004 079 013 208

Table 21 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Compost 1 (Vienna) 2063 431 617 426 199 249 1602 lt15 10521

Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Compost 1 (Vienna) 035 3496 81 375 79 55 653 60

Table 22 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Compost 1 (Vienna) 017

14

24 Agricultural soil sludge amended soil from Pavia Italy

This sludge-amended soil material was obtained during a monitoring campaign which aimed at a generic description of the over-all soil quality in Pavia Province Italy The material which was collected from the upper horizon originates from a small farm called ldquoCascina Novellordquo During the characterisation of the site the following analytical information was obtained on a pooled sample of a sub-area of the farm of 20 X 20 m2

Table 23 ndash Analytical data on Pavia soil

Parameter Result Al 713 Wgt As 224 mgkg Cd 079 mgkg Cr 59 mgkg Cu 308 mgkg Hg 008 mgkg Ni 344 mgkg Pb 246 mgkg Zn 95 mgkg C 091 Wgt 2378-TCDD 0047 pgg 12378-PeCDD 015 pgg 123478-HxCDD 019 pgg 123678-HxCDD 15 pgg 123789-HxCDD 074 pgg 1234678-HpCDD 26 pgg OCDD 382 pgg 2378-TCDF 068 pgg 12378-PeCDF 053 pgg 23478-PeCDF 071 pgg 123478-HxDF 100 pgg 123678-HxDF 066 pgg 234678-HxDF 16 pgg 123789-HxDF 027 pgg 1234678-HpDF 12 pgg 1234789-HpDF 068 pgg OCDF 33 pgg I-TEQ 20 pgg WHO-TEQ 17 pgg

In addition the screening performed at IRMM did not reveal significant quantities of PCBs and PAHs which were all below the LoDs (1 ngg for PCBs and 10 ngg for PAHs respectively)

Table 24 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 5 (Pavia) 0005 0011 154

15

Table 25 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 5

(Pavia)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

039

nq

nq

008

nq

nd

nd

670

671

Table 26 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 5 (Pavia) 033 184 573 225 426 305 206 200 lt 005 381 878

Table 27 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 5 (Pavia) 6939 129 145 224 425 116 6118 255 1789 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 5 (Pavia) 184 62 38 108 55 66 597 110

Table 28 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 5 (Pavia) 006

16

25 Sludge-amended-soil from Barcelona Spain

The sludge-amended soil material from Barcelona sampled upon indication from the Barcelorsquo- Group in Barcelona

Table 29 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 2 (Lleida T) 0015 0183 1138

Table 30 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 2

(Lleida T)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

159

045

nq

048

160

nq

nq

1000

1004

Table 31 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 2 (Lleida T) 059 141 327 536 405 186 184 224 lt 005 318 111

Table 32 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 2 (Lleida T) 4443 1067 1429 253 344 204 4116 780 3396 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 2 (Lleida T) 064 65 26 125 59 17 547 65

Table 33 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 2 (Lleida T) 010

17

26 Sludge amended soil from Essen Germany

The German sludge-amended soil from Essen which was provided as the three sludge materials by LUA NRW did not feature significant concentrations of the PCB congeners 28 52 101 118 153 105 138 156 180 170 but had detectable amounts of some PAHs

Table 34 ndash Analytical screening data on the German sludge-amended soil

Parameter Concentration(ngg)

Naphtalene lt10 Acenaphtylene lt10 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene lt10 Fluoranthene 28 Pyrene 20 Benz(a)anthracene 24 Chrysene 47 Benz(b)fluoranthene 76 Benz(k)fluoranthene 20 Benz(a)pyrene 35 Indeno(123-cd)pyrene 35 Dibenzo(ah)anthracene 10 Benzo(ghi)perylene 26

Table 35 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 4 (Essen) 0011 0302 055

Table 36 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 4

(Essen)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

nq

nq

nq

nq

nq

nq

128

191

203

18

Table 37 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 4 (Essen) 052 545 261 805 320 403 273 273 lt 005 295 781

Table 38 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 4 (Essen) 7947 442 085 06 086 007 2163 189 2019 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 4 (Essen) 045 19 42 87 683 60 462 61

Table 39 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 4 (Essen) 004

27 Long-term sludge exposed soil from Hohenheim-Stuttgart Germany

Similarly an additional sludge exposed soil was sampled at the University of Hohenheim Stuttgart were a test soil was long-term exposed to elevated concentrations of sewage sludge

Table 40 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 1 (Stuttgart) 0045 0263 1765

Table 41 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 1

(Stuttgart)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

230

006

004

004

nq

nd

nd

498

500

19

Table 42 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 1 (Stuttgart) 069 127 361 262 504 183 252 262 lt 005 266 142

Table 43 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 1 (Stuttgart) 7194 1006 133 186 366 088 7874 275 3571 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 1 (Stuttgart) 123 50 47 212 85 69 991 129

Table 44 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 1 (Stuttgart) 177

18

Annex 3

Statistical calculations

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 47)Mandels h statistics(Sludge 1 - PBD 47)

Sample Sludge 1 NUM

Element PBD 47

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00213 0001 3 -021 005 - - 10L - - NUM46L 00273 0002 4 016 021 - - 46L - - NUM64L 00059 0000 4 -116 002 NUM - 64L - - NUM12L 00188 0000 4 -036 002 - - 12L - - NUM26L 00499 0024 2 157 223 Fail - - 26L - - NUM

Totgem 0025 0005 mgkg 1-level 172 (185) NUM (10L46L64L12L26L) -1Totstd= 0016 0010 5-level 157 (162) 5

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 5 Labs rejected (10L46L64L12L26L)

000 050 100 150 200 250

k-values

10L

46L

64L

12L

26L

Mandels k statistics(Sludge 1 - PBD 47)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

10L

46L

64L

12L

26L

Labo

rato

ries

NUM

-200 -100 000 100 200

h-values

10L

46L

64L

12L

26L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 47)

Sludge 1-PBD 47

Unit mgkg

Mandels k statistics(Soil 3 - PBD 47)Mandels h statistics(Soil 3 - PBD 47)

Sample Soil 3 Soil 3 - PBD 47 -- Mean PARM = 0001 [mgkg]

Element PBD 47

General calcparmT1= 134814E-02T2= 142830E-05T3= 13T4= 45T5= 22767E-06

n= variabelp= 4

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean26L 00007 0000 2 -143 001 00007 00000 2 1 00046L 00010 0001 4 010 181 00010 00008 4 3 00010L 00011 0000 3 049 023 00011 00001 3 2 00012L 00012 0000 4 084 081 00012 00004 4 3 000

Totgem 0001 0000 mgkg 1-level 149 (177) 4 00010 () 4 3Totstd= 0000 0000 5-level 142 (159)

RESULTS Mean = 000100 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000050 --gt 5031 r = 00014Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000050 --gt 5031 R = 00014Remarks none

000 050 100 150 200

k-values

26L

46L

10L

12L

Mandels k statistics(Soil 3 - PBD 47)

00 00 00 00 00 00 00 00 00 00 00

Deviation from Mean

26L

46L

10L

12L

Labo

rato

ries

Soil 3 - PBD 47 -- Mean PARM = 0001 [mgkg]

-200 -100 000 100

h-values

26L

46L

10L

12L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 47)

Soil 3-PBD 47

Unit mgkg

Mandels k statistics(Compost 1 - PBD 99)Mandels h statistics(Compost 1 - PBD 99)

Sample Compost 1 Compost 1 - PBD 99 -- Mean PARM = 0003 [mgkg]

Element PBD 99

General calcparmT1= 492124E-02T2= 148747E-04T3= 17T4= 61T5= 93196E-06

n= variabelp= 5

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00020 0000 4 -137 053 00020 00004 4 3 000

26L 00025 0000 2 -058 024 00025 00002 2 1 00010L 00029 0000 3 012 032 00029 00003 3 2 00046L 00033 0001 4 069 161 00033 00013 4 3 00012L 00036 0001 4 114 140 00036 00011 4 3 000

Totgem 0003 0001 mgkg 1-level 172 (185) 5 00029 () 5 4Totstd= 0001 0001 5-level 157 (162)

RESULTS Mean = 000286 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000088 --gt 3086 r = 00025Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000101 --gt 3525 R = 00028Remarks none

000 050 100 150 200

k-values

4L

26L

10L

46L

12L

Mandels k statistics(Compost 1 - PBD 99)

00 00 00 00 00 00 00 00 00 00

Deviation from Mean

4L

26L

10L

46L

12L

Labo

rato

ries

Compost 1 - PBD 99 -- Mean PARM = 0003 [mgkg]

-200 -100 000 100 200

h-values

4L

26L

10L

46L

12L

Labo

rato

ries

Mandels h statistics(Compost 1 - PBD 99)

Compost 1-PBD 99

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 99)Mandels h statistics(Sludge 1 - PBD 99)

Sample Sludge 1 Sludge 1 - PBD 99 -- Mean PARM = 0024 [mgkg]

Element PBD 99

General calcparmT1= 448050E-01T2= 112113E-02T3= 19T4= 73T5= 32972E-05

n= variabelp= 5

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean64L 00173 0002 4 -118 041 Fail 00173 00019 4 3 -0014L 00183 0002 4 -104 032 00183 00015 4 3 -001

12L 00227 0001 4 -038 022 00227 00010 4 3 00010L 00290 0001 3 055 021 00290 00010 3 2 00146L 00320 0002 4 100 039 00320 00018 4 3 00126L 00323 0011 2 105 234 - - 26L - - 001

Totgem 0025 0003 mgkg 1-level 187 (177) 5 00239 (26L) 5 4Totstd= 0007 0004 5-level 166 (154) 1

RESULTS Mean = 002385 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000153 --gt 643 r = 00043Between lab variance S2L = 000004Reproducibility var S2R = 000004Reproducibility std SR = 000666 --gt 2791 R = 00186Remarks 1 Lab rejected (26L)

000 050 100 150 200 250

k-values

64L

4L

12L

10L

46L

26L

Mandels k statistics(Sludge 1 - PBD 99)

00 00 00 00 00 00 00 00 00 00

Deviation from Mean

64L

4L

12L

10L

46L

26L

Labo

rato

ries

Sludge 1 - PBD 99 -- Mean PARM = 0024 [mgkg]

-200 -100 000 100 200

h-values

64L

4L

12L

10L

46L

26L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 99)

Sludge 1-PBD 99

Unit mgkg

Mandels k statistics(Soil 3 - PBD 99)Mandels h statistics(Soil 3 - PBD 99)

Sample Soil 3 NUM

Element PBD 99

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00017 0000 4 091 068 - - 10L - - NUM46L 00017 0001 4 100 211 - - 46L - - NUM64L 00005 0000 4 -106 023 NUM - 64L - - NUM12L 00012 0000 4 015 014 - - 12L - - NUM26L 00006 0000 2 -101 012 - - 26L - - NUM

Totgem 0001 0000 mgkg 1-level 172 (173) NUM (10L46L64L12L26L) -1Totstd= 0001 0000 5-level 157 (153) 5

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 5 Labs rejected (10L46L64L12L26L)

000 050 100 150 200 250

k-values

10L

46L

64L

12L

26L

Mandels k statistics(Soil 3 - PBD 99)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

10L

46L

64L

12L

26L

Labo

rato

ries

NUM

-200 -100 000 100 200

h-values

10L

46L

64L

12L

26L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 99)

Soil 3-PBD 99

Unit mgkg

Mandels k statistics(Compost 1 - PBD 100)Mandels h statistics(Compost 1 - PBD 100)

Sample Compost 1 Compost 1 - PBD 100 -- Mean PARM = 0001 [mgkg]

Element PBD 100

General calcparmT1= 124272E-02T2= 113129E-05T3= 14T4= 52T5= 46584E-07

n= variabelp= 4

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean26L 00006 0000 2 -131 037 Fail 00006 00001 2 1 00010L 00009 0000 4 003 083 00009 00002 4 3 00046L 00009 0000 4 016 115 00009 00002 4 3 00012L 00011 0000 4 112 136 Fail 00011 00003 4 3 000

Totgem 0001 0000 mgkg 1-level 149 (167) 4 00009 () 4 3Totstd= 0000 0000 5-level 142 (15)

RESULTS Mean = 000085 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000022 --gt 2531 r = 00006Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000025 --gt 2882 R = 00007Remarks none

000 050 100 150

k-values

26L

10L

46L

12L

Mandels k statistics(Compost 1 - PBD 100)

00 00 00 00 00 00 00 00 00 00 00

Deviation from Mean

26L

10L

46L

12L

Labo

rato

ries

Compost 1 - PBD 100 -- Mean PARM = 0001 [mgkg]

-200 -100 000 100 200

h-values

26L

10L

46L

12L

Labo

rato

ries

Mandels h statistics(Compost 1 - PBD 100)

Compost 1-PBD 100

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 100)Mandels h statistics(Sludge 1 - PBD 100)

Sample Sludge 1 Sludge 1 - PBD 100 -- Mean PARM = 0005 [mgkg]

Element PBD 100

General calcparmT1= 852065E-02T2= 412762E-04T3= 18T4= 68T5= 78914E-07

n= variabelp= 5

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00039 0000 4 -042 007 Fail 00039 00002 4 3 000

12L 00044 0000 4 -041 005 Fail 00044 00001 4 3 00010L 00046 0000 4 -041 013 Fail 00046 00003 4 3 00046L 00056 0000 4 -040 012 Fail 00056 00003 4 3 00026L 00059 0000 2 -040 013 Fail 00059 00003 2 1 00038L 02168 0006 4 204 244 Fail - - 38L - - 021

Totgem 0040 0001 mgkg 1-level 187 (177) 5 00049 (38L) 5 4Totstd= 0087 0002 5-level 166 (154) 1

RESULTS Mean = 000486 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000025 --gt 507 r = 00007Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000084 --gt 1731 R = 00024Remarks 1 Lab rejected (38L)

000 050 100 150 200 250

k-values

4L

12L

10L

46L

26L

38L

Mandels k statistics(Sludge 1 - PBD 100)

-01 00 01 01 02 02 03

Deviation from Mean

4L

12L

10L

46L

26L

38L

Labo

rato

ries

Sludge 1 - PBD 100 -- Mean PARM = 0005 [mgkg]

-100 000 100 200 300

h-values

4L

12L

10L

46L

26L

38L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 100)

Sludge 1-PBD 100

Unit mgkg

Mandels k statistics(Soil 3 - PBD 100)Mandels h statistics(Soil 3 - PBD 100)

Sample Soil 3 NUM

Element PBD 100

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00003 0000 4 -050 000 Fail - - 10L - - NUM46L 00003 0000 4 -050 000 Fail NUM - 46L - - NUM3L 305500 2051 2 150 200 Fail - - 3L - - NUM

26L 00005 0000 2 -050 000 Fail - - 26L - - NUM

Totgem 7638 0513 mgkg 1-level 149 (177) NUM (10L46L3L26L) -1Totstd= 15275 1025 5-level 142 (159) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (10L46L3L26L)

000 050 100 150 200

k-values

10L

46L

3L

26L

Mandels k statistics(Soil 3 - PBD 100)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

10L

46L

3L

26L

Labo

rato

ries

NUM

-100 000 100 200

h-values

10L

46L

3L

26L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 100)

Soil 3-PBD 100

Unit mgkg

Mandels k statistics(Compost 1 - PBD 153)Mandels h statistics(Compost 1 - PBD 153)

Sample Compost 1 NUM

Element PBD 153

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean44L 00053 0001 3 150 157 Fail - - 44L - - NUM46L 00007 0000 4 -044 111 Fail - - 46L - - NUM12L 00005 0000 4 -051 055 Fail - - 12L - - NUM26L 00005 0000 2 -054 001 Fail NUM - 26L - - NUM

Totgem 0002 0000 mgkg 1-level 149 (177) NUM (44L46L12L26L) -1Totstd= 0002 0000 5-level 142 (159) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (44L46L12L26L)

000 050 100 150 200

k-values

44L

46L

12L

26L

Mandels k statistics(Compost 1 - PBD 153)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

44L

46L

12L

26L

Labo

rato

ries

NUM

-100 000 100 200

h-values

44L

46L

12L

26L

Labo

rato

ries

Mandels h statistics(Compost 1 - PBD 153)

Compost 1-PBD 153

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 153)Mandels h statistics(Sludge 1 - PBD 153)

Sample Sludge 1 Sludge 1 - PBD 153 -- Mean PARM = 0004 [mgkg]

Element PBD 153

General calcparmT1= 676738E-02T2= 267609E-04T3= 18T4= 68T5= 19626E-05

n= variabelp= 5

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00024 0000 4 -157 017 00024 00002 4 3 000

12L 00038 0002 4 006 154 00038 00018 4 3 00046L 00039 0000 4 011 026 00039 00003 4 3 00026L 00039 0000 2 018 004 00039 00000 2 1 00064L 00049 0002 4 122 159 00049 00018 4 3 000

Totgem 0004 0001 mgkg 1-level 172 (173) 5 00038 () 5 4Totstd= 0001 0001 5-level 157 (153)

RESULTS Mean = 000378 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000123 --gt 3252 r = 00034Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000142 --gt 3754 R = 00040Remarks none

000 050 100 150 200

k-values

4L

12L

46L

26L

64L

Mandels k statistics(Sludge 1 - PBD 153)

00 00 00 00 00 00 00

Deviation from Mean

4L

12L

46L

26L

64L

Labo

rato

ries

Sludge 1 - PBD 153 -- Mean PARM = 0004 [mgkg]

-200 -100 000 100 200

h-values

4L

12L

46L

26L

64L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 153)

Sludge 1-PBD 153

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 154)Mandels h statistics(Sludge 1 - PBD 154)

Sample Sludge 1 NA

Element PBD 154

General calcparmT1= NAT2= NAT3=T4=T5=

n= variabelp=

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00021 0000 3 -100 021 NA - 4L - - NA

46L 00025 0000 4 115 018 NA - 46L - - NA64L 00021 0001 4 -066 179 - - 64L - - NA12L 00023 0000 4 050 085 - - 12L - - NA

Totgem 0002 0000 mgkg 1-level 149 (167) NA (4L46L64L12L) -1Totstd= 0000 0000 5-level 142 (15) 4

RESULTS Mean = NA mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NAReproducibility var S2R = NAReproducibility std SR = NA --gt NA R = NARemarks 4 Labs rejected (4L46L64L12L)

000 050 100 150 200

k-values

4L

46L

64L

12L

Mandels k statistics(Sludge 1 - PBD 154)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

4L

46L

64L

12L

Labo

rato

ries

NA

-100 000 100 200

h-values

4L

46L

64L

12L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 154)

Sludge 1-PBD 154

Unit mgkg

Mandels k statistics(Soil 3 - PBD 154)Mandels h statistics(Soil 3 - PBD 154)

Sample Soil 3 NUM

Element PBD 154

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

4L 00010 - 1 150 Fail - - 4L - - NUM46L 00001 0000 4 -053 096 Fail - - 46L - - NUM64L 00001 0000 4 -056 105 Fail NUM - 64L - - NUM12L 00002 0000 4 -040 099 Fail - - 12L - - NUM

Totgem 000037 0000 mgkg 1-level 149 (164) NUM (4L46L64L12L) -1Totstd= 000042 0000 5-level 142 (153) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (4L46L64L12L)

000 050 100 150

k-values

4L

46L

64L

12L

Mandels k statistics(Soil 3 - PBD 154)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

4L

46L

64L

12L

Labo

rato

ries

NUM

-100 000 100 200

h-values

4L

46L

64L

12L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 154)

Soil 3-PBD 154

Unit mgkg

Mandels k statistics(Compost 1 - PBD 209)Mandels h statistics(Compost 1 - PBD 209)

Sample Compost 1 NUM

Element PBD 209

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00065 0003 2 -049 032 - - 4L - - NUM

44L 00573 0021 4 150 197 Fail - - 44L - - NUM12L 00078 0001 4 -045 011 - - 12L - - NUM26L 00049 0000 2 -056 000 NUM - 26L - - NUM

Totgem 0019 0006 mgkg 1-level 149 (177) NUM (4L44L12L26L) -1Totstd= 0025 0010 5-level 142 (159) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (4L44L12L26L)

000 050 100 150 200

k-values

4L

44L

12L

26L

Mandels k statistics(Compost 1 - PBD 209)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

4L

44L

12L

26L

Labo

rato

ries

NUM

-100 000 100 200

h-values

4L

44L

12L

26L

Labo

rato

ries

Mandels h statistics(Compost 1 - PBD 209)

Compost 1-PBD 209

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 209)Mandels h statistics(Sludge 1 - PBD 209)

Sample Sludge 1 Sludge 1 - PBD 209 -- Mean PARM = 0249 [mgkg]

Element PBD 209

General calcparmT1= 394542E+00T2= 107296E+00T3= 16T4= 56T5= 19723E-02

n= variabelp= 5

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 01550 0055 4 -112 148 Fail 01550 00551 4 3 -009

46L 02050 0007 2 -053 019 02050 00071 2 1 -00412L 02137 0058 4 -042 155 02137 00576 4 3 -00426L 03149 0021 2 078 057 Fail 03149 00210 2 1 00764L 03577 0007 4 129 020 Fail 03577 00074 4 3 011

Totgem 0249 0030 mgkg 1-level 172 (185) 5 02493 () 5 4Totstd= 0084 0025 5-level 157 (162)

RESULTS Mean = 024926 mgkg

Repeatability variance S2r = 000179Repeatability std Sr = 004234 --gt 1699 r = 01186Between lab variance S2L = 000743Reproducibility var S2R = 000922Reproducibility std SR = 009604 --gt 3853 R = 02689Remarks none

000 050 100 150 200

k-values

4L

46L

12L

26L

64L

Mandels k statistics(Sludge 1 - PBD 209)

-01 -01 00 01 01 02

Deviation from Mean

4L

46L

12L

26L

64L

Labo

rato

ries

Sludge 1 - PBD 209 -- Mean PARM = 0249 [mgkg]

-200 -100 000 100 200

h-values

4L

46L

12L

26L

64L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 209)

Sludge 1-PBD 209

Unit mgkg

Mandels k statistics(Soil 3 - PBD 209)Mandels h statistics(Soil 3 - PBD 209)

Sample Soil 3 Soil 3 - PBD 209 -- Mean PARM = 0258 [mgkg]

Element PBD 209

General calcparmT1= 596398E+00T2= 191917E+00T3= 22T4= 84T5= 13249E-02

n= variabelp= 6

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean26L 01162 0021 2 -108 074 Fail 01162 00207 2 1 -0144L 01303 0031 4 -097 111 Fail 01303 00312 4 3 -013

46L 01975 0036 4 -046 128 Fail 01975 00359 4 3 -00644L 02898 0035 4 024 124 Fail 02898 00346 4 3 00312L 03895 0018 4 100 065 Fail 03895 00181 4 3 01364L 04260 0022 4 127 078 Fail 04260 00219 4 3 017

Totgem 0258 0027 mgkg 1-level 187 (177) 6 02582 () 6 5Totstd= 0132 0008 5-level 166 (154)

RESULTS Mean = 025818 mgkg

Repeatability variance S2r = 000083Repeatability std Sr = 002878 --gt 1115 r = 00806Between lab variance S2L = 001640Reproducibility var S2R = 001723Reproducibility std SR = 013127 --gt 5084 R = 03676Remarks none

000 050 100 150

k-values

26L

4L

46L

44L

12L

64L

Mandels k statistics(Soil 3 - PBD 209)

-02 -01 -01 00 01 01 02 02

Deviation from Mean

26L

4L

46L

44L

12L

64L

Labo

rato

ries

Soil 3 - PBD 209 -- Mean PARM = 0258 [mgkg]

-200 -100 000 100 200

h-values

26L

4L

46L

44L

12L

64L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 209)

Soil 3-PBD 209

Unit mgkg

Mandels k statistics(Compost 1 - Sum PBD)Mandels h statistics(Compost 1 - Sum PBD)

Sample Compost 1 Compost 1 - Sum PBD -- Mean PARM = 0009 [mgkg]

Element Sum PBD

General calcparmT1= 154064E-01T2= 169065E-03T3= 18T4= 68T5= 11354E-04

n= variabelp= 5

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00031 0002 4 -067 016 00031 00016 4 3 -0014L 00055 0005 4 -056 048 00055 00047 4 3 000

46L 00085 0003 4 -042 031 00085 00030 4 3 00026L 00123 0000 2 -024 003 00123 00002 2 1 00012L 00154 0002 4 -011 021 00154 00021 4 3 00144L 00613 0023 4 200 237 Fail - - 44L - - 005

Totgem 0018 0006 mgkg 1-level 187 (177) 5 00089 (44L) 5 4Totstd= 0022 0009 5-level 166 (154) 1

RESULTS Mean = 000893 mgkg

Repeatability variance S2r = 000001Repeatability std Sr = 000296 --gt 3308 r = 00083Between lab variance S2L = 000002Reproducibility var S2R = 000003Reproducibility std SR = 000570 --gt 6374 R = 00159Remarks 1 Lab rejected (44L)

000 050 100 150 200 250

k-values

10L

4L

46L

26L

12L

44L

Mandels k statistics(Compost 1 - Sum PBD)

00 00 00 00 00 00 01 01

Deviation from Mean

10L

4L

46L

26L

12L

44L

Labo

rato

ries

Compost 1 - Sum PBD -- Mean PARM = 0009 [mgkg]

-100 000 100 200

h-values

10L

4L

46L

26L

12L

44L

Labo

rato

ries

Mandels h statistics(Compost 1 - Sum PBD)

Compost 1-Sum PBD

Unit mgkg

Mandels k statistics(Sludge 1 - Sum PBD)Mandels h statistics(Sludge 1 - Sum PBD)

Sample Sludge 1 Sludge 1 - Sum PBD -- Mean PARM = 0256 [mgkg]

Element Sum PBD

General calcparmT1= 531806E+00T2= 162188E+00T3= 22T4= 84T5= 25223E-02

n= variabelp= 6

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00423 0025 4 -156 044 Fail 00423 00252 4 3 -02146L 01808 0118 4 -049 205 - - 46L - - -0074L 01810 0056 4 -049 097 01810 00558 4 3 -007

38L 02168 0006 4 -022 010 02168 00059 4 3 -00412L 02890 0065 4 034 113 02890 00647 4 3 00364L 03958 0008 4 116 014 Fail 03958 00079 4 3 01426L 04094 0034 2 126 059 Fail 04094 00337 2 1 015

Totgem 0245 0044 mgkg 1-level 198 (179) 6 02557 (46L) 6 5Totstd= 0130 0039 5-level 171 (155) 1

RESULTS Mean = 025570 mgkg

Repeatability variance S2r = 000158Repeatability std Sr = 003970 --gt 1553 r = 01112Between lab variance S2L = 001807Reproducibility var S2R = 001964Reproducibility std SR = 014015 --gt 5481 R = 03924Remarks 1 Lab rejected (46L)

000 050 100 150 200 250

k-values

10L

46L

4L

38L

12L

64L

26L

Mandels k statistics(Sludge 1 - Sum PBD)

-03 -02 -02 -01 -01 00 01 01 02 02

Deviation from Mean

10L

46L

4L

38L

12L

64L

26L

Labo

rato

ries

Sludge 1 - Sum PBD -- Mean PARM = 0256 [mgkg]

-200 -100 000 100 200

h-values

10L

46L

4L

38L

12L

64L

26L

Labo

rato

ries

Mandels h statistics(Sludge 1 - Sum PBD)

Sludge 1-Sum PBD

Unit mgkg

Mandels k statistics(Soil 3 - Sum PBD)Mandels h statistics(Soil 3 - Sum PBD)

Sample Soil 3 Soil 3 - Sum PBD -- Mean PARM = 0227 [mgkg]

Element Sum PBD

General calcparmT1= 610980E+00T2= 200876E+00T3= 26T4= 100T5= 13106E-02

n= variabelp= 7

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00028 0001 4 -037 000 Fail 00028 00005 4 3 -02226L 01179 0021 2 -036 003 Fail 01179 00208 2 1 -0114L 01305 0031 4 -036 004 Fail 01305 00308 4 3 -010

46L 02065 0035 4 -036 005 Fail 02065 00350 4 3 -00244L 02923 0037 4 -035 005 Fail 02923 00365 4 3 00712L 04051 0015 4 -034 002 Fail 04051 00149 4 3 01864L 04314 0022 4 -033 003 Fail 04314 00223 4 3 0203L 305500 2051 2 247 283 Fail - - 3L - - 3032

Totgem 4017 0276 mgkg 1-level 206 (181) 7 02266 (3L) 7 6Totstd= 10722 0717 5-level 175 (156) 1

RESULTS Mean = 022663 mgkg

Repeatability variance S2r = 000069Repeatability std Sr = 002626 --gt 1159 r = 00735Between lab variance S2L = 002568Reproducibility var S2R = 002637Reproducibility std SR = 016238 --gt 7165 R = 04547Remarks 1 Lab rejected (3L)

000 050 100 150 200 250 300

k-values

10L

26L

4L

46L

44L

12L

64L

3L

Mandels k statistics(Soil 3 - Sum PBD)

-50 00 50 100 150 200 250 300 350

Deviation from Mean

10L

26L

4L

46L

44L

12L

64L

3L

Labo

rato

ries

Soil 3 - Sum PBD -- Mean PARM = 0227 [mgkg]

-100 000 100 200 300

h-values

10L

26L

4L

46L

44L

12L

64L

3L

Labo

rato

ries

Mandels h statistics(Soil 3 - Sum PBD)

Soil 3-Sum PBD

19

Annex 4

Raw data submitted

Sample Compost1 Sample Compost 1 Sample Compost 1Element PBD 99 Element PBD 100 Element PBD 153

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]4L 00021 10L 00008 44L 000504L 00024 10L 00008 44L 000604L 00014 10L 00007 44L 000504L 00020 10L 00011 46L 00004

10L 00029 46L 00007 46L 0001210L 00027 46L 00012 46L 0000410L 00032 46L 00009 46L 0000946L 00025 46L 00007 12L 0000446L 00052 12L 00008 12L 0000846L 00029 12L 00012 12L 0000446L 00026 12L 00008 12L 0000712L 00026 12L 00014 26L 0000512L 00043 26L 00007 26L 0000512L 00026 26L 0000612L 0004726L 0002626L 00024

Sample Compost 1 Sample Compost 1 Sample Compost 1Element PBD 154 Element PBD 183 Element PBD 196

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]4L 00010 46L 00002 46L 00011

46L 00003 46L 00024 46L 0000846L 00007 46L 00021 12L 0000246L 00003 46L 00003 12L 0000346L 00004 12L 00003 12L 0000112L 00003 12L 00011 12L 0000212L 00005 12L 0000312L 00031 12L 0000312L 00006

Sample Compost 1 Sample Compost 1 Sample Compost 1Element PBD 197 Element PBD 203 Element PBD 209

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00002 46L 00010 4L 0004146L 00023 12L 00002 4L 0008946L 00022 12L 00003 44L 0041012L 00004 12L 00002 44L 0084012L 00006 12L 00002 44L 0064012L 00003 44L 0040012L 00004 12L 00079

12L 0007312L 0006512L 0009326L 0004926L 00049

Sample Compost 1Element PBD 47

LAB PARM [mgkg]26L 0003826L 00039

Element PBD 99 Element PBD 47 Element PBD 209LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]

4L 00170 10L 00210 4L 010004L 00200 10L 00220 4L 018004L 00170 10L 00210 4L 012004L 00190 46L 00300 4L 0220010L 00280 46L 00280 46L 0210010L 00300 46L 00250 46L 0200010L 00290 46L 00260 64L 0351846L 00340 64L 00059 64L 0363846L 00330 64L 00057 64L 0364546L 00300 64L 00062 64L 0350846L 00310 64L 00060 12L 0220964L 00194 12L 00191 12L 0177164L 00154 12L 00187 12L 0292264L 00185 12L 00190 12L 0164664L 00159 12L 00186 26L 0329712L 00242 26L 00666 26L 0300012L 00223 26L 0033212L 0022112L 0022226L 0024626L 00400

Element PBD 203 Element PBD 197 Element PBD 196LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00022 46L 00027 46L 0002446L 00014 46L 00024 46L 0002264L 00036 12L 00161 64L 0005864L 00058 12L 00060 64L 0006512L 00063 12L 00061 12L 0004812L 00034 12L 00036 12L 0002512L 00038 12L 0003212L 00027 12L 00022

Element PBD 183 Element PBD 154 Element PBD 153LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00049 4L 00020 4L 0002246L 00035 4L 00022 4L 0002446L 00036 4L 00020 4L 0002246L 00034 46L 00025 4L 0002664L 00027 46L 00025 46L 0004064L 00023 46L 00025 46L 0004264L 00024 46L 00023 46L 0003564L 00020 64L 00034 46L 0003812L 00230 64L 00023 64L 0007412L 00032 64L 00017 64L 0004712L 00031 64L 00011 64L 0004612L 00030 12L 00030 64L 0003026L 00007 12L 00021 12L 0006526L 00008 12L 00021 12L 00029

12L 00021 12L 0003226L 00015 12L 0002926L 00019 26L 00039

26L 00040

Element PBD 100LAB PARM [mgkg]

4L 000384L 000414L 000374L 00038

38L 0219038L 0220038L 0208038L 0220010L 0004410L 0005010L 0004310L 0004646L 0005746L 0005946L 0005346L 0005312L 0004312L 0004512L 0004312L 0004326L 0006226L 00057

Sample Soil 3 Sample Soil 3 Sample Soil 3Element PBD 99 Element PBD 47 Element PBD 100

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]10L 00016 10L 00011 10L 0000310L 00019 10L 00010 10L 0000410L 00013 10L 00012 10L 0000410L 00019 46L 00007 10L 0000246L 00025 46L 00022 46L 0000246L 00025 46L 00005 46L 0000646L 00008 46L 00007 46L 0000246L 00011 12L 00010 46L 0000264L 00005 12L 00017 3L 29100064L 00005 12L 00010 3L 32000064L 00006 12L 00009 26L 0000564L 00007 26L 00007 26L 0000512L 00012 26L 0000712L 0001312L 0001312L 0001226L 0000526L 00006

Sample Soil 3 Sample Soil 3 Sample Soil 3Element PBD 153 Element PBD 154 Element PBD 196

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]44L 00050 4L 00010 46L 0000744L 00050 46L 00001 46L 0001146L 00002 46L 00002 46L 0000846L 00003 46L 00001 46L 0001146L 00002 46L 00002 64L 0002646L 00002 64L 00001 64L 0002664L 00001 64L 00001 64L 0002964L 00001 64L 00001 64L 0003464L 00001 64L 00002 12L 0004564L 00002 12L 00003 12L 00032

12L 00002 12L 0002212L 00002 12L 0002112L 00002

Sample Soil 3 Sample Soil 3 Sample Soil 3Element PBD 197 Element PBD 203 Element PBD 209

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00006 46L 00011 4L 0091046L 00013 46L 00017 4L 0150046L 00011 46L 00015 4L 0120046L 00013 46L 00018 4L 0160012L 00090 64L 00013 44L 0337012L 00056 64L 00014 44L 0281012L 00033 64L 00016 44L 0287012L 00032 64L 00015 44L 02540

12L 00055 46L 0230012L 00041 46L 0220012L 00027 46L 0150012L 00026 46L 01900

64L 0438164L 0401664L 0414464L 0449812L 0367112L 0397812L 0409112L 03838

Sample Soil 3 26L 0102Element PBD 183 26L 0131

LAB PARM [mgkg]46L 0000746L 0000846L 0005846L 0000764L 0000264L 0000364L 0000364L 0000312L 0001512L 0001112L 0000712L 00007

European Commission EUR 23003 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on polybrominated diphenylethers Author(s) E Sobiecka H van der Sloot D Barcelo B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 68 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07403-5 Abstract Project HORIZONTAL is interdisciplinary aiming at a harmonisation and horizontal standardisation of test procedures in particular for sludge soils and biowastes In the context of this standardization project a series of draft technical specification were designed upon an extensive desk study fine-tuned after expert consultations and finally validated in international intercomparisons exercise This report summarises the work performed within the validation study of the draft standard for the determination of polybrominated diphenylethers (PBDE) in soils sludge and treated bio-waste using gas-chromatography method with mass selective detection (GC-MS) It further explains the underlying statistical concept for the calculation of reproducibility and repeatability from intercomparisons data In addition all single values results of the statistical evaluation as well as background information on the validation materials used are described and explained

The mission of the JRC is to provide customer-driven scientific and technical support for the conception development implementation and monitoring of EU policies As a service of the European Commission the JRC functions as a reference centre of science and technology for the Union Close to the policy-making process it serves the common interest of the Member States while being independent of special interests whether private or national

LB

-NA

-23003-EN

-C

Summary Project HORIZONTAL is interdisciplinary aiming at a harmonisation and horizontal standardisation of test procedures in particular for sludge soils and biowastes In the context of this standardization project a series of draft technical specification were designed upon an extensive desk study fine-tuned after expert consultations and finally validated in international intercomparisons exercise This report summarises the work performed within the validation study of the draft standard for the determination of polybrominated diphenylethers (PBDE) in soils sludge and treated bio-waste using gas-chromatography method with mass selective detection (GC-MS) It further explains the underlying statistical concept for the calculation of reproducibility and repeatability from intercomparisons data In addition all single values results of the statistical evaluation as well as background information on the validation materials used are described and explained

Abbreviations Throughout this report the following abbreviations are used ANOVA Analysis of variances

CAS Chemical Abstracts System

CEN Comitteeacute Europeacuteen de Normalisation

DG Directorate General

ECD Electron Capture Detector

ECN Energy Research Centre for the Netherlands

EU European Union

IES Institute for Environment and Sustainability

IT Information Technology

ISO International Organization for Standardisation

JRC Joint Research Centre

GC Gas Chromatography

MILC Measure Interlaboratory Comparison

MS Mass Spectroscopy

p Number of labs

PBDE Polybrominated Diphenylethers

r Repeatability limit

R Reproducibility limit

sr Repeatability standard deviation

sR Reproducibility standard deviation

TC Technical Committee

4

Table of Contents Summary 2 Abbreviations 3 Table of Contents 4

Introduction to the validation project 5 11 Statistical concept underlying the validation 6

111 Introduction to the statistical model 6 112 Requirements for precision experiment 7 113 Statistical analysis 8

12 Validation exercise for PBDE 8 121 Compounds to be measured 8 122 Samples dispatched for the validation of PBDE 8 123 Draft standards to be followed 8 124 Analytical programm 8 125 Timing and Submission of data 9 126 Participants 10

13 Summary results and derived performance characteristics 11 14 Annexes 15

5

Introduction to the validation project Project HORIZONTAL is interdisciplinary aiming at a harmonisation and horizontal standardisation of test procedures in particular for sludges soils and biowastes It was created as in response to the European Commission Mandate M 330 given to CEN asking for the development and validation of those standards in support of forthcoming EU Directives such as

o The revision of the Sewage Sludge Directive 86278EEC o The Directive on the biological treatment of biodegradable waste o The initiative on a legal framework for soil monitoring in Europe

This mandate explicitly considers standards for the entire analytical procedure (ie sampling pre-treatment and analytical measurement methods for inorganic organic hygiene and biological parameters) These are grouped into classes according to their physicalchemical properties which in turn determine the methods needed to quantify the potential impact on human and animal health plant uptake soil function and groundwater quality As the materials generally feature a mixture of different types of contaminants it is important to provide an integrated answer covering evaluation of all relevant pollutants In order to fulfil the requirements of the aforementioned mandate the European Commissions Joint Research Centre (JRC) and its Directorate-General for Environment (DG ENV) together with the Technical Committees of the European Standardisation Committee (CEN TCs) concerned designed a pre-normative research initiative called Project HORIZONTAL and presented it to the Commission and the Environmental Authorities in the Member States After an extensive literature research and careful evaluation of the feasibility of a given horizontal standard the standards were drafted and finally validated in an European laboratory intercomparison The underlying statistical concept information about the materials used details about the participants measurement results obtained as well as the derived performance characteristics obtained for the determination of polybrominated diphenylethers (PBDE) are described hereafter

6

11 Statistical concept underlying the validation According to the requirements of the work package concerning data handling amp interpretation of the project HORIZONTAL-ORG the respective validation intercomparisons have to be evaluated according to the principles laid down in ISO standard 5725-21994 In particular repeatability and reproducibility of the draft standard methods have to be determined The determination of trueness would require the availability of independent reference values for the materials investigated This however is not possible and was not requested in the frame of this work In the following the approach chosen is explained

111 Introduction to the statistical model The statistical model used in ISO 5725 for estimation of accuracy of a measurement method assumes that every test result is the sum of three components

eBmy ++= y test result m general mean B laboratory component of bias under repeatability conditions e random error occurring in every measurement under repeatability conditions

In the workprogram the quantification of term e is explicitly asked for (ie repeatability and reproducibility) The repeatability variance is measured directly as the variance of the error term e but the reproducibility depends on the sum of the repeatability variance and the between-laboratory variance

( )er var=σ 22rLR σσσ += with ( )BL var=σ

However soil biowaste and sludge are multi-phase materials ie they contain two or more distinct types of particles which are fundamentally different in their properties and composition As a consequence this introduces an important source of variation for the intercomparison exercise which needs to be considered ie the inherent heterogeneity of the materials Thus a contribution of variation between samples H is introduced to the general statistical model

HeBmy +++= Using ANOVA techniques the different variances are calculated and separated for the evaluation

7

112 Requirements for precision experiment

Layout of the experiment A suite of 10 to 12 different materials (soil sludge and biowaste) has been made available for the intercomparison exercise For each parameter investigated at least 10 to laboratories should be nominated to participate The same laboratories should be used for different parameters as far as possible Due to the complexity of analysis and the respective workload to the laboratories it was decided to propose three materials for the validation of the PBDE draft standard Each laboratory received two bottles of each material and was be requested to perform 4 independent analyses per material1 (2 per bottle) using the respective draft standard methods The 4 analysis per material should be carried out under repeatability conditions (ie same operator2 same equipment within a short period of time) As far as possible also the different materials should be measured under repeatability conditions however changes of eg operator or equipment are permitted but must be reported Likewise different materials can be analysed on different days if necessary Equipment used in the experiment needed to be checked prior to the experiment according to the requirements of the draft standard The results of these checks have to be documented Similarly date and time of each measurement had to be recorded for verification of repeatability conditions An appropriate timeframe for the entire exercise has been set and was to be respected

Recruitment of the laboratories Each sub-workpackage leader of HORIZONTAL was asked to select the laboratories using the information from section 52 of ISO 5725-21994 and provide the signed questionnaires (see also Annex 1) The workpackage leaders were responsible for providing the laboratories with the draft standard method and explaining the context of this exercise

Preparation and use of the materials Materials used for the exercise were prepared according to the general requirements for reference materials as laid down in ISO Guide 34 Materials were accompanied by instructions for use

Reporting of results Online submissions of results using an internet-based IT platform as well as XLS-Spreadsheets were used In case of online data submission the participating laboratories received a unique and confidential login and password in due time enabling them to

1 Independent analysis means analysis of independent test portions applying the entire analytical scheme to this test portion from eg extraction to quantification For instance it does not mean replicate injections of aliquots into a GC-MS instrument 2 Operator in this context may also consist of a fixed team of persons eg one person performing extraction one clean-up one quantification

8

enter their data in a structured form For authentication purposes a signed printout had to be submitted by mail The online data submission included a detailed questionnaire for additional information on the measurements

113 Statistical analysis Statistical analysis of data followed the requirements of ISO 5725-21994 and ISO 5725-51998 Appropriate tests for the homogeneity of variance detection of outliers and normal distribution were applied Statistical evaluation was done using an Excel Macro developed tested and successfully applied in other occasion by ECN Evaluation was executed jointly by JRC and ECN

12 Validation exercise for PBDE

121 Compounds to be measured The following compound were selected for the validation exercise Tetra-BDE-47 Penta-BDE-100 Penta-BDE-99 Hexa-BDE-154 Hexa-BDE-153 Hepta-BDE-183 Octa-BDE-196 Octa-BDE-197 Octa-BDE-203 Deca-BDE-209

122 Samples dispatched for the validation of PBDE After a preliminary rough screening the following materials were used for the validation round of PBDE

bull Compost 1 A pollutant loaded compost material from Vienna bull Sewage Sludge 1 A mixed sewage sludge from Essen bull Soil 3 A sludge amended soil from Barcelona

A more detailed description of background concentrations can be found in Annex 2 to this report The samples were dispatched simultaneously to all participants using a private courier service

123 Draft standards to be followed The draft standards to be followed could be downloaded following this link which is situated on the website of the Project HORIZONTAL httpwwwecnnldocssocietyhorizontalBFR_Standard_for_validationpdf

124 Analytical programm Of each of the three materials 2 bottles had to be analysed and each bottle had to analysed independently twice As mentioned above analyses were to be done under repeatability conditions Results were to be reported referring to DRY MATTER content The choice how to apply dm correction was free for each participant

9

125 Timing and Submission of data Dispatch of samples was done on the 18th of October 2006 For users of the Online data submission system (MILC) User Registration was possible from 14th of November 2006 with opening of the MILC Data Submission on 1st of December 2006 The deadline for submission of results has been set for PBDE to the 12th of January 2007 but was extended to the end of the same months After that no further submission was possible Alternatively the participants were allowed to submit data electronically as Excel sheet using simply Email All data were treated in a confidential way Any presentation hereafter will refer only to numerical data and it will not be possible to identify the originating laboratory Lab Codes displayed are NOT related to the order of laboratories hereafter In addition to the information provide an Helpdesk was implemented in order to give quick and individual response to the participants during and immediately after the validation study In case of doubt and suspected transcription errors further enquires were conducted by JRC

10

126 Participants The following table lists the participating organisations and entities in the validation exercise for the horizontal PBDE standard

bull Austria o Umweltbundesamt

bull Czech Republic o Povodi Labe statni podnik - OVHL Laboratory

bull France o CIRSEE o CTC Environnement o INERIS

bull Germany o Federal Environmental Agency Section III 34 Laboratory Methods for

the Surveillance of Waste and Wastewater (UBA) bull Italy

o European Commission DG JRC IES bull Spain

o Consejo Superior de Investigaciones Cientificas (CSIC)

bull Sweden o ALCONTROL AB

11

13 Summary results and derived performance characteristics The result of the various statistical evaluation including outlier tests calculation of repeatability and reproducibility standard deviation for the congeners of interest can be found in Annex 3 of this report In addition all data submitted by the participants as well as those considered for the calculation of the performance characteristics are listed in Annex 3 to this report Based on these calculations the following results were obtained in the validation round upon statistical evaluation according to ISO 5725-2 The average values the repeatability standard deviation (sr) and the reproducibility standard deviation (sR) were obtained (Table1) The repeatability is determined as an interval around a measurement result (ie repeatability limit) This interval corresponds to the maximum difference that can be expected (with a 95 statistical confidence) between one test result and another both test results being obtained under the following conditions The tests are performed in accordance with all the requirements of the present standard by the same laboratory using its own facilities and testing laboratory samples obtained from the same primary field sample and prepared under identical procedures The repeatability limit was calculated using the relationship r test = f radic2 s rtest with the critical range factor f = 2 The reproducibility like repeatability is also determined as an interval around a measurement result (ie reproducibility limit) This interval corresponds to the maximum difference that can be expected (with a 95 statistical confidence) between one test result and another test result obtained by another laboratory both test results being obtained under the following conditions The tests are performed in accordance with all the requirements of the present standard by two different laboratories using their own facilities and testing laboratory samples obtained from the same primary field sample and prepared under identical procedures The reproducibility limit was calculated using the relationship R = f radic2 sR with the critical range factor f = 2

12

Table 1 - Results of the interlaboratory comparison studies of the determination of selected polybrominated diphenyl ethers (PBDE) by gaschromatography with mass spectrometric detection (GC-MS) in soil sludge and treated biowaste All concentrations are expressed in mgkg dm

Matrix Parameter Mean sr sR r R p Outliers Used No of data

No of data reported below

detection

Total no of data

Sludge 1 PBD 47 00181 461 4 15 5 20 Compost 1 00039 94 3 12 0 12 Soil 3 00010 50 50 00014 00014 4 0 13 10 23 Sludge 1 PBD 99 00239 64 28 00043 00186 5 1 19 0 23 Compost 1 00029 31 35 00025 00028 5 0 17 4 21 Soil 3 00013 499 4 16 8 24 Sludge 1 PBD 100 00049 51 17 00007 00024 5 1 18 2 24 Compost 1 00009 25 29 00006 00007 4 0 14 7 21 Soil 3 61103 211 3 10 15 25 Sludge 1 PBD 153 00038 33 38 00034 0004 5 0 18 0 18 Compost 1 00019 116 3 11 3 14 Soil 3 00011 177 2 10 10 20 Sludge 1 PBD 154 00023 234 4 15 2 17 Compost 1 00008 1118 3 9 5 14

13

Matrix Parameter Mean sr sR r R p Outliers Used No of data

No of data reported below

detection

Total no of data

Soil 3 00002 1049 4 13 6 19 Sludge 1 PBD 183 00048 1217 3 12 2 14 Compost 1 00009 1048 2 8 5 13 Soil 3 00011 1395 3 12 6 18 Sludge 1 PBD 196 00037 470 2 8 7 15 Compost 1 00004 950 2 6 4 10 Soil 3 00023 519 3 12 2 14 Sludge 1 PBD 197 00062 834 2 6 8 14 Compost 1 00009 1001 2 7 7 14 Soil 3 00032 904 2 8 6 14 Sludge 1 PBD 203 00037 461 2 8 4 12 Compost 1 00004 978 2 5 3 8 Soil 3 00022 598 3 12 0 12 Sludge 1 PBD 209 02493 170 39 01186 02689 5 0 16 2 18 Compost 1 00273 104 3 10 5 15 Soil 3 02582 1115 51 00806 03676 6 0 22 0 22

14

Matrix Parameter Mean sr sR r R p Outliers Used No of data

No of data reported below

detection

Total no of data

Sludge 1 Sum PBD 0256 155 548 0111 0392 6 1 22 Compost 1 0009 331 637 0008 0016 5 1 18 Soil 3 0227 116 717 0074 0455 7 1 26 Abbreviations sr Repeatability standard deviation SR Reproducibility standard deviation r Repeatability limit (comparing two measurements) R Reproducibility limit (comparing two measurements) p Number of labs determination not possible

15

14 Annexes Annex 1 Model questionnaire to be filled by the participating laboratories Annex 3 Report on the validation materials used Annex 2 Statistical calculations Annex 3 Data submitted

16

Annex 1

Model questionnaire to be filled by the participating laboratories

Model questionnaire to be filled by the participating laboratories Name of laboratory Contact person Contact details email Phone Fax Mail address of lab Dispatch address of lab for shipment of samples (no PO boxes) Title of measurement method (copy attached) Our laboratory is willing to participate in the precision experiment for this draft standard method

Yes No As participant we understand that

bull All essential apparatus chemicals and other requirements specified in the method must be available in our laboratory when the programme begins

bull Specified timing requirements such as starting and finishing date of the programme must be rigidly met

bull The method must be strictly adhered to bull Samples must be handled in accordance with instructions bull A qualified operator must perform the measurements

Having studied the method and having made a fair appraisal of our capabilities and facilities we feel that we will be adequately prepared for cooperative testing of this method Comments helliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphellip Signature Date

17

Annex 2

Report on the validation materials used

VI

Abstract This report gives an overview on the available analytical information on the following raw materials to be used for the production of validation materials of the so-called Project HORIZONTAL

bull Four sludge materials from Duumlsseldorf Germany

bull An agricultural soil material from Reading United Kingdom

bull A compost material from Vienna Austria

bull A compost material from Korschenbroich Germany

bull A sludge-amended agricultural soil from Pavia Province Italy

bull A sludge-amended soil from Barcelona Spain

bull A sludge-amended soil from Essen Germany

bull A long-term sludge exposed soil from Hohenheim Germany

VII

List of Abbreviations Throughout this report the following abbreviations are used

AOX absorbable organic halogens

Corg organic carbon content

Ctotal total carbon content

CAT cation exchangeable

CDD chlorinated dibenzodioxin

CDF chlorinated dibenzofuran

DEHP di(2-ethylhexyl)phthalate

DM dry matter

EPA Environment Protection Agency

EU European Union

FM fresh matter

Hp hepta

Hx hexa

IES Institute for Environment and Sustainability

IRMM Institute for Reference Materials and Measurements

JRC Joint Research Centre

LAS linear alkylsulfonates

LoD limit of detection

LUA Landesumweltamt

Ntotal total nitrogen content

NH4-N Ammonium nitrogen

NO3-N Nitrate nitrogen

NP nonylphenol

NRW North Rhine Westphalia

O octa

P poly

PAH polycyclic aromatic hydrocarbon

PCB polychlorinated biphenyl

Pe penta

T tetra

TEQ toxicity equivalent

UBA Umweltbundesamt

WHO World Health Organization

WWTP waste water treatment plant

6

1 Introduction This report gives an overview on the available analytical information on the following raw materials to be used for the production of validation materials of the so-called Project HORIZONTAL

bull Four sludge materials from Duumlsseldorf Germany

bull An agricultural soil material from Reading United Kingdom

bull A compost material from Vienna Austria

bull A compost material from Korschenbroich Germany

bull A sludge-amended agricultural soil from Pavia Province Italy

bull A sludge-amended soil from Barcelona Spain

bull A sludge-amended soil from Essen Germany

bull A long-term sludge exposed soil from Hohenheim Germany

The following analytical information was gathered partly before and during the sampling of the raw materials to be used for the production of the HORIZONTAL validation materials The material were sampled by IES and shipped to IRMM in the course of the year 2005 The information gathered was then completed by various analytical screenings for PAHs and PCBs done by the Institute for Reference Materials and Measurements Geel Belgium for phthalates done by UBA Berlin Germany for PBDE done by IIQAB-CSIC Barcelona Spain for trace elements and some selected major and minor elements by the Institute for Environment and Sustainability Ispra Italy

The work compiled hereafter is based on the numerous additional efforts of the scientists working at various members of the consortium Project HORIZONTAL-Org and contributing organisations

This work is gratefully acknowledged

2 Overview on property values

21 Sludge materials from Duumlsseldorf Germany

The various sewage sludge materials originate from various installations in the North Rhine Westphalia and were produced and sampled by staff from the Landesumweltamt (LUA) NRW under the responsibility from Dr K Furtmann

In total four sludge materials (Sludge A and D from a major municipal WWTP Sludge B from a municipal WWTP with industrial input and Sludge C from a municipal WWTP with high PCB-Content) were obtained and will be blended to two final materials Before sampling the following analytical data for a typical sample were received

7

Table 1 ndash Analytical data obtained on an average sludge sample in LUA NRW (with courtesy of K Furtmann LUA Duumlsseldorf)

Parameter Concentration PCB 120 ugkg DEHP 110 mgkg PAH 5 mgkg (EPA) PCDDF 15 ng TEkg PBDE 400 ugkg NP 40 mgkg LAS 3 gkg AOX 300 mgkg

Subsequent screening led to the information displayed hereafter It should be stressed that the data were obtained as SCREENING information on the UNTREATED or partially treated raw materials Therefore the final target values which are relevant for the validation intercomparison can be different

Table 2 ndash Analytical data obtained on a first screening on the sludge samples from LUA NRW

Sewage sludge A

Dusseldorf

sewage sludge D

Dusseldorf PCB (ngg) 28 62 35 52 101 65 101 31 38 118 49 40 153 30 33 105 24 11 138 46 38 156 lt1 lt1 180 34 23 170 23 19 PAH (ngg) Naphtalene 34 381 Acenaphtylene 15 43 Acenaphthene 81 108 Fluorene 94 1167 Phenantrene 3440 Anthracene 22 344 Flouranthene 316 4817 Pyrene 235 3011 Benz(a)anthracene 473 791 Chrysene 691 1078 Benz(b)fluoranthene 538 1688 Benz(k)fluoranthene 228 635 Benz(a)pyrene 383 1114 Indeno(123-cd)pyrene 92 229 Dibenzo(ah)anthracene 71 70 Benzo(ghi)perylene 80 185

8

Table 3 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Sludge D (1) 0135 41474 385 Sludge B (2) 0538 0034 30634 547 Sludge A (3) 0184 0037 31399 146 Sludge C (4) 0354 1528 6678 229

Table 4 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Sludge 2

(B)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

554

959

694

591

772

509

nq

nq

970

2216

2379

Table 5 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena IES Ispra Spain) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Sludge 1 (D) 265 290 533 359 1231 338 784 438 lt 005 232 786 Sludge 2 (B) 119 311 626 202 278 299 722 251 lt 005 118 625 Sludge 3 (A) 168 360 621 332 847 416 119 451 lt 005 116 1237 Sludge 4 (C) 563 198 116 273 726 511 473 618 lt 005 444 2015

Table 6 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Sludge 1 (D) 2154 58 844 099 103 101 4367 lt15 50448 Sludge 2 (B) 1067 366 692 046 1491 077 5217 lt15 57633 Sludge 3 (A) 731 663 684 035 1287 068 3733 lt15 60369 Sludge 4 (C) 4379 965 527 163 522 107 5628 lt15 23945

Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM)Sludge 1 (D) 03 2403 101 1002 350 15 1944 132Sludge 2 (B) 031 315 97 879 172 12 514 180Sludge 3 (A) 031 1281 153 1567 265 16 1440 168Sludge 4 (C) 055 231 628 2625 371 81 1101 244

9

22 Agricultural soil material from Reading United Kingdom

The material was proposed by the University of Reading (S Nortcliff) and was sampled from a site called ldquoFrogmore Farmrdquo which was featured in the ldquoMetalsrdquo Report for HORIZONTAL This site is close to Reading with soils developed on flintyloamy periglacial materials over Chalk has a long and well documented history of sludge application The focus of the work of Nortcliff et al undertook at this site and the monitoring and control at the site (by Thames Water and the subsequent subsidiary bodies dealing with sludge application to soil) was on metals (and metal loads) with no analysis or indeed any form of investigation in to organics in the broadest sense

The analytical information produced in the context of the screening of the raw material is displayed below

Table 7 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 3

(Reading) 0032 0119 669

Table 8 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 3 (Reading) 015 706 279 138 152 901 267 300 lt 005 258 931

Table 9 ndash Analytical data obtained on a first screening on the sludge-amended soil from Reading (courtesy of IRMM)

Parameter Concentration

PCB ngg 28 lt1 52 lt1 101 lt1 118 lt1 153 lt1 105 lt1 138 lt1 156 lt1 180 lt1 170 lt1 PAH ngg Naphtalene lt10 Acenaphtylene 21 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene lt10 Flouranthene 818 Pyrene 776 Benz(a)anthracene 565

10

Parameter Concentration

Chrysene 608 Benz(b)fluoranthene 824 Benz(k)fluoranthene 329 Benz(a)pyrene 799 Indeno(123-cd)pyrene

779

Dibenzo(ah)anthracene 118 Benzo(ghi)perylene 394

Table 10 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 3

(Reading)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

103

003

nq

nq

nq

nd

nd

272

273

Table 11 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 3 (Reading) 015 706 279 138 152 901 267 300 lt 005 258 931

Table 12 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 3 (Reading) 7936 477 112 096 194 017 4107 443 2102 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 3 (Reading) 042 13 45 69 69 69 216 92

Table 13 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 3 (Reading) 012

11

23 Compost from Vienna Austria

The fresh compost material was obtained from the Austrian Federal Environment Agency (UBA Vienna) which had used a sub-batch of the raw material for national intercomparson The remainder of the material was stored at 4degC until shipment to IRMM for further processing The following analytical information was provided by UBA Austria and completed with various screenings

Table 14 ndash Analytical data on compost material received from UBA Austria Inorganic and sum parameters

Parameter Unit Sample fraction used Observed mean B CAT mgl FM Fresh sample lt10mm 61 K CAT mgl FM Fresh sample lt10mm 2624 Mg CAT mgl FM Fresh sample lt10mm 242 P CAT mgl FM Fresh sample lt10mm 49 B CAT DM Fresh sample lt10mm 00017 K CAT DM Fresh sample lt10mm 072 Mg CAT DM Fresh sample lt10mm 007 P CAT DM Fresh sample lt10mm 001 NO3-N mgkg FM Fresh sample lt10mm 35 NH4-N mgkg FM Fresh sample lt10mm 230 Ctotal DM lt45degdry milled 29 Corg DM lt45degdry milled 27 Ntotal DM lt45degdry milled 17 P mgkg DM lt45degdry milled 2596 K mgkg DM lt45degdry milled 11019 K DM lt45degdry milled 110 B mgkg DM lt45degdry milled 60 Cd mgkg DM lt45degdry milled 046 Cr mgkg DM lt45degdry milled 25 Cu mgkg DM lt45degdry milled 46 Hg mgkg DM lt45degdry milled 020 Ni mgkg DM lt45degdry milled 18 Pb mgkg DM lt45degdry milled 45 Zn mgkg DM lt45degdry milled 198 Ca mgkg DM lt45degdry milled 68776 Ca DM lt45degdry milled 69 Mo mgkg DM lt45degdry milled 08 S mgkg DM lt45degdry milled 2137 Fe mgkg DM lt45degdry milled 9959 Mn mgkg DM lt45degdry milled 418 Na mgkg DM lt45degdry milled 742 Co mgkg DM lt45degdry milled 41 AOX mgkg DM lt30deg dry milled 62

Table 15 ndash Analytical data on compost material received from UBA Austria Polycyclic aromatic hydrocarbons

PAH Unit Result Naphthaline microgkg DM 93 Acenaphthylene microgkg DM 86 Acenaphthene microgkg DM 5 Fluorene microgkg DM 80 Phenanthrene microgkg DM 89 Anthracene microgkg DM 27 Fluoranthene microgkg DM 487 Pyrene microgkg DM 380

12

PAH Unit Result Benzo(a)anthracene microgkg DM 278 Chrysene microgkg DM 317 Benzo(b)fluoranthene microgkg DM 365 Benzo(k)fluoranthene microgkg DM 193 Benz(a)pyrene microgkg DM 320 Indeno(123-cd)pyrene microgkg DM 233 Dibenz(ah)anthracene microgkg DM 67 Benzo(ghi)perylene microgkg DM 225 Sum EPA microgkg DM 3013 Sum EPA mgkg DM 30

Table 16 ndash Analytical data on compost material received from UBA Austria Sum PCDDs and PCBs

Parameter

Dioxine TEQ (ITEF) ngkg DM 73 TEQ (WHO) ngkg DM 35 PCB Σ Ballschmiter mgkg DM 005

Table 17 ndash Analytical data on compost material obtained by screening in IRMM

Parameter Result in ngg

PCB 28 2 52 2 101 4 118 3 153 10 105 1 138 8 156 1 180 5 170 lt1 PAH Naphtalene lt10 Acenaphtylene lt10 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene 26 Fluoranthene 611 Pyrene 510 Benz(a)anthracene 888 Chrysene 957 Benz(b)fluoranthene 1531 Benz(k)fluoranthene 547 Benz(a)pyrene 1101 Indeno(123-cd)pyrene 416 Dibenzo(ah)anthracene 81 Benzo(ghi)perylene 295

13

Table 18 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Compost 1

(Vienna)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

402

019

259

nq

023

004

nq

nq

144

174

259

Table 19 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Compost 1

(Vienna) 0058 1426 557

Table 20 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Compost 1 (Vienna) 039 736 319 410 365 127 495 004 079 013 208

Table 21 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Compost 1 (Vienna) 2063 431 617 426 199 249 1602 lt15 10521

Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Compost 1 (Vienna) 035 3496 81 375 79 55 653 60

Table 22 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Compost 1 (Vienna) 017

14

24 Agricultural soil sludge amended soil from Pavia Italy

This sludge-amended soil material was obtained during a monitoring campaign which aimed at a generic description of the over-all soil quality in Pavia Province Italy The material which was collected from the upper horizon originates from a small farm called ldquoCascina Novellordquo During the characterisation of the site the following analytical information was obtained on a pooled sample of a sub-area of the farm of 20 X 20 m2

Table 23 ndash Analytical data on Pavia soil

Parameter Result Al 713 Wgt As 224 mgkg Cd 079 mgkg Cr 59 mgkg Cu 308 mgkg Hg 008 mgkg Ni 344 mgkg Pb 246 mgkg Zn 95 mgkg C 091 Wgt 2378-TCDD 0047 pgg 12378-PeCDD 015 pgg 123478-HxCDD 019 pgg 123678-HxCDD 15 pgg 123789-HxCDD 074 pgg 1234678-HpCDD 26 pgg OCDD 382 pgg 2378-TCDF 068 pgg 12378-PeCDF 053 pgg 23478-PeCDF 071 pgg 123478-HxDF 100 pgg 123678-HxDF 066 pgg 234678-HxDF 16 pgg 123789-HxDF 027 pgg 1234678-HpDF 12 pgg 1234789-HpDF 068 pgg OCDF 33 pgg I-TEQ 20 pgg WHO-TEQ 17 pgg

In addition the screening performed at IRMM did not reveal significant quantities of PCBs and PAHs which were all below the LoDs (1 ngg for PCBs and 10 ngg for PAHs respectively)

Table 24 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 5 (Pavia) 0005 0011 154

15

Table 25 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 5

(Pavia)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

039

nq

nq

008

nq

nd

nd

670

671

Table 26 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 5 (Pavia) 033 184 573 225 426 305 206 200 lt 005 381 878

Table 27 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 5 (Pavia) 6939 129 145 224 425 116 6118 255 1789 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 5 (Pavia) 184 62 38 108 55 66 597 110

Table 28 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 5 (Pavia) 006

16

25 Sludge-amended-soil from Barcelona Spain

The sludge-amended soil material from Barcelona sampled upon indication from the Barcelorsquo- Group in Barcelona

Table 29 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 2 (Lleida T) 0015 0183 1138

Table 30 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 2

(Lleida T)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

159

045

nq

048

160

nq

nq

1000

1004

Table 31 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 2 (Lleida T) 059 141 327 536 405 186 184 224 lt 005 318 111

Table 32 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 2 (Lleida T) 4443 1067 1429 253 344 204 4116 780 3396 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 2 (Lleida T) 064 65 26 125 59 17 547 65

Table 33 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 2 (Lleida T) 010

17

26 Sludge amended soil from Essen Germany

The German sludge-amended soil from Essen which was provided as the three sludge materials by LUA NRW did not feature significant concentrations of the PCB congeners 28 52 101 118 153 105 138 156 180 170 but had detectable amounts of some PAHs

Table 34 ndash Analytical screening data on the German sludge-amended soil

Parameter Concentration(ngg)

Naphtalene lt10 Acenaphtylene lt10 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene lt10 Fluoranthene 28 Pyrene 20 Benz(a)anthracene 24 Chrysene 47 Benz(b)fluoranthene 76 Benz(k)fluoranthene 20 Benz(a)pyrene 35 Indeno(123-cd)pyrene 35 Dibenzo(ah)anthracene 10 Benzo(ghi)perylene 26

Table 35 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 4 (Essen) 0011 0302 055

Table 36 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 4

(Essen)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

nq

nq

nq

nq

nq

nq

128

191

203

18

Table 37 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 4 (Essen) 052 545 261 805 320 403 273 273 lt 005 295 781

Table 38 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 4 (Essen) 7947 442 085 06 086 007 2163 189 2019 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 4 (Essen) 045 19 42 87 683 60 462 61

Table 39 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 4 (Essen) 004

27 Long-term sludge exposed soil from Hohenheim-Stuttgart Germany

Similarly an additional sludge exposed soil was sampled at the University of Hohenheim Stuttgart were a test soil was long-term exposed to elevated concentrations of sewage sludge

Table 40 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 1 (Stuttgart) 0045 0263 1765

Table 41 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 1

(Stuttgart)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

230

006

004

004

nq

nd

nd

498

500

19

Table 42 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 1 (Stuttgart) 069 127 361 262 504 183 252 262 lt 005 266 142

Table 43 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 1 (Stuttgart) 7194 1006 133 186 366 088 7874 275 3571 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 1 (Stuttgart) 123 50 47 212 85 69 991 129

Table 44 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 1 (Stuttgart) 177

18

Annex 3

Statistical calculations

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 47)Mandels h statistics(Sludge 1 - PBD 47)

Sample Sludge 1 NUM

Element PBD 47

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00213 0001 3 -021 005 - - 10L - - NUM46L 00273 0002 4 016 021 - - 46L - - NUM64L 00059 0000 4 -116 002 NUM - 64L - - NUM12L 00188 0000 4 -036 002 - - 12L - - NUM26L 00499 0024 2 157 223 Fail - - 26L - - NUM

Totgem 0025 0005 mgkg 1-level 172 (185) NUM (10L46L64L12L26L) -1Totstd= 0016 0010 5-level 157 (162) 5

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 5 Labs rejected (10L46L64L12L26L)

000 050 100 150 200 250

k-values

10L

46L

64L

12L

26L

Mandels k statistics(Sludge 1 - PBD 47)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

10L

46L

64L

12L

26L

Labo

rato

ries

NUM

-200 -100 000 100 200

h-values

10L

46L

64L

12L

26L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 47)

Sludge 1-PBD 47

Unit mgkg

Mandels k statistics(Soil 3 - PBD 47)Mandels h statistics(Soil 3 - PBD 47)

Sample Soil 3 Soil 3 - PBD 47 -- Mean PARM = 0001 [mgkg]

Element PBD 47

General calcparmT1= 134814E-02T2= 142830E-05T3= 13T4= 45T5= 22767E-06

n= variabelp= 4

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean26L 00007 0000 2 -143 001 00007 00000 2 1 00046L 00010 0001 4 010 181 00010 00008 4 3 00010L 00011 0000 3 049 023 00011 00001 3 2 00012L 00012 0000 4 084 081 00012 00004 4 3 000

Totgem 0001 0000 mgkg 1-level 149 (177) 4 00010 () 4 3Totstd= 0000 0000 5-level 142 (159)

RESULTS Mean = 000100 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000050 --gt 5031 r = 00014Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000050 --gt 5031 R = 00014Remarks none

000 050 100 150 200

k-values

26L

46L

10L

12L

Mandels k statistics(Soil 3 - PBD 47)

00 00 00 00 00 00 00 00 00 00 00

Deviation from Mean

26L

46L

10L

12L

Labo

rato

ries

Soil 3 - PBD 47 -- Mean PARM = 0001 [mgkg]

-200 -100 000 100

h-values

26L

46L

10L

12L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 47)

Soil 3-PBD 47

Unit mgkg

Mandels k statistics(Compost 1 - PBD 99)Mandels h statistics(Compost 1 - PBD 99)

Sample Compost 1 Compost 1 - PBD 99 -- Mean PARM = 0003 [mgkg]

Element PBD 99

General calcparmT1= 492124E-02T2= 148747E-04T3= 17T4= 61T5= 93196E-06

n= variabelp= 5

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00020 0000 4 -137 053 00020 00004 4 3 000

26L 00025 0000 2 -058 024 00025 00002 2 1 00010L 00029 0000 3 012 032 00029 00003 3 2 00046L 00033 0001 4 069 161 00033 00013 4 3 00012L 00036 0001 4 114 140 00036 00011 4 3 000

Totgem 0003 0001 mgkg 1-level 172 (185) 5 00029 () 5 4Totstd= 0001 0001 5-level 157 (162)

RESULTS Mean = 000286 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000088 --gt 3086 r = 00025Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000101 --gt 3525 R = 00028Remarks none

000 050 100 150 200

k-values

4L

26L

10L

46L

12L

Mandels k statistics(Compost 1 - PBD 99)

00 00 00 00 00 00 00 00 00 00

Deviation from Mean

4L

26L

10L

46L

12L

Labo

rato

ries

Compost 1 - PBD 99 -- Mean PARM = 0003 [mgkg]

-200 -100 000 100 200

h-values

4L

26L

10L

46L

12L

Labo

rato

ries

Mandels h statistics(Compost 1 - PBD 99)

Compost 1-PBD 99

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 99)Mandels h statistics(Sludge 1 - PBD 99)

Sample Sludge 1 Sludge 1 - PBD 99 -- Mean PARM = 0024 [mgkg]

Element PBD 99

General calcparmT1= 448050E-01T2= 112113E-02T3= 19T4= 73T5= 32972E-05

n= variabelp= 5

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean64L 00173 0002 4 -118 041 Fail 00173 00019 4 3 -0014L 00183 0002 4 -104 032 00183 00015 4 3 -001

12L 00227 0001 4 -038 022 00227 00010 4 3 00010L 00290 0001 3 055 021 00290 00010 3 2 00146L 00320 0002 4 100 039 00320 00018 4 3 00126L 00323 0011 2 105 234 - - 26L - - 001

Totgem 0025 0003 mgkg 1-level 187 (177) 5 00239 (26L) 5 4Totstd= 0007 0004 5-level 166 (154) 1

RESULTS Mean = 002385 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000153 --gt 643 r = 00043Between lab variance S2L = 000004Reproducibility var S2R = 000004Reproducibility std SR = 000666 --gt 2791 R = 00186Remarks 1 Lab rejected (26L)

000 050 100 150 200 250

k-values

64L

4L

12L

10L

46L

26L

Mandels k statistics(Sludge 1 - PBD 99)

00 00 00 00 00 00 00 00 00 00

Deviation from Mean

64L

4L

12L

10L

46L

26L

Labo

rato

ries

Sludge 1 - PBD 99 -- Mean PARM = 0024 [mgkg]

-200 -100 000 100 200

h-values

64L

4L

12L

10L

46L

26L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 99)

Sludge 1-PBD 99

Unit mgkg

Mandels k statistics(Soil 3 - PBD 99)Mandels h statistics(Soil 3 - PBD 99)

Sample Soil 3 NUM

Element PBD 99

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00017 0000 4 091 068 - - 10L - - NUM46L 00017 0001 4 100 211 - - 46L - - NUM64L 00005 0000 4 -106 023 NUM - 64L - - NUM12L 00012 0000 4 015 014 - - 12L - - NUM26L 00006 0000 2 -101 012 - - 26L - - NUM

Totgem 0001 0000 mgkg 1-level 172 (173) NUM (10L46L64L12L26L) -1Totstd= 0001 0000 5-level 157 (153) 5

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 5 Labs rejected (10L46L64L12L26L)

000 050 100 150 200 250

k-values

10L

46L

64L

12L

26L

Mandels k statistics(Soil 3 - PBD 99)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

10L

46L

64L

12L

26L

Labo

rato

ries

NUM

-200 -100 000 100 200

h-values

10L

46L

64L

12L

26L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 99)

Soil 3-PBD 99

Unit mgkg

Mandels k statistics(Compost 1 - PBD 100)Mandels h statistics(Compost 1 - PBD 100)

Sample Compost 1 Compost 1 - PBD 100 -- Mean PARM = 0001 [mgkg]

Element PBD 100

General calcparmT1= 124272E-02T2= 113129E-05T3= 14T4= 52T5= 46584E-07

n= variabelp= 4

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean26L 00006 0000 2 -131 037 Fail 00006 00001 2 1 00010L 00009 0000 4 003 083 00009 00002 4 3 00046L 00009 0000 4 016 115 00009 00002 4 3 00012L 00011 0000 4 112 136 Fail 00011 00003 4 3 000

Totgem 0001 0000 mgkg 1-level 149 (167) 4 00009 () 4 3Totstd= 0000 0000 5-level 142 (15)

RESULTS Mean = 000085 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000022 --gt 2531 r = 00006Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000025 --gt 2882 R = 00007Remarks none

000 050 100 150

k-values

26L

10L

46L

12L

Mandels k statistics(Compost 1 - PBD 100)

00 00 00 00 00 00 00 00 00 00 00

Deviation from Mean

26L

10L

46L

12L

Labo

rato

ries

Compost 1 - PBD 100 -- Mean PARM = 0001 [mgkg]

-200 -100 000 100 200

h-values

26L

10L

46L

12L

Labo

rato

ries

Mandels h statistics(Compost 1 - PBD 100)

Compost 1-PBD 100

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 100)Mandels h statistics(Sludge 1 - PBD 100)

Sample Sludge 1 Sludge 1 - PBD 100 -- Mean PARM = 0005 [mgkg]

Element PBD 100

General calcparmT1= 852065E-02T2= 412762E-04T3= 18T4= 68T5= 78914E-07

n= variabelp= 5

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00039 0000 4 -042 007 Fail 00039 00002 4 3 000

12L 00044 0000 4 -041 005 Fail 00044 00001 4 3 00010L 00046 0000 4 -041 013 Fail 00046 00003 4 3 00046L 00056 0000 4 -040 012 Fail 00056 00003 4 3 00026L 00059 0000 2 -040 013 Fail 00059 00003 2 1 00038L 02168 0006 4 204 244 Fail - - 38L - - 021

Totgem 0040 0001 mgkg 1-level 187 (177) 5 00049 (38L) 5 4Totstd= 0087 0002 5-level 166 (154) 1

RESULTS Mean = 000486 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000025 --gt 507 r = 00007Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000084 --gt 1731 R = 00024Remarks 1 Lab rejected (38L)

000 050 100 150 200 250

k-values

4L

12L

10L

46L

26L

38L

Mandels k statistics(Sludge 1 - PBD 100)

-01 00 01 01 02 02 03

Deviation from Mean

4L

12L

10L

46L

26L

38L

Labo

rato

ries

Sludge 1 - PBD 100 -- Mean PARM = 0005 [mgkg]

-100 000 100 200 300

h-values

4L

12L

10L

46L

26L

38L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 100)

Sludge 1-PBD 100

Unit mgkg

Mandels k statistics(Soil 3 - PBD 100)Mandels h statistics(Soil 3 - PBD 100)

Sample Soil 3 NUM

Element PBD 100

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00003 0000 4 -050 000 Fail - - 10L - - NUM46L 00003 0000 4 -050 000 Fail NUM - 46L - - NUM3L 305500 2051 2 150 200 Fail - - 3L - - NUM

26L 00005 0000 2 -050 000 Fail - - 26L - - NUM

Totgem 7638 0513 mgkg 1-level 149 (177) NUM (10L46L3L26L) -1Totstd= 15275 1025 5-level 142 (159) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (10L46L3L26L)

000 050 100 150 200

k-values

10L

46L

3L

26L

Mandels k statistics(Soil 3 - PBD 100)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

10L

46L

3L

26L

Labo

rato

ries

NUM

-100 000 100 200

h-values

10L

46L

3L

26L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 100)

Soil 3-PBD 100

Unit mgkg

Mandels k statistics(Compost 1 - PBD 153)Mandels h statistics(Compost 1 - PBD 153)

Sample Compost 1 NUM

Element PBD 153

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean44L 00053 0001 3 150 157 Fail - - 44L - - NUM46L 00007 0000 4 -044 111 Fail - - 46L - - NUM12L 00005 0000 4 -051 055 Fail - - 12L - - NUM26L 00005 0000 2 -054 001 Fail NUM - 26L - - NUM

Totgem 0002 0000 mgkg 1-level 149 (177) NUM (44L46L12L26L) -1Totstd= 0002 0000 5-level 142 (159) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (44L46L12L26L)

000 050 100 150 200

k-values

44L

46L

12L

26L

Mandels k statistics(Compost 1 - PBD 153)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

44L

46L

12L

26L

Labo

rato

ries

NUM

-100 000 100 200

h-values

44L

46L

12L

26L

Labo

rato

ries

Mandels h statistics(Compost 1 - PBD 153)

Compost 1-PBD 153

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 153)Mandels h statistics(Sludge 1 - PBD 153)

Sample Sludge 1 Sludge 1 - PBD 153 -- Mean PARM = 0004 [mgkg]

Element PBD 153

General calcparmT1= 676738E-02T2= 267609E-04T3= 18T4= 68T5= 19626E-05

n= variabelp= 5

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00024 0000 4 -157 017 00024 00002 4 3 000

12L 00038 0002 4 006 154 00038 00018 4 3 00046L 00039 0000 4 011 026 00039 00003 4 3 00026L 00039 0000 2 018 004 00039 00000 2 1 00064L 00049 0002 4 122 159 00049 00018 4 3 000

Totgem 0004 0001 mgkg 1-level 172 (173) 5 00038 () 5 4Totstd= 0001 0001 5-level 157 (153)

RESULTS Mean = 000378 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000123 --gt 3252 r = 00034Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000142 --gt 3754 R = 00040Remarks none

000 050 100 150 200

k-values

4L

12L

46L

26L

64L

Mandels k statistics(Sludge 1 - PBD 153)

00 00 00 00 00 00 00

Deviation from Mean

4L

12L

46L

26L

64L

Labo

rato

ries

Sludge 1 - PBD 153 -- Mean PARM = 0004 [mgkg]

-200 -100 000 100 200

h-values

4L

12L

46L

26L

64L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 153)

Sludge 1-PBD 153

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 154)Mandels h statistics(Sludge 1 - PBD 154)

Sample Sludge 1 NA

Element PBD 154

General calcparmT1= NAT2= NAT3=T4=T5=

n= variabelp=

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00021 0000 3 -100 021 NA - 4L - - NA

46L 00025 0000 4 115 018 NA - 46L - - NA64L 00021 0001 4 -066 179 - - 64L - - NA12L 00023 0000 4 050 085 - - 12L - - NA

Totgem 0002 0000 mgkg 1-level 149 (167) NA (4L46L64L12L) -1Totstd= 0000 0000 5-level 142 (15) 4

RESULTS Mean = NA mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NAReproducibility var S2R = NAReproducibility std SR = NA --gt NA R = NARemarks 4 Labs rejected (4L46L64L12L)

000 050 100 150 200

k-values

4L

46L

64L

12L

Mandels k statistics(Sludge 1 - PBD 154)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

4L

46L

64L

12L

Labo

rato

ries

NA

-100 000 100 200

h-values

4L

46L

64L

12L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 154)

Sludge 1-PBD 154

Unit mgkg

Mandels k statistics(Soil 3 - PBD 154)Mandels h statistics(Soil 3 - PBD 154)

Sample Soil 3 NUM

Element PBD 154

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

4L 00010 - 1 150 Fail - - 4L - - NUM46L 00001 0000 4 -053 096 Fail - - 46L - - NUM64L 00001 0000 4 -056 105 Fail NUM - 64L - - NUM12L 00002 0000 4 -040 099 Fail - - 12L - - NUM

Totgem 000037 0000 mgkg 1-level 149 (164) NUM (4L46L64L12L) -1Totstd= 000042 0000 5-level 142 (153) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (4L46L64L12L)

000 050 100 150

k-values

4L

46L

64L

12L

Mandels k statistics(Soil 3 - PBD 154)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

4L

46L

64L

12L

Labo

rato

ries

NUM

-100 000 100 200

h-values

4L

46L

64L

12L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 154)

Soil 3-PBD 154

Unit mgkg

Mandels k statistics(Compost 1 - PBD 209)Mandels h statistics(Compost 1 - PBD 209)

Sample Compost 1 NUM

Element PBD 209

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00065 0003 2 -049 032 - - 4L - - NUM

44L 00573 0021 4 150 197 Fail - - 44L - - NUM12L 00078 0001 4 -045 011 - - 12L - - NUM26L 00049 0000 2 -056 000 NUM - 26L - - NUM

Totgem 0019 0006 mgkg 1-level 149 (177) NUM (4L44L12L26L) -1Totstd= 0025 0010 5-level 142 (159) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (4L44L12L26L)

000 050 100 150 200

k-values

4L

44L

12L

26L

Mandels k statistics(Compost 1 - PBD 209)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

4L

44L

12L

26L

Labo

rato

ries

NUM

-100 000 100 200

h-values

4L

44L

12L

26L

Labo

rato

ries

Mandels h statistics(Compost 1 - PBD 209)

Compost 1-PBD 209

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 209)Mandels h statistics(Sludge 1 - PBD 209)

Sample Sludge 1 Sludge 1 - PBD 209 -- Mean PARM = 0249 [mgkg]

Element PBD 209

General calcparmT1= 394542E+00T2= 107296E+00T3= 16T4= 56T5= 19723E-02

n= variabelp= 5

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 01550 0055 4 -112 148 Fail 01550 00551 4 3 -009

46L 02050 0007 2 -053 019 02050 00071 2 1 -00412L 02137 0058 4 -042 155 02137 00576 4 3 -00426L 03149 0021 2 078 057 Fail 03149 00210 2 1 00764L 03577 0007 4 129 020 Fail 03577 00074 4 3 011

Totgem 0249 0030 mgkg 1-level 172 (185) 5 02493 () 5 4Totstd= 0084 0025 5-level 157 (162)

RESULTS Mean = 024926 mgkg

Repeatability variance S2r = 000179Repeatability std Sr = 004234 --gt 1699 r = 01186Between lab variance S2L = 000743Reproducibility var S2R = 000922Reproducibility std SR = 009604 --gt 3853 R = 02689Remarks none

000 050 100 150 200

k-values

4L

46L

12L

26L

64L

Mandels k statistics(Sludge 1 - PBD 209)

-01 -01 00 01 01 02

Deviation from Mean

4L

46L

12L

26L

64L

Labo

rato

ries

Sludge 1 - PBD 209 -- Mean PARM = 0249 [mgkg]

-200 -100 000 100 200

h-values

4L

46L

12L

26L

64L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 209)

Sludge 1-PBD 209

Unit mgkg

Mandels k statistics(Soil 3 - PBD 209)Mandels h statistics(Soil 3 - PBD 209)

Sample Soil 3 Soil 3 - PBD 209 -- Mean PARM = 0258 [mgkg]

Element PBD 209

General calcparmT1= 596398E+00T2= 191917E+00T3= 22T4= 84T5= 13249E-02

n= variabelp= 6

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean26L 01162 0021 2 -108 074 Fail 01162 00207 2 1 -0144L 01303 0031 4 -097 111 Fail 01303 00312 4 3 -013

46L 01975 0036 4 -046 128 Fail 01975 00359 4 3 -00644L 02898 0035 4 024 124 Fail 02898 00346 4 3 00312L 03895 0018 4 100 065 Fail 03895 00181 4 3 01364L 04260 0022 4 127 078 Fail 04260 00219 4 3 017

Totgem 0258 0027 mgkg 1-level 187 (177) 6 02582 () 6 5Totstd= 0132 0008 5-level 166 (154)

RESULTS Mean = 025818 mgkg

Repeatability variance S2r = 000083Repeatability std Sr = 002878 --gt 1115 r = 00806Between lab variance S2L = 001640Reproducibility var S2R = 001723Reproducibility std SR = 013127 --gt 5084 R = 03676Remarks none

000 050 100 150

k-values

26L

4L

46L

44L

12L

64L

Mandels k statistics(Soil 3 - PBD 209)

-02 -01 -01 00 01 01 02 02

Deviation from Mean

26L

4L

46L

44L

12L

64L

Labo

rato

ries

Soil 3 - PBD 209 -- Mean PARM = 0258 [mgkg]

-200 -100 000 100 200

h-values

26L

4L

46L

44L

12L

64L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 209)

Soil 3-PBD 209

Unit mgkg

Mandels k statistics(Compost 1 - Sum PBD)Mandels h statistics(Compost 1 - Sum PBD)

Sample Compost 1 Compost 1 - Sum PBD -- Mean PARM = 0009 [mgkg]

Element Sum PBD

General calcparmT1= 154064E-01T2= 169065E-03T3= 18T4= 68T5= 11354E-04

n= variabelp= 5

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00031 0002 4 -067 016 00031 00016 4 3 -0014L 00055 0005 4 -056 048 00055 00047 4 3 000

46L 00085 0003 4 -042 031 00085 00030 4 3 00026L 00123 0000 2 -024 003 00123 00002 2 1 00012L 00154 0002 4 -011 021 00154 00021 4 3 00144L 00613 0023 4 200 237 Fail - - 44L - - 005

Totgem 0018 0006 mgkg 1-level 187 (177) 5 00089 (44L) 5 4Totstd= 0022 0009 5-level 166 (154) 1

RESULTS Mean = 000893 mgkg

Repeatability variance S2r = 000001Repeatability std Sr = 000296 --gt 3308 r = 00083Between lab variance S2L = 000002Reproducibility var S2R = 000003Reproducibility std SR = 000570 --gt 6374 R = 00159Remarks 1 Lab rejected (44L)

000 050 100 150 200 250

k-values

10L

4L

46L

26L

12L

44L

Mandels k statistics(Compost 1 - Sum PBD)

00 00 00 00 00 00 01 01

Deviation from Mean

10L

4L

46L

26L

12L

44L

Labo

rato

ries

Compost 1 - Sum PBD -- Mean PARM = 0009 [mgkg]

-100 000 100 200

h-values

10L

4L

46L

26L

12L

44L

Labo

rato

ries

Mandels h statistics(Compost 1 - Sum PBD)

Compost 1-Sum PBD

Unit mgkg

Mandels k statistics(Sludge 1 - Sum PBD)Mandels h statistics(Sludge 1 - Sum PBD)

Sample Sludge 1 Sludge 1 - Sum PBD -- Mean PARM = 0256 [mgkg]

Element Sum PBD

General calcparmT1= 531806E+00T2= 162188E+00T3= 22T4= 84T5= 25223E-02

n= variabelp= 6

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00423 0025 4 -156 044 Fail 00423 00252 4 3 -02146L 01808 0118 4 -049 205 - - 46L - - -0074L 01810 0056 4 -049 097 01810 00558 4 3 -007

38L 02168 0006 4 -022 010 02168 00059 4 3 -00412L 02890 0065 4 034 113 02890 00647 4 3 00364L 03958 0008 4 116 014 Fail 03958 00079 4 3 01426L 04094 0034 2 126 059 Fail 04094 00337 2 1 015

Totgem 0245 0044 mgkg 1-level 198 (179) 6 02557 (46L) 6 5Totstd= 0130 0039 5-level 171 (155) 1

RESULTS Mean = 025570 mgkg

Repeatability variance S2r = 000158Repeatability std Sr = 003970 --gt 1553 r = 01112Between lab variance S2L = 001807Reproducibility var S2R = 001964Reproducibility std SR = 014015 --gt 5481 R = 03924Remarks 1 Lab rejected (46L)

000 050 100 150 200 250

k-values

10L

46L

4L

38L

12L

64L

26L

Mandels k statistics(Sludge 1 - Sum PBD)

-03 -02 -02 -01 -01 00 01 01 02 02

Deviation from Mean

10L

46L

4L

38L

12L

64L

26L

Labo

rato

ries

Sludge 1 - Sum PBD -- Mean PARM = 0256 [mgkg]

-200 -100 000 100 200

h-values

10L

46L

4L

38L

12L

64L

26L

Labo

rato

ries

Mandels h statistics(Sludge 1 - Sum PBD)

Sludge 1-Sum PBD

Unit mgkg

Mandels k statistics(Soil 3 - Sum PBD)Mandels h statistics(Soil 3 - Sum PBD)

Sample Soil 3 Soil 3 - Sum PBD -- Mean PARM = 0227 [mgkg]

Element Sum PBD

General calcparmT1= 610980E+00T2= 200876E+00T3= 26T4= 100T5= 13106E-02

n= variabelp= 7

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00028 0001 4 -037 000 Fail 00028 00005 4 3 -02226L 01179 0021 2 -036 003 Fail 01179 00208 2 1 -0114L 01305 0031 4 -036 004 Fail 01305 00308 4 3 -010

46L 02065 0035 4 -036 005 Fail 02065 00350 4 3 -00244L 02923 0037 4 -035 005 Fail 02923 00365 4 3 00712L 04051 0015 4 -034 002 Fail 04051 00149 4 3 01864L 04314 0022 4 -033 003 Fail 04314 00223 4 3 0203L 305500 2051 2 247 283 Fail - - 3L - - 3032

Totgem 4017 0276 mgkg 1-level 206 (181) 7 02266 (3L) 7 6Totstd= 10722 0717 5-level 175 (156) 1

RESULTS Mean = 022663 mgkg

Repeatability variance S2r = 000069Repeatability std Sr = 002626 --gt 1159 r = 00735Between lab variance S2L = 002568Reproducibility var S2R = 002637Reproducibility std SR = 016238 --gt 7165 R = 04547Remarks 1 Lab rejected (3L)

000 050 100 150 200 250 300

k-values

10L

26L

4L

46L

44L

12L

64L

3L

Mandels k statistics(Soil 3 - Sum PBD)

-50 00 50 100 150 200 250 300 350

Deviation from Mean

10L

26L

4L

46L

44L

12L

64L

3L

Labo

rato

ries

Soil 3 - Sum PBD -- Mean PARM = 0227 [mgkg]

-100 000 100 200 300

h-values

10L

26L

4L

46L

44L

12L

64L

3L

Labo

rato

ries

Mandels h statistics(Soil 3 - Sum PBD)

Soil 3-Sum PBD

19

Annex 4

Raw data submitted

Sample Compost1 Sample Compost 1 Sample Compost 1Element PBD 99 Element PBD 100 Element PBD 153

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]4L 00021 10L 00008 44L 000504L 00024 10L 00008 44L 000604L 00014 10L 00007 44L 000504L 00020 10L 00011 46L 00004

10L 00029 46L 00007 46L 0001210L 00027 46L 00012 46L 0000410L 00032 46L 00009 46L 0000946L 00025 46L 00007 12L 0000446L 00052 12L 00008 12L 0000846L 00029 12L 00012 12L 0000446L 00026 12L 00008 12L 0000712L 00026 12L 00014 26L 0000512L 00043 26L 00007 26L 0000512L 00026 26L 0000612L 0004726L 0002626L 00024

Sample Compost 1 Sample Compost 1 Sample Compost 1Element PBD 154 Element PBD 183 Element PBD 196

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]4L 00010 46L 00002 46L 00011

46L 00003 46L 00024 46L 0000846L 00007 46L 00021 12L 0000246L 00003 46L 00003 12L 0000346L 00004 12L 00003 12L 0000112L 00003 12L 00011 12L 0000212L 00005 12L 0000312L 00031 12L 0000312L 00006

Sample Compost 1 Sample Compost 1 Sample Compost 1Element PBD 197 Element PBD 203 Element PBD 209

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00002 46L 00010 4L 0004146L 00023 12L 00002 4L 0008946L 00022 12L 00003 44L 0041012L 00004 12L 00002 44L 0084012L 00006 12L 00002 44L 0064012L 00003 44L 0040012L 00004 12L 00079

12L 0007312L 0006512L 0009326L 0004926L 00049

Sample Compost 1Element PBD 47

LAB PARM [mgkg]26L 0003826L 00039

Element PBD 99 Element PBD 47 Element PBD 209LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]

4L 00170 10L 00210 4L 010004L 00200 10L 00220 4L 018004L 00170 10L 00210 4L 012004L 00190 46L 00300 4L 0220010L 00280 46L 00280 46L 0210010L 00300 46L 00250 46L 0200010L 00290 46L 00260 64L 0351846L 00340 64L 00059 64L 0363846L 00330 64L 00057 64L 0364546L 00300 64L 00062 64L 0350846L 00310 64L 00060 12L 0220964L 00194 12L 00191 12L 0177164L 00154 12L 00187 12L 0292264L 00185 12L 00190 12L 0164664L 00159 12L 00186 26L 0329712L 00242 26L 00666 26L 0300012L 00223 26L 0033212L 0022112L 0022226L 0024626L 00400

Element PBD 203 Element PBD 197 Element PBD 196LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00022 46L 00027 46L 0002446L 00014 46L 00024 46L 0002264L 00036 12L 00161 64L 0005864L 00058 12L 00060 64L 0006512L 00063 12L 00061 12L 0004812L 00034 12L 00036 12L 0002512L 00038 12L 0003212L 00027 12L 00022

Element PBD 183 Element PBD 154 Element PBD 153LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00049 4L 00020 4L 0002246L 00035 4L 00022 4L 0002446L 00036 4L 00020 4L 0002246L 00034 46L 00025 4L 0002664L 00027 46L 00025 46L 0004064L 00023 46L 00025 46L 0004264L 00024 46L 00023 46L 0003564L 00020 64L 00034 46L 0003812L 00230 64L 00023 64L 0007412L 00032 64L 00017 64L 0004712L 00031 64L 00011 64L 0004612L 00030 12L 00030 64L 0003026L 00007 12L 00021 12L 0006526L 00008 12L 00021 12L 00029

12L 00021 12L 0003226L 00015 12L 0002926L 00019 26L 00039

26L 00040

Element PBD 100LAB PARM [mgkg]

4L 000384L 000414L 000374L 00038

38L 0219038L 0220038L 0208038L 0220010L 0004410L 0005010L 0004310L 0004646L 0005746L 0005946L 0005346L 0005312L 0004312L 0004512L 0004312L 0004326L 0006226L 00057

Sample Soil 3 Sample Soil 3 Sample Soil 3Element PBD 99 Element PBD 47 Element PBD 100

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]10L 00016 10L 00011 10L 0000310L 00019 10L 00010 10L 0000410L 00013 10L 00012 10L 0000410L 00019 46L 00007 10L 0000246L 00025 46L 00022 46L 0000246L 00025 46L 00005 46L 0000646L 00008 46L 00007 46L 0000246L 00011 12L 00010 46L 0000264L 00005 12L 00017 3L 29100064L 00005 12L 00010 3L 32000064L 00006 12L 00009 26L 0000564L 00007 26L 00007 26L 0000512L 00012 26L 0000712L 0001312L 0001312L 0001226L 0000526L 00006

Sample Soil 3 Sample Soil 3 Sample Soil 3Element PBD 153 Element PBD 154 Element PBD 196

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]44L 00050 4L 00010 46L 0000744L 00050 46L 00001 46L 0001146L 00002 46L 00002 46L 0000846L 00003 46L 00001 46L 0001146L 00002 46L 00002 64L 0002646L 00002 64L 00001 64L 0002664L 00001 64L 00001 64L 0002964L 00001 64L 00001 64L 0003464L 00001 64L 00002 12L 0004564L 00002 12L 00003 12L 00032

12L 00002 12L 0002212L 00002 12L 0002112L 00002

Sample Soil 3 Sample Soil 3 Sample Soil 3Element PBD 197 Element PBD 203 Element PBD 209

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00006 46L 00011 4L 0091046L 00013 46L 00017 4L 0150046L 00011 46L 00015 4L 0120046L 00013 46L 00018 4L 0160012L 00090 64L 00013 44L 0337012L 00056 64L 00014 44L 0281012L 00033 64L 00016 44L 0287012L 00032 64L 00015 44L 02540

12L 00055 46L 0230012L 00041 46L 0220012L 00027 46L 0150012L 00026 46L 01900

64L 0438164L 0401664L 0414464L 0449812L 0367112L 0397812L 0409112L 03838

Sample Soil 3 26L 0102Element PBD 183 26L 0131

LAB PARM [mgkg]46L 0000746L 0000846L 0005846L 0000764L 0000264L 0000364L 0000364L 0000312L 0001512L 0001112L 0000712L 00007

European Commission EUR 23003 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on polybrominated diphenylethers Author(s) E Sobiecka H van der Sloot D Barcelo B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 68 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07403-5 Abstract Project HORIZONTAL is interdisciplinary aiming at a harmonisation and horizontal standardisation of test procedures in particular for sludge soils and biowastes In the context of this standardization project a series of draft technical specification were designed upon an extensive desk study fine-tuned after expert consultations and finally validated in international intercomparisons exercise This report summarises the work performed within the validation study of the draft standard for the determination of polybrominated diphenylethers (PBDE) in soils sludge and treated bio-waste using gas-chromatography method with mass selective detection (GC-MS) It further explains the underlying statistical concept for the calculation of reproducibility and repeatability from intercomparisons data In addition all single values results of the statistical evaluation as well as background information on the validation materials used are described and explained

The mission of the JRC is to provide customer-driven scientific and technical support for the conception development implementation and monitoring of EU policies As a service of the European Commission the JRC functions as a reference centre of science and technology for the Union Close to the policy-making process it serves the common interest of the Member States while being independent of special interests whether private or national

LB

-NA

-23003-EN

-C

Abbreviations Throughout this report the following abbreviations are used ANOVA Analysis of variances

CAS Chemical Abstracts System

CEN Comitteeacute Europeacuteen de Normalisation

DG Directorate General

ECD Electron Capture Detector

ECN Energy Research Centre for the Netherlands

EU European Union

IES Institute for Environment and Sustainability

IT Information Technology

ISO International Organization for Standardisation

JRC Joint Research Centre

GC Gas Chromatography

MILC Measure Interlaboratory Comparison

MS Mass Spectroscopy

p Number of labs

PBDE Polybrominated Diphenylethers

r Repeatability limit

R Reproducibility limit

sr Repeatability standard deviation

sR Reproducibility standard deviation

TC Technical Committee

4

Table of Contents Summary 2 Abbreviations 3 Table of Contents 4

Introduction to the validation project 5 11 Statistical concept underlying the validation 6

111 Introduction to the statistical model 6 112 Requirements for precision experiment 7 113 Statistical analysis 8

12 Validation exercise for PBDE 8 121 Compounds to be measured 8 122 Samples dispatched for the validation of PBDE 8 123 Draft standards to be followed 8 124 Analytical programm 8 125 Timing and Submission of data 9 126 Participants 10

13 Summary results and derived performance characteristics 11 14 Annexes 15

5

Introduction to the validation project Project HORIZONTAL is interdisciplinary aiming at a harmonisation and horizontal standardisation of test procedures in particular for sludges soils and biowastes It was created as in response to the European Commission Mandate M 330 given to CEN asking for the development and validation of those standards in support of forthcoming EU Directives such as

o The revision of the Sewage Sludge Directive 86278EEC o The Directive on the biological treatment of biodegradable waste o The initiative on a legal framework for soil monitoring in Europe

This mandate explicitly considers standards for the entire analytical procedure (ie sampling pre-treatment and analytical measurement methods for inorganic organic hygiene and biological parameters) These are grouped into classes according to their physicalchemical properties which in turn determine the methods needed to quantify the potential impact on human and animal health plant uptake soil function and groundwater quality As the materials generally feature a mixture of different types of contaminants it is important to provide an integrated answer covering evaluation of all relevant pollutants In order to fulfil the requirements of the aforementioned mandate the European Commissions Joint Research Centre (JRC) and its Directorate-General for Environment (DG ENV) together with the Technical Committees of the European Standardisation Committee (CEN TCs) concerned designed a pre-normative research initiative called Project HORIZONTAL and presented it to the Commission and the Environmental Authorities in the Member States After an extensive literature research and careful evaluation of the feasibility of a given horizontal standard the standards were drafted and finally validated in an European laboratory intercomparison The underlying statistical concept information about the materials used details about the participants measurement results obtained as well as the derived performance characteristics obtained for the determination of polybrominated diphenylethers (PBDE) are described hereafter

6

11 Statistical concept underlying the validation According to the requirements of the work package concerning data handling amp interpretation of the project HORIZONTAL-ORG the respective validation intercomparisons have to be evaluated according to the principles laid down in ISO standard 5725-21994 In particular repeatability and reproducibility of the draft standard methods have to be determined The determination of trueness would require the availability of independent reference values for the materials investigated This however is not possible and was not requested in the frame of this work In the following the approach chosen is explained

111 Introduction to the statistical model The statistical model used in ISO 5725 for estimation of accuracy of a measurement method assumes that every test result is the sum of three components

eBmy ++= y test result m general mean B laboratory component of bias under repeatability conditions e random error occurring in every measurement under repeatability conditions

In the workprogram the quantification of term e is explicitly asked for (ie repeatability and reproducibility) The repeatability variance is measured directly as the variance of the error term e but the reproducibility depends on the sum of the repeatability variance and the between-laboratory variance

( )er var=σ 22rLR σσσ += with ( )BL var=σ

However soil biowaste and sludge are multi-phase materials ie they contain two or more distinct types of particles which are fundamentally different in their properties and composition As a consequence this introduces an important source of variation for the intercomparison exercise which needs to be considered ie the inherent heterogeneity of the materials Thus a contribution of variation between samples H is introduced to the general statistical model

HeBmy +++= Using ANOVA techniques the different variances are calculated and separated for the evaluation

7

112 Requirements for precision experiment

Layout of the experiment A suite of 10 to 12 different materials (soil sludge and biowaste) has been made available for the intercomparison exercise For each parameter investigated at least 10 to laboratories should be nominated to participate The same laboratories should be used for different parameters as far as possible Due to the complexity of analysis and the respective workload to the laboratories it was decided to propose three materials for the validation of the PBDE draft standard Each laboratory received two bottles of each material and was be requested to perform 4 independent analyses per material1 (2 per bottle) using the respective draft standard methods The 4 analysis per material should be carried out under repeatability conditions (ie same operator2 same equipment within a short period of time) As far as possible also the different materials should be measured under repeatability conditions however changes of eg operator or equipment are permitted but must be reported Likewise different materials can be analysed on different days if necessary Equipment used in the experiment needed to be checked prior to the experiment according to the requirements of the draft standard The results of these checks have to be documented Similarly date and time of each measurement had to be recorded for verification of repeatability conditions An appropriate timeframe for the entire exercise has been set and was to be respected

Recruitment of the laboratories Each sub-workpackage leader of HORIZONTAL was asked to select the laboratories using the information from section 52 of ISO 5725-21994 and provide the signed questionnaires (see also Annex 1) The workpackage leaders were responsible for providing the laboratories with the draft standard method and explaining the context of this exercise

Preparation and use of the materials Materials used for the exercise were prepared according to the general requirements for reference materials as laid down in ISO Guide 34 Materials were accompanied by instructions for use

Reporting of results Online submissions of results using an internet-based IT platform as well as XLS-Spreadsheets were used In case of online data submission the participating laboratories received a unique and confidential login and password in due time enabling them to

1 Independent analysis means analysis of independent test portions applying the entire analytical scheme to this test portion from eg extraction to quantification For instance it does not mean replicate injections of aliquots into a GC-MS instrument 2 Operator in this context may also consist of a fixed team of persons eg one person performing extraction one clean-up one quantification

8

enter their data in a structured form For authentication purposes a signed printout had to be submitted by mail The online data submission included a detailed questionnaire for additional information on the measurements

113 Statistical analysis Statistical analysis of data followed the requirements of ISO 5725-21994 and ISO 5725-51998 Appropriate tests for the homogeneity of variance detection of outliers and normal distribution were applied Statistical evaluation was done using an Excel Macro developed tested and successfully applied in other occasion by ECN Evaluation was executed jointly by JRC and ECN

12 Validation exercise for PBDE

121 Compounds to be measured The following compound were selected for the validation exercise Tetra-BDE-47 Penta-BDE-100 Penta-BDE-99 Hexa-BDE-154 Hexa-BDE-153 Hepta-BDE-183 Octa-BDE-196 Octa-BDE-197 Octa-BDE-203 Deca-BDE-209

122 Samples dispatched for the validation of PBDE After a preliminary rough screening the following materials were used for the validation round of PBDE

bull Compost 1 A pollutant loaded compost material from Vienna bull Sewage Sludge 1 A mixed sewage sludge from Essen bull Soil 3 A sludge amended soil from Barcelona

A more detailed description of background concentrations can be found in Annex 2 to this report The samples were dispatched simultaneously to all participants using a private courier service

123 Draft standards to be followed The draft standards to be followed could be downloaded following this link which is situated on the website of the Project HORIZONTAL httpwwwecnnldocssocietyhorizontalBFR_Standard_for_validationpdf

124 Analytical programm Of each of the three materials 2 bottles had to be analysed and each bottle had to analysed independently twice As mentioned above analyses were to be done under repeatability conditions Results were to be reported referring to DRY MATTER content The choice how to apply dm correction was free for each participant

9

125 Timing and Submission of data Dispatch of samples was done on the 18th of October 2006 For users of the Online data submission system (MILC) User Registration was possible from 14th of November 2006 with opening of the MILC Data Submission on 1st of December 2006 The deadline for submission of results has been set for PBDE to the 12th of January 2007 but was extended to the end of the same months After that no further submission was possible Alternatively the participants were allowed to submit data electronically as Excel sheet using simply Email All data were treated in a confidential way Any presentation hereafter will refer only to numerical data and it will not be possible to identify the originating laboratory Lab Codes displayed are NOT related to the order of laboratories hereafter In addition to the information provide an Helpdesk was implemented in order to give quick and individual response to the participants during and immediately after the validation study In case of doubt and suspected transcription errors further enquires were conducted by JRC

10

126 Participants The following table lists the participating organisations and entities in the validation exercise for the horizontal PBDE standard

bull Austria o Umweltbundesamt

bull Czech Republic o Povodi Labe statni podnik - OVHL Laboratory

bull France o CIRSEE o CTC Environnement o INERIS

bull Germany o Federal Environmental Agency Section III 34 Laboratory Methods for

the Surveillance of Waste and Wastewater (UBA) bull Italy

o European Commission DG JRC IES bull Spain

o Consejo Superior de Investigaciones Cientificas (CSIC)

bull Sweden o ALCONTROL AB

11

13 Summary results and derived performance characteristics The result of the various statistical evaluation including outlier tests calculation of repeatability and reproducibility standard deviation for the congeners of interest can be found in Annex 3 of this report In addition all data submitted by the participants as well as those considered for the calculation of the performance characteristics are listed in Annex 3 to this report Based on these calculations the following results were obtained in the validation round upon statistical evaluation according to ISO 5725-2 The average values the repeatability standard deviation (sr) and the reproducibility standard deviation (sR) were obtained (Table1) The repeatability is determined as an interval around a measurement result (ie repeatability limit) This interval corresponds to the maximum difference that can be expected (with a 95 statistical confidence) between one test result and another both test results being obtained under the following conditions The tests are performed in accordance with all the requirements of the present standard by the same laboratory using its own facilities and testing laboratory samples obtained from the same primary field sample and prepared under identical procedures The repeatability limit was calculated using the relationship r test = f radic2 s rtest with the critical range factor f = 2 The reproducibility like repeatability is also determined as an interval around a measurement result (ie reproducibility limit) This interval corresponds to the maximum difference that can be expected (with a 95 statistical confidence) between one test result and another test result obtained by another laboratory both test results being obtained under the following conditions The tests are performed in accordance with all the requirements of the present standard by two different laboratories using their own facilities and testing laboratory samples obtained from the same primary field sample and prepared under identical procedures The reproducibility limit was calculated using the relationship R = f radic2 sR with the critical range factor f = 2

12

Table 1 - Results of the interlaboratory comparison studies of the determination of selected polybrominated diphenyl ethers (PBDE) by gaschromatography with mass spectrometric detection (GC-MS) in soil sludge and treated biowaste All concentrations are expressed in mgkg dm

Matrix Parameter Mean sr sR r R p Outliers Used No of data

No of data reported below

detection

Total no of data

Sludge 1 PBD 47 00181 461 4 15 5 20 Compost 1 00039 94 3 12 0 12 Soil 3 00010 50 50 00014 00014 4 0 13 10 23 Sludge 1 PBD 99 00239 64 28 00043 00186 5 1 19 0 23 Compost 1 00029 31 35 00025 00028 5 0 17 4 21 Soil 3 00013 499 4 16 8 24 Sludge 1 PBD 100 00049 51 17 00007 00024 5 1 18 2 24 Compost 1 00009 25 29 00006 00007 4 0 14 7 21 Soil 3 61103 211 3 10 15 25 Sludge 1 PBD 153 00038 33 38 00034 0004 5 0 18 0 18 Compost 1 00019 116 3 11 3 14 Soil 3 00011 177 2 10 10 20 Sludge 1 PBD 154 00023 234 4 15 2 17 Compost 1 00008 1118 3 9 5 14

13

Matrix Parameter Mean sr sR r R p Outliers Used No of data

No of data reported below

detection

Total no of data

Soil 3 00002 1049 4 13 6 19 Sludge 1 PBD 183 00048 1217 3 12 2 14 Compost 1 00009 1048 2 8 5 13 Soil 3 00011 1395 3 12 6 18 Sludge 1 PBD 196 00037 470 2 8 7 15 Compost 1 00004 950 2 6 4 10 Soil 3 00023 519 3 12 2 14 Sludge 1 PBD 197 00062 834 2 6 8 14 Compost 1 00009 1001 2 7 7 14 Soil 3 00032 904 2 8 6 14 Sludge 1 PBD 203 00037 461 2 8 4 12 Compost 1 00004 978 2 5 3 8 Soil 3 00022 598 3 12 0 12 Sludge 1 PBD 209 02493 170 39 01186 02689 5 0 16 2 18 Compost 1 00273 104 3 10 5 15 Soil 3 02582 1115 51 00806 03676 6 0 22 0 22

14

Matrix Parameter Mean sr sR r R p Outliers Used No of data

No of data reported below

detection

Total no of data

Sludge 1 Sum PBD 0256 155 548 0111 0392 6 1 22 Compost 1 0009 331 637 0008 0016 5 1 18 Soil 3 0227 116 717 0074 0455 7 1 26 Abbreviations sr Repeatability standard deviation SR Reproducibility standard deviation r Repeatability limit (comparing two measurements) R Reproducibility limit (comparing two measurements) p Number of labs determination not possible

15

14 Annexes Annex 1 Model questionnaire to be filled by the participating laboratories Annex 3 Report on the validation materials used Annex 2 Statistical calculations Annex 3 Data submitted

16

Annex 1

Model questionnaire to be filled by the participating laboratories

Model questionnaire to be filled by the participating laboratories Name of laboratory Contact person Contact details email Phone Fax Mail address of lab Dispatch address of lab for shipment of samples (no PO boxes) Title of measurement method (copy attached) Our laboratory is willing to participate in the precision experiment for this draft standard method

Yes No As participant we understand that

bull All essential apparatus chemicals and other requirements specified in the method must be available in our laboratory when the programme begins

bull Specified timing requirements such as starting and finishing date of the programme must be rigidly met

bull The method must be strictly adhered to bull Samples must be handled in accordance with instructions bull A qualified operator must perform the measurements

Having studied the method and having made a fair appraisal of our capabilities and facilities we feel that we will be adequately prepared for cooperative testing of this method Comments helliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphellip Signature Date

17

Annex 2

Report on the validation materials used

VI

Abstract This report gives an overview on the available analytical information on the following raw materials to be used for the production of validation materials of the so-called Project HORIZONTAL

bull Four sludge materials from Duumlsseldorf Germany

bull An agricultural soil material from Reading United Kingdom

bull A compost material from Vienna Austria

bull A compost material from Korschenbroich Germany

bull A sludge-amended agricultural soil from Pavia Province Italy

bull A sludge-amended soil from Barcelona Spain

bull A sludge-amended soil from Essen Germany

bull A long-term sludge exposed soil from Hohenheim Germany

VII

List of Abbreviations Throughout this report the following abbreviations are used

AOX absorbable organic halogens

Corg organic carbon content

Ctotal total carbon content

CAT cation exchangeable

CDD chlorinated dibenzodioxin

CDF chlorinated dibenzofuran

DEHP di(2-ethylhexyl)phthalate

DM dry matter

EPA Environment Protection Agency

EU European Union

FM fresh matter

Hp hepta

Hx hexa

IES Institute for Environment and Sustainability

IRMM Institute for Reference Materials and Measurements

JRC Joint Research Centre

LAS linear alkylsulfonates

LoD limit of detection

LUA Landesumweltamt

Ntotal total nitrogen content

NH4-N Ammonium nitrogen

NO3-N Nitrate nitrogen

NP nonylphenol

NRW North Rhine Westphalia

O octa

P poly

PAH polycyclic aromatic hydrocarbon

PCB polychlorinated biphenyl

Pe penta

T tetra

TEQ toxicity equivalent

UBA Umweltbundesamt

WHO World Health Organization

WWTP waste water treatment plant

6

1 Introduction This report gives an overview on the available analytical information on the following raw materials to be used for the production of validation materials of the so-called Project HORIZONTAL

bull Four sludge materials from Duumlsseldorf Germany

bull An agricultural soil material from Reading United Kingdom

bull A compost material from Vienna Austria

bull A compost material from Korschenbroich Germany

bull A sludge-amended agricultural soil from Pavia Province Italy

bull A sludge-amended soil from Barcelona Spain

bull A sludge-amended soil from Essen Germany

bull A long-term sludge exposed soil from Hohenheim Germany

The following analytical information was gathered partly before and during the sampling of the raw materials to be used for the production of the HORIZONTAL validation materials The material were sampled by IES and shipped to IRMM in the course of the year 2005 The information gathered was then completed by various analytical screenings for PAHs and PCBs done by the Institute for Reference Materials and Measurements Geel Belgium for phthalates done by UBA Berlin Germany for PBDE done by IIQAB-CSIC Barcelona Spain for trace elements and some selected major and minor elements by the Institute for Environment and Sustainability Ispra Italy

The work compiled hereafter is based on the numerous additional efforts of the scientists working at various members of the consortium Project HORIZONTAL-Org and contributing organisations

This work is gratefully acknowledged

2 Overview on property values

21 Sludge materials from Duumlsseldorf Germany

The various sewage sludge materials originate from various installations in the North Rhine Westphalia and were produced and sampled by staff from the Landesumweltamt (LUA) NRW under the responsibility from Dr K Furtmann

In total four sludge materials (Sludge A and D from a major municipal WWTP Sludge B from a municipal WWTP with industrial input and Sludge C from a municipal WWTP with high PCB-Content) were obtained and will be blended to two final materials Before sampling the following analytical data for a typical sample were received

7

Table 1 ndash Analytical data obtained on an average sludge sample in LUA NRW (with courtesy of K Furtmann LUA Duumlsseldorf)

Parameter Concentration PCB 120 ugkg DEHP 110 mgkg PAH 5 mgkg (EPA) PCDDF 15 ng TEkg PBDE 400 ugkg NP 40 mgkg LAS 3 gkg AOX 300 mgkg

Subsequent screening led to the information displayed hereafter It should be stressed that the data were obtained as SCREENING information on the UNTREATED or partially treated raw materials Therefore the final target values which are relevant for the validation intercomparison can be different

Table 2 ndash Analytical data obtained on a first screening on the sludge samples from LUA NRW

Sewage sludge A

Dusseldorf

sewage sludge D

Dusseldorf PCB (ngg) 28 62 35 52 101 65 101 31 38 118 49 40 153 30 33 105 24 11 138 46 38 156 lt1 lt1 180 34 23 170 23 19 PAH (ngg) Naphtalene 34 381 Acenaphtylene 15 43 Acenaphthene 81 108 Fluorene 94 1167 Phenantrene 3440 Anthracene 22 344 Flouranthene 316 4817 Pyrene 235 3011 Benz(a)anthracene 473 791 Chrysene 691 1078 Benz(b)fluoranthene 538 1688 Benz(k)fluoranthene 228 635 Benz(a)pyrene 383 1114 Indeno(123-cd)pyrene 92 229 Dibenzo(ah)anthracene 71 70 Benzo(ghi)perylene 80 185

8

Table 3 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Sludge D (1) 0135 41474 385 Sludge B (2) 0538 0034 30634 547 Sludge A (3) 0184 0037 31399 146 Sludge C (4) 0354 1528 6678 229

Table 4 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Sludge 2

(B)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

554

959

694

591

772

509

nq

nq

970

2216

2379

Table 5 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena IES Ispra Spain) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Sludge 1 (D) 265 290 533 359 1231 338 784 438 lt 005 232 786 Sludge 2 (B) 119 311 626 202 278 299 722 251 lt 005 118 625 Sludge 3 (A) 168 360 621 332 847 416 119 451 lt 005 116 1237 Sludge 4 (C) 563 198 116 273 726 511 473 618 lt 005 444 2015

Table 6 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Sludge 1 (D) 2154 58 844 099 103 101 4367 lt15 50448 Sludge 2 (B) 1067 366 692 046 1491 077 5217 lt15 57633 Sludge 3 (A) 731 663 684 035 1287 068 3733 lt15 60369 Sludge 4 (C) 4379 965 527 163 522 107 5628 lt15 23945

Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM)Sludge 1 (D) 03 2403 101 1002 350 15 1944 132Sludge 2 (B) 031 315 97 879 172 12 514 180Sludge 3 (A) 031 1281 153 1567 265 16 1440 168Sludge 4 (C) 055 231 628 2625 371 81 1101 244

9

22 Agricultural soil material from Reading United Kingdom

The material was proposed by the University of Reading (S Nortcliff) and was sampled from a site called ldquoFrogmore Farmrdquo which was featured in the ldquoMetalsrdquo Report for HORIZONTAL This site is close to Reading with soils developed on flintyloamy periglacial materials over Chalk has a long and well documented history of sludge application The focus of the work of Nortcliff et al undertook at this site and the monitoring and control at the site (by Thames Water and the subsequent subsidiary bodies dealing with sludge application to soil) was on metals (and metal loads) with no analysis or indeed any form of investigation in to organics in the broadest sense

The analytical information produced in the context of the screening of the raw material is displayed below

Table 7 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 3

(Reading) 0032 0119 669

Table 8 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 3 (Reading) 015 706 279 138 152 901 267 300 lt 005 258 931

Table 9 ndash Analytical data obtained on a first screening on the sludge-amended soil from Reading (courtesy of IRMM)

Parameter Concentration

PCB ngg 28 lt1 52 lt1 101 lt1 118 lt1 153 lt1 105 lt1 138 lt1 156 lt1 180 lt1 170 lt1 PAH ngg Naphtalene lt10 Acenaphtylene 21 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene lt10 Flouranthene 818 Pyrene 776 Benz(a)anthracene 565

10

Parameter Concentration

Chrysene 608 Benz(b)fluoranthene 824 Benz(k)fluoranthene 329 Benz(a)pyrene 799 Indeno(123-cd)pyrene

779

Dibenzo(ah)anthracene 118 Benzo(ghi)perylene 394

Table 10 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 3

(Reading)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

103

003

nq

nq

nq

nd

nd

272

273

Table 11 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 3 (Reading) 015 706 279 138 152 901 267 300 lt 005 258 931

Table 12 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 3 (Reading) 7936 477 112 096 194 017 4107 443 2102 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 3 (Reading) 042 13 45 69 69 69 216 92

Table 13 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 3 (Reading) 012

11

23 Compost from Vienna Austria

The fresh compost material was obtained from the Austrian Federal Environment Agency (UBA Vienna) which had used a sub-batch of the raw material for national intercomparson The remainder of the material was stored at 4degC until shipment to IRMM for further processing The following analytical information was provided by UBA Austria and completed with various screenings

Table 14 ndash Analytical data on compost material received from UBA Austria Inorganic and sum parameters

Parameter Unit Sample fraction used Observed mean B CAT mgl FM Fresh sample lt10mm 61 K CAT mgl FM Fresh sample lt10mm 2624 Mg CAT mgl FM Fresh sample lt10mm 242 P CAT mgl FM Fresh sample lt10mm 49 B CAT DM Fresh sample lt10mm 00017 K CAT DM Fresh sample lt10mm 072 Mg CAT DM Fresh sample lt10mm 007 P CAT DM Fresh sample lt10mm 001 NO3-N mgkg FM Fresh sample lt10mm 35 NH4-N mgkg FM Fresh sample lt10mm 230 Ctotal DM lt45degdry milled 29 Corg DM lt45degdry milled 27 Ntotal DM lt45degdry milled 17 P mgkg DM lt45degdry milled 2596 K mgkg DM lt45degdry milled 11019 K DM lt45degdry milled 110 B mgkg DM lt45degdry milled 60 Cd mgkg DM lt45degdry milled 046 Cr mgkg DM lt45degdry milled 25 Cu mgkg DM lt45degdry milled 46 Hg mgkg DM lt45degdry milled 020 Ni mgkg DM lt45degdry milled 18 Pb mgkg DM lt45degdry milled 45 Zn mgkg DM lt45degdry milled 198 Ca mgkg DM lt45degdry milled 68776 Ca DM lt45degdry milled 69 Mo mgkg DM lt45degdry milled 08 S mgkg DM lt45degdry milled 2137 Fe mgkg DM lt45degdry milled 9959 Mn mgkg DM lt45degdry milled 418 Na mgkg DM lt45degdry milled 742 Co mgkg DM lt45degdry milled 41 AOX mgkg DM lt30deg dry milled 62

Table 15 ndash Analytical data on compost material received from UBA Austria Polycyclic aromatic hydrocarbons

PAH Unit Result Naphthaline microgkg DM 93 Acenaphthylene microgkg DM 86 Acenaphthene microgkg DM 5 Fluorene microgkg DM 80 Phenanthrene microgkg DM 89 Anthracene microgkg DM 27 Fluoranthene microgkg DM 487 Pyrene microgkg DM 380

12

PAH Unit Result Benzo(a)anthracene microgkg DM 278 Chrysene microgkg DM 317 Benzo(b)fluoranthene microgkg DM 365 Benzo(k)fluoranthene microgkg DM 193 Benz(a)pyrene microgkg DM 320 Indeno(123-cd)pyrene microgkg DM 233 Dibenz(ah)anthracene microgkg DM 67 Benzo(ghi)perylene microgkg DM 225 Sum EPA microgkg DM 3013 Sum EPA mgkg DM 30

Table 16 ndash Analytical data on compost material received from UBA Austria Sum PCDDs and PCBs

Parameter

Dioxine TEQ (ITEF) ngkg DM 73 TEQ (WHO) ngkg DM 35 PCB Σ Ballschmiter mgkg DM 005

Table 17 ndash Analytical data on compost material obtained by screening in IRMM

Parameter Result in ngg

PCB 28 2 52 2 101 4 118 3 153 10 105 1 138 8 156 1 180 5 170 lt1 PAH Naphtalene lt10 Acenaphtylene lt10 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene 26 Fluoranthene 611 Pyrene 510 Benz(a)anthracene 888 Chrysene 957 Benz(b)fluoranthene 1531 Benz(k)fluoranthene 547 Benz(a)pyrene 1101 Indeno(123-cd)pyrene 416 Dibenzo(ah)anthracene 81 Benzo(ghi)perylene 295

13

Table 18 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Compost 1

(Vienna)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

402

019

259

nq

023

004

nq

nq

144

174

259

Table 19 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Compost 1

(Vienna) 0058 1426 557

Table 20 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Compost 1 (Vienna) 039 736 319 410 365 127 495 004 079 013 208

Table 21 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Compost 1 (Vienna) 2063 431 617 426 199 249 1602 lt15 10521

Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Compost 1 (Vienna) 035 3496 81 375 79 55 653 60

Table 22 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Compost 1 (Vienna) 017

14

24 Agricultural soil sludge amended soil from Pavia Italy

This sludge-amended soil material was obtained during a monitoring campaign which aimed at a generic description of the over-all soil quality in Pavia Province Italy The material which was collected from the upper horizon originates from a small farm called ldquoCascina Novellordquo During the characterisation of the site the following analytical information was obtained on a pooled sample of a sub-area of the farm of 20 X 20 m2

Table 23 ndash Analytical data on Pavia soil

Parameter Result Al 713 Wgt As 224 mgkg Cd 079 mgkg Cr 59 mgkg Cu 308 mgkg Hg 008 mgkg Ni 344 mgkg Pb 246 mgkg Zn 95 mgkg C 091 Wgt 2378-TCDD 0047 pgg 12378-PeCDD 015 pgg 123478-HxCDD 019 pgg 123678-HxCDD 15 pgg 123789-HxCDD 074 pgg 1234678-HpCDD 26 pgg OCDD 382 pgg 2378-TCDF 068 pgg 12378-PeCDF 053 pgg 23478-PeCDF 071 pgg 123478-HxDF 100 pgg 123678-HxDF 066 pgg 234678-HxDF 16 pgg 123789-HxDF 027 pgg 1234678-HpDF 12 pgg 1234789-HpDF 068 pgg OCDF 33 pgg I-TEQ 20 pgg WHO-TEQ 17 pgg

In addition the screening performed at IRMM did not reveal significant quantities of PCBs and PAHs which were all below the LoDs (1 ngg for PCBs and 10 ngg for PAHs respectively)

Table 24 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 5 (Pavia) 0005 0011 154

15

Table 25 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 5

(Pavia)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

039

nq

nq

008

nq

nd

nd

670

671

Table 26 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 5 (Pavia) 033 184 573 225 426 305 206 200 lt 005 381 878

Table 27 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 5 (Pavia) 6939 129 145 224 425 116 6118 255 1789 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 5 (Pavia) 184 62 38 108 55 66 597 110

Table 28 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 5 (Pavia) 006

16

25 Sludge-amended-soil from Barcelona Spain

The sludge-amended soil material from Barcelona sampled upon indication from the Barcelorsquo- Group in Barcelona

Table 29 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 2 (Lleida T) 0015 0183 1138

Table 30 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 2

(Lleida T)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

159

045

nq

048

160

nq

nq

1000

1004

Table 31 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 2 (Lleida T) 059 141 327 536 405 186 184 224 lt 005 318 111

Table 32 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 2 (Lleida T) 4443 1067 1429 253 344 204 4116 780 3396 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 2 (Lleida T) 064 65 26 125 59 17 547 65

Table 33 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 2 (Lleida T) 010

17

26 Sludge amended soil from Essen Germany

The German sludge-amended soil from Essen which was provided as the three sludge materials by LUA NRW did not feature significant concentrations of the PCB congeners 28 52 101 118 153 105 138 156 180 170 but had detectable amounts of some PAHs

Table 34 ndash Analytical screening data on the German sludge-amended soil

Parameter Concentration(ngg)

Naphtalene lt10 Acenaphtylene lt10 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene lt10 Fluoranthene 28 Pyrene 20 Benz(a)anthracene 24 Chrysene 47 Benz(b)fluoranthene 76 Benz(k)fluoranthene 20 Benz(a)pyrene 35 Indeno(123-cd)pyrene 35 Dibenzo(ah)anthracene 10 Benzo(ghi)perylene 26

Table 35 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 4 (Essen) 0011 0302 055

Table 36 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 4

(Essen)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

nq

nq

nq

nq

nq

nq

128

191

203

18

Table 37 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 4 (Essen) 052 545 261 805 320 403 273 273 lt 005 295 781

Table 38 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 4 (Essen) 7947 442 085 06 086 007 2163 189 2019 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 4 (Essen) 045 19 42 87 683 60 462 61

Table 39 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 4 (Essen) 004

27 Long-term sludge exposed soil from Hohenheim-Stuttgart Germany

Similarly an additional sludge exposed soil was sampled at the University of Hohenheim Stuttgart were a test soil was long-term exposed to elevated concentrations of sewage sludge

Table 40 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 1 (Stuttgart) 0045 0263 1765

Table 41 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 1

(Stuttgart)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

230

006

004

004

nq

nd

nd

498

500

19

Table 42 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 1 (Stuttgart) 069 127 361 262 504 183 252 262 lt 005 266 142

Table 43 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 1 (Stuttgart) 7194 1006 133 186 366 088 7874 275 3571 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 1 (Stuttgart) 123 50 47 212 85 69 991 129

Table 44 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 1 (Stuttgart) 177

18

Annex 3

Statistical calculations

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 47)Mandels h statistics(Sludge 1 - PBD 47)

Sample Sludge 1 NUM

Element PBD 47

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00213 0001 3 -021 005 - - 10L - - NUM46L 00273 0002 4 016 021 - - 46L - - NUM64L 00059 0000 4 -116 002 NUM - 64L - - NUM12L 00188 0000 4 -036 002 - - 12L - - NUM26L 00499 0024 2 157 223 Fail - - 26L - - NUM

Totgem 0025 0005 mgkg 1-level 172 (185) NUM (10L46L64L12L26L) -1Totstd= 0016 0010 5-level 157 (162) 5

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 5 Labs rejected (10L46L64L12L26L)

000 050 100 150 200 250

k-values

10L

46L

64L

12L

26L

Mandels k statistics(Sludge 1 - PBD 47)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

10L

46L

64L

12L

26L

Labo

rato

ries

NUM

-200 -100 000 100 200

h-values

10L

46L

64L

12L

26L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 47)

Sludge 1-PBD 47

Unit mgkg

Mandels k statistics(Soil 3 - PBD 47)Mandels h statistics(Soil 3 - PBD 47)

Sample Soil 3 Soil 3 - PBD 47 -- Mean PARM = 0001 [mgkg]

Element PBD 47

General calcparmT1= 134814E-02T2= 142830E-05T3= 13T4= 45T5= 22767E-06

n= variabelp= 4

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean26L 00007 0000 2 -143 001 00007 00000 2 1 00046L 00010 0001 4 010 181 00010 00008 4 3 00010L 00011 0000 3 049 023 00011 00001 3 2 00012L 00012 0000 4 084 081 00012 00004 4 3 000

Totgem 0001 0000 mgkg 1-level 149 (177) 4 00010 () 4 3Totstd= 0000 0000 5-level 142 (159)

RESULTS Mean = 000100 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000050 --gt 5031 r = 00014Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000050 --gt 5031 R = 00014Remarks none

000 050 100 150 200

k-values

26L

46L

10L

12L

Mandels k statistics(Soil 3 - PBD 47)

00 00 00 00 00 00 00 00 00 00 00

Deviation from Mean

26L

46L

10L

12L

Labo

rato

ries

Soil 3 - PBD 47 -- Mean PARM = 0001 [mgkg]

-200 -100 000 100

h-values

26L

46L

10L

12L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 47)

Soil 3-PBD 47

Unit mgkg

Mandels k statistics(Compost 1 - PBD 99)Mandels h statistics(Compost 1 - PBD 99)

Sample Compost 1 Compost 1 - PBD 99 -- Mean PARM = 0003 [mgkg]

Element PBD 99

General calcparmT1= 492124E-02T2= 148747E-04T3= 17T4= 61T5= 93196E-06

n= variabelp= 5

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00020 0000 4 -137 053 00020 00004 4 3 000

26L 00025 0000 2 -058 024 00025 00002 2 1 00010L 00029 0000 3 012 032 00029 00003 3 2 00046L 00033 0001 4 069 161 00033 00013 4 3 00012L 00036 0001 4 114 140 00036 00011 4 3 000

Totgem 0003 0001 mgkg 1-level 172 (185) 5 00029 () 5 4Totstd= 0001 0001 5-level 157 (162)

RESULTS Mean = 000286 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000088 --gt 3086 r = 00025Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000101 --gt 3525 R = 00028Remarks none

000 050 100 150 200

k-values

4L

26L

10L

46L

12L

Mandels k statistics(Compost 1 - PBD 99)

00 00 00 00 00 00 00 00 00 00

Deviation from Mean

4L

26L

10L

46L

12L

Labo

rato

ries

Compost 1 - PBD 99 -- Mean PARM = 0003 [mgkg]

-200 -100 000 100 200

h-values

4L

26L

10L

46L

12L

Labo

rato

ries

Mandels h statistics(Compost 1 - PBD 99)

Compost 1-PBD 99

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 99)Mandels h statistics(Sludge 1 - PBD 99)

Sample Sludge 1 Sludge 1 - PBD 99 -- Mean PARM = 0024 [mgkg]

Element PBD 99

General calcparmT1= 448050E-01T2= 112113E-02T3= 19T4= 73T5= 32972E-05

n= variabelp= 5

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean64L 00173 0002 4 -118 041 Fail 00173 00019 4 3 -0014L 00183 0002 4 -104 032 00183 00015 4 3 -001

12L 00227 0001 4 -038 022 00227 00010 4 3 00010L 00290 0001 3 055 021 00290 00010 3 2 00146L 00320 0002 4 100 039 00320 00018 4 3 00126L 00323 0011 2 105 234 - - 26L - - 001

Totgem 0025 0003 mgkg 1-level 187 (177) 5 00239 (26L) 5 4Totstd= 0007 0004 5-level 166 (154) 1

RESULTS Mean = 002385 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000153 --gt 643 r = 00043Between lab variance S2L = 000004Reproducibility var S2R = 000004Reproducibility std SR = 000666 --gt 2791 R = 00186Remarks 1 Lab rejected (26L)

000 050 100 150 200 250

k-values

64L

4L

12L

10L

46L

26L

Mandels k statistics(Sludge 1 - PBD 99)

00 00 00 00 00 00 00 00 00 00

Deviation from Mean

64L

4L

12L

10L

46L

26L

Labo

rato

ries

Sludge 1 - PBD 99 -- Mean PARM = 0024 [mgkg]

-200 -100 000 100 200

h-values

64L

4L

12L

10L

46L

26L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 99)

Sludge 1-PBD 99

Unit mgkg

Mandels k statistics(Soil 3 - PBD 99)Mandels h statistics(Soil 3 - PBD 99)

Sample Soil 3 NUM

Element PBD 99

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00017 0000 4 091 068 - - 10L - - NUM46L 00017 0001 4 100 211 - - 46L - - NUM64L 00005 0000 4 -106 023 NUM - 64L - - NUM12L 00012 0000 4 015 014 - - 12L - - NUM26L 00006 0000 2 -101 012 - - 26L - - NUM

Totgem 0001 0000 mgkg 1-level 172 (173) NUM (10L46L64L12L26L) -1Totstd= 0001 0000 5-level 157 (153) 5

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 5 Labs rejected (10L46L64L12L26L)

000 050 100 150 200 250

k-values

10L

46L

64L

12L

26L

Mandels k statistics(Soil 3 - PBD 99)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

10L

46L

64L

12L

26L

Labo

rato

ries

NUM

-200 -100 000 100 200

h-values

10L

46L

64L

12L

26L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 99)

Soil 3-PBD 99

Unit mgkg

Mandels k statistics(Compost 1 - PBD 100)Mandels h statistics(Compost 1 - PBD 100)

Sample Compost 1 Compost 1 - PBD 100 -- Mean PARM = 0001 [mgkg]

Element PBD 100

General calcparmT1= 124272E-02T2= 113129E-05T3= 14T4= 52T5= 46584E-07

n= variabelp= 4

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean26L 00006 0000 2 -131 037 Fail 00006 00001 2 1 00010L 00009 0000 4 003 083 00009 00002 4 3 00046L 00009 0000 4 016 115 00009 00002 4 3 00012L 00011 0000 4 112 136 Fail 00011 00003 4 3 000

Totgem 0001 0000 mgkg 1-level 149 (167) 4 00009 () 4 3Totstd= 0000 0000 5-level 142 (15)

RESULTS Mean = 000085 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000022 --gt 2531 r = 00006Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000025 --gt 2882 R = 00007Remarks none

000 050 100 150

k-values

26L

10L

46L

12L

Mandels k statistics(Compost 1 - PBD 100)

00 00 00 00 00 00 00 00 00 00 00

Deviation from Mean

26L

10L

46L

12L

Labo

rato

ries

Compost 1 - PBD 100 -- Mean PARM = 0001 [mgkg]

-200 -100 000 100 200

h-values

26L

10L

46L

12L

Labo

rato

ries

Mandels h statistics(Compost 1 - PBD 100)

Compost 1-PBD 100

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 100)Mandels h statistics(Sludge 1 - PBD 100)

Sample Sludge 1 Sludge 1 - PBD 100 -- Mean PARM = 0005 [mgkg]

Element PBD 100

General calcparmT1= 852065E-02T2= 412762E-04T3= 18T4= 68T5= 78914E-07

n= variabelp= 5

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00039 0000 4 -042 007 Fail 00039 00002 4 3 000

12L 00044 0000 4 -041 005 Fail 00044 00001 4 3 00010L 00046 0000 4 -041 013 Fail 00046 00003 4 3 00046L 00056 0000 4 -040 012 Fail 00056 00003 4 3 00026L 00059 0000 2 -040 013 Fail 00059 00003 2 1 00038L 02168 0006 4 204 244 Fail - - 38L - - 021

Totgem 0040 0001 mgkg 1-level 187 (177) 5 00049 (38L) 5 4Totstd= 0087 0002 5-level 166 (154) 1

RESULTS Mean = 000486 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000025 --gt 507 r = 00007Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000084 --gt 1731 R = 00024Remarks 1 Lab rejected (38L)

000 050 100 150 200 250

k-values

4L

12L

10L

46L

26L

38L

Mandels k statistics(Sludge 1 - PBD 100)

-01 00 01 01 02 02 03

Deviation from Mean

4L

12L

10L

46L

26L

38L

Labo

rato

ries

Sludge 1 - PBD 100 -- Mean PARM = 0005 [mgkg]

-100 000 100 200 300

h-values

4L

12L

10L

46L

26L

38L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 100)

Sludge 1-PBD 100

Unit mgkg

Mandels k statistics(Soil 3 - PBD 100)Mandels h statistics(Soil 3 - PBD 100)

Sample Soil 3 NUM

Element PBD 100

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00003 0000 4 -050 000 Fail - - 10L - - NUM46L 00003 0000 4 -050 000 Fail NUM - 46L - - NUM3L 305500 2051 2 150 200 Fail - - 3L - - NUM

26L 00005 0000 2 -050 000 Fail - - 26L - - NUM

Totgem 7638 0513 mgkg 1-level 149 (177) NUM (10L46L3L26L) -1Totstd= 15275 1025 5-level 142 (159) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (10L46L3L26L)

000 050 100 150 200

k-values

10L

46L

3L

26L

Mandels k statistics(Soil 3 - PBD 100)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

10L

46L

3L

26L

Labo

rato

ries

NUM

-100 000 100 200

h-values

10L

46L

3L

26L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 100)

Soil 3-PBD 100

Unit mgkg

Mandels k statistics(Compost 1 - PBD 153)Mandels h statistics(Compost 1 - PBD 153)

Sample Compost 1 NUM

Element PBD 153

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean44L 00053 0001 3 150 157 Fail - - 44L - - NUM46L 00007 0000 4 -044 111 Fail - - 46L - - NUM12L 00005 0000 4 -051 055 Fail - - 12L - - NUM26L 00005 0000 2 -054 001 Fail NUM - 26L - - NUM

Totgem 0002 0000 mgkg 1-level 149 (177) NUM (44L46L12L26L) -1Totstd= 0002 0000 5-level 142 (159) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (44L46L12L26L)

000 050 100 150 200

k-values

44L

46L

12L

26L

Mandels k statistics(Compost 1 - PBD 153)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

44L

46L

12L

26L

Labo

rato

ries

NUM

-100 000 100 200

h-values

44L

46L

12L

26L

Labo

rato

ries

Mandels h statistics(Compost 1 - PBD 153)

Compost 1-PBD 153

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 153)Mandels h statistics(Sludge 1 - PBD 153)

Sample Sludge 1 Sludge 1 - PBD 153 -- Mean PARM = 0004 [mgkg]

Element PBD 153

General calcparmT1= 676738E-02T2= 267609E-04T3= 18T4= 68T5= 19626E-05

n= variabelp= 5

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00024 0000 4 -157 017 00024 00002 4 3 000

12L 00038 0002 4 006 154 00038 00018 4 3 00046L 00039 0000 4 011 026 00039 00003 4 3 00026L 00039 0000 2 018 004 00039 00000 2 1 00064L 00049 0002 4 122 159 00049 00018 4 3 000

Totgem 0004 0001 mgkg 1-level 172 (173) 5 00038 () 5 4Totstd= 0001 0001 5-level 157 (153)

RESULTS Mean = 000378 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000123 --gt 3252 r = 00034Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000142 --gt 3754 R = 00040Remarks none

000 050 100 150 200

k-values

4L

12L

46L

26L

64L

Mandels k statistics(Sludge 1 - PBD 153)

00 00 00 00 00 00 00

Deviation from Mean

4L

12L

46L

26L

64L

Labo

rato

ries

Sludge 1 - PBD 153 -- Mean PARM = 0004 [mgkg]

-200 -100 000 100 200

h-values

4L

12L

46L

26L

64L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 153)

Sludge 1-PBD 153

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 154)Mandels h statistics(Sludge 1 - PBD 154)

Sample Sludge 1 NA

Element PBD 154

General calcparmT1= NAT2= NAT3=T4=T5=

n= variabelp=

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00021 0000 3 -100 021 NA - 4L - - NA

46L 00025 0000 4 115 018 NA - 46L - - NA64L 00021 0001 4 -066 179 - - 64L - - NA12L 00023 0000 4 050 085 - - 12L - - NA

Totgem 0002 0000 mgkg 1-level 149 (167) NA (4L46L64L12L) -1Totstd= 0000 0000 5-level 142 (15) 4

RESULTS Mean = NA mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NAReproducibility var S2R = NAReproducibility std SR = NA --gt NA R = NARemarks 4 Labs rejected (4L46L64L12L)

000 050 100 150 200

k-values

4L

46L

64L

12L

Mandels k statistics(Sludge 1 - PBD 154)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

4L

46L

64L

12L

Labo

rato

ries

NA

-100 000 100 200

h-values

4L

46L

64L

12L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 154)

Sludge 1-PBD 154

Unit mgkg

Mandels k statistics(Soil 3 - PBD 154)Mandels h statistics(Soil 3 - PBD 154)

Sample Soil 3 NUM

Element PBD 154

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

4L 00010 - 1 150 Fail - - 4L - - NUM46L 00001 0000 4 -053 096 Fail - - 46L - - NUM64L 00001 0000 4 -056 105 Fail NUM - 64L - - NUM12L 00002 0000 4 -040 099 Fail - - 12L - - NUM

Totgem 000037 0000 mgkg 1-level 149 (164) NUM (4L46L64L12L) -1Totstd= 000042 0000 5-level 142 (153) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (4L46L64L12L)

000 050 100 150

k-values

4L

46L

64L

12L

Mandels k statistics(Soil 3 - PBD 154)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

4L

46L

64L

12L

Labo

rato

ries

NUM

-100 000 100 200

h-values

4L

46L

64L

12L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 154)

Soil 3-PBD 154

Unit mgkg

Mandels k statistics(Compost 1 - PBD 209)Mandels h statistics(Compost 1 - PBD 209)

Sample Compost 1 NUM

Element PBD 209

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00065 0003 2 -049 032 - - 4L - - NUM

44L 00573 0021 4 150 197 Fail - - 44L - - NUM12L 00078 0001 4 -045 011 - - 12L - - NUM26L 00049 0000 2 -056 000 NUM - 26L - - NUM

Totgem 0019 0006 mgkg 1-level 149 (177) NUM (4L44L12L26L) -1Totstd= 0025 0010 5-level 142 (159) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (4L44L12L26L)

000 050 100 150 200

k-values

4L

44L

12L

26L

Mandels k statistics(Compost 1 - PBD 209)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

4L

44L

12L

26L

Labo

rato

ries

NUM

-100 000 100 200

h-values

4L

44L

12L

26L

Labo

rato

ries

Mandels h statistics(Compost 1 - PBD 209)

Compost 1-PBD 209

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 209)Mandels h statistics(Sludge 1 - PBD 209)

Sample Sludge 1 Sludge 1 - PBD 209 -- Mean PARM = 0249 [mgkg]

Element PBD 209

General calcparmT1= 394542E+00T2= 107296E+00T3= 16T4= 56T5= 19723E-02

n= variabelp= 5

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 01550 0055 4 -112 148 Fail 01550 00551 4 3 -009

46L 02050 0007 2 -053 019 02050 00071 2 1 -00412L 02137 0058 4 -042 155 02137 00576 4 3 -00426L 03149 0021 2 078 057 Fail 03149 00210 2 1 00764L 03577 0007 4 129 020 Fail 03577 00074 4 3 011

Totgem 0249 0030 mgkg 1-level 172 (185) 5 02493 () 5 4Totstd= 0084 0025 5-level 157 (162)

RESULTS Mean = 024926 mgkg

Repeatability variance S2r = 000179Repeatability std Sr = 004234 --gt 1699 r = 01186Between lab variance S2L = 000743Reproducibility var S2R = 000922Reproducibility std SR = 009604 --gt 3853 R = 02689Remarks none

000 050 100 150 200

k-values

4L

46L

12L

26L

64L

Mandels k statistics(Sludge 1 - PBD 209)

-01 -01 00 01 01 02

Deviation from Mean

4L

46L

12L

26L

64L

Labo

rato

ries

Sludge 1 - PBD 209 -- Mean PARM = 0249 [mgkg]

-200 -100 000 100 200

h-values

4L

46L

12L

26L

64L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 209)

Sludge 1-PBD 209

Unit mgkg

Mandels k statistics(Soil 3 - PBD 209)Mandels h statistics(Soil 3 - PBD 209)

Sample Soil 3 Soil 3 - PBD 209 -- Mean PARM = 0258 [mgkg]

Element PBD 209

General calcparmT1= 596398E+00T2= 191917E+00T3= 22T4= 84T5= 13249E-02

n= variabelp= 6

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean26L 01162 0021 2 -108 074 Fail 01162 00207 2 1 -0144L 01303 0031 4 -097 111 Fail 01303 00312 4 3 -013

46L 01975 0036 4 -046 128 Fail 01975 00359 4 3 -00644L 02898 0035 4 024 124 Fail 02898 00346 4 3 00312L 03895 0018 4 100 065 Fail 03895 00181 4 3 01364L 04260 0022 4 127 078 Fail 04260 00219 4 3 017

Totgem 0258 0027 mgkg 1-level 187 (177) 6 02582 () 6 5Totstd= 0132 0008 5-level 166 (154)

RESULTS Mean = 025818 mgkg

Repeatability variance S2r = 000083Repeatability std Sr = 002878 --gt 1115 r = 00806Between lab variance S2L = 001640Reproducibility var S2R = 001723Reproducibility std SR = 013127 --gt 5084 R = 03676Remarks none

000 050 100 150

k-values

26L

4L

46L

44L

12L

64L

Mandels k statistics(Soil 3 - PBD 209)

-02 -01 -01 00 01 01 02 02

Deviation from Mean

26L

4L

46L

44L

12L

64L

Labo

rato

ries

Soil 3 - PBD 209 -- Mean PARM = 0258 [mgkg]

-200 -100 000 100 200

h-values

26L

4L

46L

44L

12L

64L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 209)

Soil 3-PBD 209

Unit mgkg

Mandels k statistics(Compost 1 - Sum PBD)Mandels h statistics(Compost 1 - Sum PBD)

Sample Compost 1 Compost 1 - Sum PBD -- Mean PARM = 0009 [mgkg]

Element Sum PBD

General calcparmT1= 154064E-01T2= 169065E-03T3= 18T4= 68T5= 11354E-04

n= variabelp= 5

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00031 0002 4 -067 016 00031 00016 4 3 -0014L 00055 0005 4 -056 048 00055 00047 4 3 000

46L 00085 0003 4 -042 031 00085 00030 4 3 00026L 00123 0000 2 -024 003 00123 00002 2 1 00012L 00154 0002 4 -011 021 00154 00021 4 3 00144L 00613 0023 4 200 237 Fail - - 44L - - 005

Totgem 0018 0006 mgkg 1-level 187 (177) 5 00089 (44L) 5 4Totstd= 0022 0009 5-level 166 (154) 1

RESULTS Mean = 000893 mgkg

Repeatability variance S2r = 000001Repeatability std Sr = 000296 --gt 3308 r = 00083Between lab variance S2L = 000002Reproducibility var S2R = 000003Reproducibility std SR = 000570 --gt 6374 R = 00159Remarks 1 Lab rejected (44L)

000 050 100 150 200 250

k-values

10L

4L

46L

26L

12L

44L

Mandels k statistics(Compost 1 - Sum PBD)

00 00 00 00 00 00 01 01

Deviation from Mean

10L

4L

46L

26L

12L

44L

Labo

rato

ries

Compost 1 - Sum PBD -- Mean PARM = 0009 [mgkg]

-100 000 100 200

h-values

10L

4L

46L

26L

12L

44L

Labo

rato

ries

Mandels h statistics(Compost 1 - Sum PBD)

Compost 1-Sum PBD

Unit mgkg

Mandels k statistics(Sludge 1 - Sum PBD)Mandels h statistics(Sludge 1 - Sum PBD)

Sample Sludge 1 Sludge 1 - Sum PBD -- Mean PARM = 0256 [mgkg]

Element Sum PBD

General calcparmT1= 531806E+00T2= 162188E+00T3= 22T4= 84T5= 25223E-02

n= variabelp= 6

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00423 0025 4 -156 044 Fail 00423 00252 4 3 -02146L 01808 0118 4 -049 205 - - 46L - - -0074L 01810 0056 4 -049 097 01810 00558 4 3 -007

38L 02168 0006 4 -022 010 02168 00059 4 3 -00412L 02890 0065 4 034 113 02890 00647 4 3 00364L 03958 0008 4 116 014 Fail 03958 00079 4 3 01426L 04094 0034 2 126 059 Fail 04094 00337 2 1 015

Totgem 0245 0044 mgkg 1-level 198 (179) 6 02557 (46L) 6 5Totstd= 0130 0039 5-level 171 (155) 1

RESULTS Mean = 025570 mgkg

Repeatability variance S2r = 000158Repeatability std Sr = 003970 --gt 1553 r = 01112Between lab variance S2L = 001807Reproducibility var S2R = 001964Reproducibility std SR = 014015 --gt 5481 R = 03924Remarks 1 Lab rejected (46L)

000 050 100 150 200 250

k-values

10L

46L

4L

38L

12L

64L

26L

Mandels k statistics(Sludge 1 - Sum PBD)

-03 -02 -02 -01 -01 00 01 01 02 02

Deviation from Mean

10L

46L

4L

38L

12L

64L

26L

Labo

rato

ries

Sludge 1 - Sum PBD -- Mean PARM = 0256 [mgkg]

-200 -100 000 100 200

h-values

10L

46L

4L

38L

12L

64L

26L

Labo

rato

ries

Mandels h statistics(Sludge 1 - Sum PBD)

Sludge 1-Sum PBD

Unit mgkg

Mandels k statistics(Soil 3 - Sum PBD)Mandels h statistics(Soil 3 - Sum PBD)

Sample Soil 3 Soil 3 - Sum PBD -- Mean PARM = 0227 [mgkg]

Element Sum PBD

General calcparmT1= 610980E+00T2= 200876E+00T3= 26T4= 100T5= 13106E-02

n= variabelp= 7

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00028 0001 4 -037 000 Fail 00028 00005 4 3 -02226L 01179 0021 2 -036 003 Fail 01179 00208 2 1 -0114L 01305 0031 4 -036 004 Fail 01305 00308 4 3 -010

46L 02065 0035 4 -036 005 Fail 02065 00350 4 3 -00244L 02923 0037 4 -035 005 Fail 02923 00365 4 3 00712L 04051 0015 4 -034 002 Fail 04051 00149 4 3 01864L 04314 0022 4 -033 003 Fail 04314 00223 4 3 0203L 305500 2051 2 247 283 Fail - - 3L - - 3032

Totgem 4017 0276 mgkg 1-level 206 (181) 7 02266 (3L) 7 6Totstd= 10722 0717 5-level 175 (156) 1

RESULTS Mean = 022663 mgkg

Repeatability variance S2r = 000069Repeatability std Sr = 002626 --gt 1159 r = 00735Between lab variance S2L = 002568Reproducibility var S2R = 002637Reproducibility std SR = 016238 --gt 7165 R = 04547Remarks 1 Lab rejected (3L)

000 050 100 150 200 250 300

k-values

10L

26L

4L

46L

44L

12L

64L

3L

Mandels k statistics(Soil 3 - Sum PBD)

-50 00 50 100 150 200 250 300 350

Deviation from Mean

10L

26L

4L

46L

44L

12L

64L

3L

Labo

rato

ries

Soil 3 - Sum PBD -- Mean PARM = 0227 [mgkg]

-100 000 100 200 300

h-values

10L

26L

4L

46L

44L

12L

64L

3L

Labo

rato

ries

Mandels h statistics(Soil 3 - Sum PBD)

Soil 3-Sum PBD

19

Annex 4

Raw data submitted

Sample Compost1 Sample Compost 1 Sample Compost 1Element PBD 99 Element PBD 100 Element PBD 153

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]4L 00021 10L 00008 44L 000504L 00024 10L 00008 44L 000604L 00014 10L 00007 44L 000504L 00020 10L 00011 46L 00004

10L 00029 46L 00007 46L 0001210L 00027 46L 00012 46L 0000410L 00032 46L 00009 46L 0000946L 00025 46L 00007 12L 0000446L 00052 12L 00008 12L 0000846L 00029 12L 00012 12L 0000446L 00026 12L 00008 12L 0000712L 00026 12L 00014 26L 0000512L 00043 26L 00007 26L 0000512L 00026 26L 0000612L 0004726L 0002626L 00024

Sample Compost 1 Sample Compost 1 Sample Compost 1Element PBD 154 Element PBD 183 Element PBD 196

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]4L 00010 46L 00002 46L 00011

46L 00003 46L 00024 46L 0000846L 00007 46L 00021 12L 0000246L 00003 46L 00003 12L 0000346L 00004 12L 00003 12L 0000112L 00003 12L 00011 12L 0000212L 00005 12L 0000312L 00031 12L 0000312L 00006

Sample Compost 1 Sample Compost 1 Sample Compost 1Element PBD 197 Element PBD 203 Element PBD 209

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00002 46L 00010 4L 0004146L 00023 12L 00002 4L 0008946L 00022 12L 00003 44L 0041012L 00004 12L 00002 44L 0084012L 00006 12L 00002 44L 0064012L 00003 44L 0040012L 00004 12L 00079

12L 0007312L 0006512L 0009326L 0004926L 00049

Sample Compost 1Element PBD 47

LAB PARM [mgkg]26L 0003826L 00039

Element PBD 99 Element PBD 47 Element PBD 209LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]

4L 00170 10L 00210 4L 010004L 00200 10L 00220 4L 018004L 00170 10L 00210 4L 012004L 00190 46L 00300 4L 0220010L 00280 46L 00280 46L 0210010L 00300 46L 00250 46L 0200010L 00290 46L 00260 64L 0351846L 00340 64L 00059 64L 0363846L 00330 64L 00057 64L 0364546L 00300 64L 00062 64L 0350846L 00310 64L 00060 12L 0220964L 00194 12L 00191 12L 0177164L 00154 12L 00187 12L 0292264L 00185 12L 00190 12L 0164664L 00159 12L 00186 26L 0329712L 00242 26L 00666 26L 0300012L 00223 26L 0033212L 0022112L 0022226L 0024626L 00400

Element PBD 203 Element PBD 197 Element PBD 196LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00022 46L 00027 46L 0002446L 00014 46L 00024 46L 0002264L 00036 12L 00161 64L 0005864L 00058 12L 00060 64L 0006512L 00063 12L 00061 12L 0004812L 00034 12L 00036 12L 0002512L 00038 12L 0003212L 00027 12L 00022

Element PBD 183 Element PBD 154 Element PBD 153LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00049 4L 00020 4L 0002246L 00035 4L 00022 4L 0002446L 00036 4L 00020 4L 0002246L 00034 46L 00025 4L 0002664L 00027 46L 00025 46L 0004064L 00023 46L 00025 46L 0004264L 00024 46L 00023 46L 0003564L 00020 64L 00034 46L 0003812L 00230 64L 00023 64L 0007412L 00032 64L 00017 64L 0004712L 00031 64L 00011 64L 0004612L 00030 12L 00030 64L 0003026L 00007 12L 00021 12L 0006526L 00008 12L 00021 12L 00029

12L 00021 12L 0003226L 00015 12L 0002926L 00019 26L 00039

26L 00040

Element PBD 100LAB PARM [mgkg]

4L 000384L 000414L 000374L 00038

38L 0219038L 0220038L 0208038L 0220010L 0004410L 0005010L 0004310L 0004646L 0005746L 0005946L 0005346L 0005312L 0004312L 0004512L 0004312L 0004326L 0006226L 00057

Sample Soil 3 Sample Soil 3 Sample Soil 3Element PBD 99 Element PBD 47 Element PBD 100

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]10L 00016 10L 00011 10L 0000310L 00019 10L 00010 10L 0000410L 00013 10L 00012 10L 0000410L 00019 46L 00007 10L 0000246L 00025 46L 00022 46L 0000246L 00025 46L 00005 46L 0000646L 00008 46L 00007 46L 0000246L 00011 12L 00010 46L 0000264L 00005 12L 00017 3L 29100064L 00005 12L 00010 3L 32000064L 00006 12L 00009 26L 0000564L 00007 26L 00007 26L 0000512L 00012 26L 0000712L 0001312L 0001312L 0001226L 0000526L 00006

Sample Soil 3 Sample Soil 3 Sample Soil 3Element PBD 153 Element PBD 154 Element PBD 196

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]44L 00050 4L 00010 46L 0000744L 00050 46L 00001 46L 0001146L 00002 46L 00002 46L 0000846L 00003 46L 00001 46L 0001146L 00002 46L 00002 64L 0002646L 00002 64L 00001 64L 0002664L 00001 64L 00001 64L 0002964L 00001 64L 00001 64L 0003464L 00001 64L 00002 12L 0004564L 00002 12L 00003 12L 00032

12L 00002 12L 0002212L 00002 12L 0002112L 00002

Sample Soil 3 Sample Soil 3 Sample Soil 3Element PBD 197 Element PBD 203 Element PBD 209

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00006 46L 00011 4L 0091046L 00013 46L 00017 4L 0150046L 00011 46L 00015 4L 0120046L 00013 46L 00018 4L 0160012L 00090 64L 00013 44L 0337012L 00056 64L 00014 44L 0281012L 00033 64L 00016 44L 0287012L 00032 64L 00015 44L 02540

12L 00055 46L 0230012L 00041 46L 0220012L 00027 46L 0150012L 00026 46L 01900

64L 0438164L 0401664L 0414464L 0449812L 0367112L 0397812L 0409112L 03838

Sample Soil 3 26L 0102Element PBD 183 26L 0131

LAB PARM [mgkg]46L 0000746L 0000846L 0005846L 0000764L 0000264L 0000364L 0000364L 0000312L 0001512L 0001112L 0000712L 00007

European Commission EUR 23003 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on polybrominated diphenylethers Author(s) E Sobiecka H van der Sloot D Barcelo B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 68 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07403-5 Abstract Project HORIZONTAL is interdisciplinary aiming at a harmonisation and horizontal standardisation of test procedures in particular for sludge soils and biowastes In the context of this standardization project a series of draft technical specification were designed upon an extensive desk study fine-tuned after expert consultations and finally validated in international intercomparisons exercise This report summarises the work performed within the validation study of the draft standard for the determination of polybrominated diphenylethers (PBDE) in soils sludge and treated bio-waste using gas-chromatography method with mass selective detection (GC-MS) It further explains the underlying statistical concept for the calculation of reproducibility and repeatability from intercomparisons data In addition all single values results of the statistical evaluation as well as background information on the validation materials used are described and explained

The mission of the JRC is to provide customer-driven scientific and technical support for the conception development implementation and monitoring of EU policies As a service of the European Commission the JRC functions as a reference centre of science and technology for the Union Close to the policy-making process it serves the common interest of the Member States while being independent of special interests whether private or national

LB

-NA

-23003-EN

-C

4

Table of Contents Summary 2 Abbreviations 3 Table of Contents 4

Introduction to the validation project 5 11 Statistical concept underlying the validation 6

111 Introduction to the statistical model 6 112 Requirements for precision experiment 7 113 Statistical analysis 8

12 Validation exercise for PBDE 8 121 Compounds to be measured 8 122 Samples dispatched for the validation of PBDE 8 123 Draft standards to be followed 8 124 Analytical programm 8 125 Timing and Submission of data 9 126 Participants 10

13 Summary results and derived performance characteristics 11 14 Annexes 15

5

Introduction to the validation project Project HORIZONTAL is interdisciplinary aiming at a harmonisation and horizontal standardisation of test procedures in particular for sludges soils and biowastes It was created as in response to the European Commission Mandate M 330 given to CEN asking for the development and validation of those standards in support of forthcoming EU Directives such as

o The revision of the Sewage Sludge Directive 86278EEC o The Directive on the biological treatment of biodegradable waste o The initiative on a legal framework for soil monitoring in Europe

This mandate explicitly considers standards for the entire analytical procedure (ie sampling pre-treatment and analytical measurement methods for inorganic organic hygiene and biological parameters) These are grouped into classes according to their physicalchemical properties which in turn determine the methods needed to quantify the potential impact on human and animal health plant uptake soil function and groundwater quality As the materials generally feature a mixture of different types of contaminants it is important to provide an integrated answer covering evaluation of all relevant pollutants In order to fulfil the requirements of the aforementioned mandate the European Commissions Joint Research Centre (JRC) and its Directorate-General for Environment (DG ENV) together with the Technical Committees of the European Standardisation Committee (CEN TCs) concerned designed a pre-normative research initiative called Project HORIZONTAL and presented it to the Commission and the Environmental Authorities in the Member States After an extensive literature research and careful evaluation of the feasibility of a given horizontal standard the standards were drafted and finally validated in an European laboratory intercomparison The underlying statistical concept information about the materials used details about the participants measurement results obtained as well as the derived performance characteristics obtained for the determination of polybrominated diphenylethers (PBDE) are described hereafter

6

11 Statistical concept underlying the validation According to the requirements of the work package concerning data handling amp interpretation of the project HORIZONTAL-ORG the respective validation intercomparisons have to be evaluated according to the principles laid down in ISO standard 5725-21994 In particular repeatability and reproducibility of the draft standard methods have to be determined The determination of trueness would require the availability of independent reference values for the materials investigated This however is not possible and was not requested in the frame of this work In the following the approach chosen is explained

111 Introduction to the statistical model The statistical model used in ISO 5725 for estimation of accuracy of a measurement method assumes that every test result is the sum of three components

eBmy ++= y test result m general mean B laboratory component of bias under repeatability conditions e random error occurring in every measurement under repeatability conditions

In the workprogram the quantification of term e is explicitly asked for (ie repeatability and reproducibility) The repeatability variance is measured directly as the variance of the error term e but the reproducibility depends on the sum of the repeatability variance and the between-laboratory variance

( )er var=σ 22rLR σσσ += with ( )BL var=σ

However soil biowaste and sludge are multi-phase materials ie they contain two or more distinct types of particles which are fundamentally different in their properties and composition As a consequence this introduces an important source of variation for the intercomparison exercise which needs to be considered ie the inherent heterogeneity of the materials Thus a contribution of variation between samples H is introduced to the general statistical model

HeBmy +++= Using ANOVA techniques the different variances are calculated and separated for the evaluation

7

112 Requirements for precision experiment

Layout of the experiment A suite of 10 to 12 different materials (soil sludge and biowaste) has been made available for the intercomparison exercise For each parameter investigated at least 10 to laboratories should be nominated to participate The same laboratories should be used for different parameters as far as possible Due to the complexity of analysis and the respective workload to the laboratories it was decided to propose three materials for the validation of the PBDE draft standard Each laboratory received two bottles of each material and was be requested to perform 4 independent analyses per material1 (2 per bottle) using the respective draft standard methods The 4 analysis per material should be carried out under repeatability conditions (ie same operator2 same equipment within a short period of time) As far as possible also the different materials should be measured under repeatability conditions however changes of eg operator or equipment are permitted but must be reported Likewise different materials can be analysed on different days if necessary Equipment used in the experiment needed to be checked prior to the experiment according to the requirements of the draft standard The results of these checks have to be documented Similarly date and time of each measurement had to be recorded for verification of repeatability conditions An appropriate timeframe for the entire exercise has been set and was to be respected

Recruitment of the laboratories Each sub-workpackage leader of HORIZONTAL was asked to select the laboratories using the information from section 52 of ISO 5725-21994 and provide the signed questionnaires (see also Annex 1) The workpackage leaders were responsible for providing the laboratories with the draft standard method and explaining the context of this exercise

Preparation and use of the materials Materials used for the exercise were prepared according to the general requirements for reference materials as laid down in ISO Guide 34 Materials were accompanied by instructions for use

Reporting of results Online submissions of results using an internet-based IT platform as well as XLS-Spreadsheets were used In case of online data submission the participating laboratories received a unique and confidential login and password in due time enabling them to

1 Independent analysis means analysis of independent test portions applying the entire analytical scheme to this test portion from eg extraction to quantification For instance it does not mean replicate injections of aliquots into a GC-MS instrument 2 Operator in this context may also consist of a fixed team of persons eg one person performing extraction one clean-up one quantification

8

enter their data in a structured form For authentication purposes a signed printout had to be submitted by mail The online data submission included a detailed questionnaire for additional information on the measurements

113 Statistical analysis Statistical analysis of data followed the requirements of ISO 5725-21994 and ISO 5725-51998 Appropriate tests for the homogeneity of variance detection of outliers and normal distribution were applied Statistical evaluation was done using an Excel Macro developed tested and successfully applied in other occasion by ECN Evaluation was executed jointly by JRC and ECN

12 Validation exercise for PBDE

121 Compounds to be measured The following compound were selected for the validation exercise Tetra-BDE-47 Penta-BDE-100 Penta-BDE-99 Hexa-BDE-154 Hexa-BDE-153 Hepta-BDE-183 Octa-BDE-196 Octa-BDE-197 Octa-BDE-203 Deca-BDE-209

122 Samples dispatched for the validation of PBDE After a preliminary rough screening the following materials were used for the validation round of PBDE

bull Compost 1 A pollutant loaded compost material from Vienna bull Sewage Sludge 1 A mixed sewage sludge from Essen bull Soil 3 A sludge amended soil from Barcelona

A more detailed description of background concentrations can be found in Annex 2 to this report The samples were dispatched simultaneously to all participants using a private courier service

123 Draft standards to be followed The draft standards to be followed could be downloaded following this link which is situated on the website of the Project HORIZONTAL httpwwwecnnldocssocietyhorizontalBFR_Standard_for_validationpdf

124 Analytical programm Of each of the three materials 2 bottles had to be analysed and each bottle had to analysed independently twice As mentioned above analyses were to be done under repeatability conditions Results were to be reported referring to DRY MATTER content The choice how to apply dm correction was free for each participant

9

125 Timing and Submission of data Dispatch of samples was done on the 18th of October 2006 For users of the Online data submission system (MILC) User Registration was possible from 14th of November 2006 with opening of the MILC Data Submission on 1st of December 2006 The deadline for submission of results has been set for PBDE to the 12th of January 2007 but was extended to the end of the same months After that no further submission was possible Alternatively the participants were allowed to submit data electronically as Excel sheet using simply Email All data were treated in a confidential way Any presentation hereafter will refer only to numerical data and it will not be possible to identify the originating laboratory Lab Codes displayed are NOT related to the order of laboratories hereafter In addition to the information provide an Helpdesk was implemented in order to give quick and individual response to the participants during and immediately after the validation study In case of doubt and suspected transcription errors further enquires were conducted by JRC

10

126 Participants The following table lists the participating organisations and entities in the validation exercise for the horizontal PBDE standard

bull Austria o Umweltbundesamt

bull Czech Republic o Povodi Labe statni podnik - OVHL Laboratory

bull France o CIRSEE o CTC Environnement o INERIS

bull Germany o Federal Environmental Agency Section III 34 Laboratory Methods for

the Surveillance of Waste and Wastewater (UBA) bull Italy

o European Commission DG JRC IES bull Spain

o Consejo Superior de Investigaciones Cientificas (CSIC)

bull Sweden o ALCONTROL AB

11

13 Summary results and derived performance characteristics The result of the various statistical evaluation including outlier tests calculation of repeatability and reproducibility standard deviation for the congeners of interest can be found in Annex 3 of this report In addition all data submitted by the participants as well as those considered for the calculation of the performance characteristics are listed in Annex 3 to this report Based on these calculations the following results were obtained in the validation round upon statistical evaluation according to ISO 5725-2 The average values the repeatability standard deviation (sr) and the reproducibility standard deviation (sR) were obtained (Table1) The repeatability is determined as an interval around a measurement result (ie repeatability limit) This interval corresponds to the maximum difference that can be expected (with a 95 statistical confidence) between one test result and another both test results being obtained under the following conditions The tests are performed in accordance with all the requirements of the present standard by the same laboratory using its own facilities and testing laboratory samples obtained from the same primary field sample and prepared under identical procedures The repeatability limit was calculated using the relationship r test = f radic2 s rtest with the critical range factor f = 2 The reproducibility like repeatability is also determined as an interval around a measurement result (ie reproducibility limit) This interval corresponds to the maximum difference that can be expected (with a 95 statistical confidence) between one test result and another test result obtained by another laboratory both test results being obtained under the following conditions The tests are performed in accordance with all the requirements of the present standard by two different laboratories using their own facilities and testing laboratory samples obtained from the same primary field sample and prepared under identical procedures The reproducibility limit was calculated using the relationship R = f radic2 sR with the critical range factor f = 2

12

Table 1 - Results of the interlaboratory comparison studies of the determination of selected polybrominated diphenyl ethers (PBDE) by gaschromatography with mass spectrometric detection (GC-MS) in soil sludge and treated biowaste All concentrations are expressed in mgkg dm

Matrix Parameter Mean sr sR r R p Outliers Used No of data

No of data reported below

detection

Total no of data

Sludge 1 PBD 47 00181 461 4 15 5 20 Compost 1 00039 94 3 12 0 12 Soil 3 00010 50 50 00014 00014 4 0 13 10 23 Sludge 1 PBD 99 00239 64 28 00043 00186 5 1 19 0 23 Compost 1 00029 31 35 00025 00028 5 0 17 4 21 Soil 3 00013 499 4 16 8 24 Sludge 1 PBD 100 00049 51 17 00007 00024 5 1 18 2 24 Compost 1 00009 25 29 00006 00007 4 0 14 7 21 Soil 3 61103 211 3 10 15 25 Sludge 1 PBD 153 00038 33 38 00034 0004 5 0 18 0 18 Compost 1 00019 116 3 11 3 14 Soil 3 00011 177 2 10 10 20 Sludge 1 PBD 154 00023 234 4 15 2 17 Compost 1 00008 1118 3 9 5 14

13

Matrix Parameter Mean sr sR r R p Outliers Used No of data

No of data reported below

detection

Total no of data

Soil 3 00002 1049 4 13 6 19 Sludge 1 PBD 183 00048 1217 3 12 2 14 Compost 1 00009 1048 2 8 5 13 Soil 3 00011 1395 3 12 6 18 Sludge 1 PBD 196 00037 470 2 8 7 15 Compost 1 00004 950 2 6 4 10 Soil 3 00023 519 3 12 2 14 Sludge 1 PBD 197 00062 834 2 6 8 14 Compost 1 00009 1001 2 7 7 14 Soil 3 00032 904 2 8 6 14 Sludge 1 PBD 203 00037 461 2 8 4 12 Compost 1 00004 978 2 5 3 8 Soil 3 00022 598 3 12 0 12 Sludge 1 PBD 209 02493 170 39 01186 02689 5 0 16 2 18 Compost 1 00273 104 3 10 5 15 Soil 3 02582 1115 51 00806 03676 6 0 22 0 22

14

Matrix Parameter Mean sr sR r R p Outliers Used No of data

No of data reported below

detection

Total no of data

Sludge 1 Sum PBD 0256 155 548 0111 0392 6 1 22 Compost 1 0009 331 637 0008 0016 5 1 18 Soil 3 0227 116 717 0074 0455 7 1 26 Abbreviations sr Repeatability standard deviation SR Reproducibility standard deviation r Repeatability limit (comparing two measurements) R Reproducibility limit (comparing two measurements) p Number of labs determination not possible

15

14 Annexes Annex 1 Model questionnaire to be filled by the participating laboratories Annex 3 Report on the validation materials used Annex 2 Statistical calculations Annex 3 Data submitted

16

Annex 1

Model questionnaire to be filled by the participating laboratories

Model questionnaire to be filled by the participating laboratories Name of laboratory Contact person Contact details email Phone Fax Mail address of lab Dispatch address of lab for shipment of samples (no PO boxes) Title of measurement method (copy attached) Our laboratory is willing to participate in the precision experiment for this draft standard method

Yes No As participant we understand that

bull All essential apparatus chemicals and other requirements specified in the method must be available in our laboratory when the programme begins

bull Specified timing requirements such as starting and finishing date of the programme must be rigidly met

bull The method must be strictly adhered to bull Samples must be handled in accordance with instructions bull A qualified operator must perform the measurements

Having studied the method and having made a fair appraisal of our capabilities and facilities we feel that we will be adequately prepared for cooperative testing of this method Comments helliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphellip Signature Date

17

Annex 2

Report on the validation materials used

VI

Abstract This report gives an overview on the available analytical information on the following raw materials to be used for the production of validation materials of the so-called Project HORIZONTAL

bull Four sludge materials from Duumlsseldorf Germany

bull An agricultural soil material from Reading United Kingdom

bull A compost material from Vienna Austria

bull A compost material from Korschenbroich Germany

bull A sludge-amended agricultural soil from Pavia Province Italy

bull A sludge-amended soil from Barcelona Spain

bull A sludge-amended soil from Essen Germany

bull A long-term sludge exposed soil from Hohenheim Germany

VII

List of Abbreviations Throughout this report the following abbreviations are used

AOX absorbable organic halogens

Corg organic carbon content

Ctotal total carbon content

CAT cation exchangeable

CDD chlorinated dibenzodioxin

CDF chlorinated dibenzofuran

DEHP di(2-ethylhexyl)phthalate

DM dry matter

EPA Environment Protection Agency

EU European Union

FM fresh matter

Hp hepta

Hx hexa

IES Institute for Environment and Sustainability

IRMM Institute for Reference Materials and Measurements

JRC Joint Research Centre

LAS linear alkylsulfonates

LoD limit of detection

LUA Landesumweltamt

Ntotal total nitrogen content

NH4-N Ammonium nitrogen

NO3-N Nitrate nitrogen

NP nonylphenol

NRW North Rhine Westphalia

O octa

P poly

PAH polycyclic aromatic hydrocarbon

PCB polychlorinated biphenyl

Pe penta

T tetra

TEQ toxicity equivalent

UBA Umweltbundesamt

WHO World Health Organization

WWTP waste water treatment plant

6

1 Introduction This report gives an overview on the available analytical information on the following raw materials to be used for the production of validation materials of the so-called Project HORIZONTAL

bull Four sludge materials from Duumlsseldorf Germany

bull An agricultural soil material from Reading United Kingdom

bull A compost material from Vienna Austria

bull A compost material from Korschenbroich Germany

bull A sludge-amended agricultural soil from Pavia Province Italy

bull A sludge-amended soil from Barcelona Spain

bull A sludge-amended soil from Essen Germany

bull A long-term sludge exposed soil from Hohenheim Germany

The following analytical information was gathered partly before and during the sampling of the raw materials to be used for the production of the HORIZONTAL validation materials The material were sampled by IES and shipped to IRMM in the course of the year 2005 The information gathered was then completed by various analytical screenings for PAHs and PCBs done by the Institute for Reference Materials and Measurements Geel Belgium for phthalates done by UBA Berlin Germany for PBDE done by IIQAB-CSIC Barcelona Spain for trace elements and some selected major and minor elements by the Institute for Environment and Sustainability Ispra Italy

The work compiled hereafter is based on the numerous additional efforts of the scientists working at various members of the consortium Project HORIZONTAL-Org and contributing organisations

This work is gratefully acknowledged

2 Overview on property values

21 Sludge materials from Duumlsseldorf Germany

The various sewage sludge materials originate from various installations in the North Rhine Westphalia and were produced and sampled by staff from the Landesumweltamt (LUA) NRW under the responsibility from Dr K Furtmann

In total four sludge materials (Sludge A and D from a major municipal WWTP Sludge B from a municipal WWTP with industrial input and Sludge C from a municipal WWTP with high PCB-Content) were obtained and will be blended to two final materials Before sampling the following analytical data for a typical sample were received

7

Table 1 ndash Analytical data obtained on an average sludge sample in LUA NRW (with courtesy of K Furtmann LUA Duumlsseldorf)

Parameter Concentration PCB 120 ugkg DEHP 110 mgkg PAH 5 mgkg (EPA) PCDDF 15 ng TEkg PBDE 400 ugkg NP 40 mgkg LAS 3 gkg AOX 300 mgkg

Subsequent screening led to the information displayed hereafter It should be stressed that the data were obtained as SCREENING information on the UNTREATED or partially treated raw materials Therefore the final target values which are relevant for the validation intercomparison can be different

Table 2 ndash Analytical data obtained on a first screening on the sludge samples from LUA NRW

Sewage sludge A

Dusseldorf

sewage sludge D

Dusseldorf PCB (ngg) 28 62 35 52 101 65 101 31 38 118 49 40 153 30 33 105 24 11 138 46 38 156 lt1 lt1 180 34 23 170 23 19 PAH (ngg) Naphtalene 34 381 Acenaphtylene 15 43 Acenaphthene 81 108 Fluorene 94 1167 Phenantrene 3440 Anthracene 22 344 Flouranthene 316 4817 Pyrene 235 3011 Benz(a)anthracene 473 791 Chrysene 691 1078 Benz(b)fluoranthene 538 1688 Benz(k)fluoranthene 228 635 Benz(a)pyrene 383 1114 Indeno(123-cd)pyrene 92 229 Dibenzo(ah)anthracene 71 70 Benzo(ghi)perylene 80 185

8

Table 3 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Sludge D (1) 0135 41474 385 Sludge B (2) 0538 0034 30634 547 Sludge A (3) 0184 0037 31399 146 Sludge C (4) 0354 1528 6678 229

Table 4 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Sludge 2

(B)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

554

959

694

591

772

509

nq

nq

970

2216

2379

Table 5 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena IES Ispra Spain) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Sludge 1 (D) 265 290 533 359 1231 338 784 438 lt 005 232 786 Sludge 2 (B) 119 311 626 202 278 299 722 251 lt 005 118 625 Sludge 3 (A) 168 360 621 332 847 416 119 451 lt 005 116 1237 Sludge 4 (C) 563 198 116 273 726 511 473 618 lt 005 444 2015

Table 6 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Sludge 1 (D) 2154 58 844 099 103 101 4367 lt15 50448 Sludge 2 (B) 1067 366 692 046 1491 077 5217 lt15 57633 Sludge 3 (A) 731 663 684 035 1287 068 3733 lt15 60369 Sludge 4 (C) 4379 965 527 163 522 107 5628 lt15 23945

Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM)Sludge 1 (D) 03 2403 101 1002 350 15 1944 132Sludge 2 (B) 031 315 97 879 172 12 514 180Sludge 3 (A) 031 1281 153 1567 265 16 1440 168Sludge 4 (C) 055 231 628 2625 371 81 1101 244

9

22 Agricultural soil material from Reading United Kingdom

The material was proposed by the University of Reading (S Nortcliff) and was sampled from a site called ldquoFrogmore Farmrdquo which was featured in the ldquoMetalsrdquo Report for HORIZONTAL This site is close to Reading with soils developed on flintyloamy periglacial materials over Chalk has a long and well documented history of sludge application The focus of the work of Nortcliff et al undertook at this site and the monitoring and control at the site (by Thames Water and the subsequent subsidiary bodies dealing with sludge application to soil) was on metals (and metal loads) with no analysis or indeed any form of investigation in to organics in the broadest sense

The analytical information produced in the context of the screening of the raw material is displayed below

Table 7 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 3

(Reading) 0032 0119 669

Table 8 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 3 (Reading) 015 706 279 138 152 901 267 300 lt 005 258 931

Table 9 ndash Analytical data obtained on a first screening on the sludge-amended soil from Reading (courtesy of IRMM)

Parameter Concentration

PCB ngg 28 lt1 52 lt1 101 lt1 118 lt1 153 lt1 105 lt1 138 lt1 156 lt1 180 lt1 170 lt1 PAH ngg Naphtalene lt10 Acenaphtylene 21 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene lt10 Flouranthene 818 Pyrene 776 Benz(a)anthracene 565

10

Parameter Concentration

Chrysene 608 Benz(b)fluoranthene 824 Benz(k)fluoranthene 329 Benz(a)pyrene 799 Indeno(123-cd)pyrene

779

Dibenzo(ah)anthracene 118 Benzo(ghi)perylene 394

Table 10 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 3

(Reading)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

103

003

nq

nq

nq

nd

nd

272

273

Table 11 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 3 (Reading) 015 706 279 138 152 901 267 300 lt 005 258 931

Table 12 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 3 (Reading) 7936 477 112 096 194 017 4107 443 2102 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 3 (Reading) 042 13 45 69 69 69 216 92

Table 13 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 3 (Reading) 012

11

23 Compost from Vienna Austria

The fresh compost material was obtained from the Austrian Federal Environment Agency (UBA Vienna) which had used a sub-batch of the raw material for national intercomparson The remainder of the material was stored at 4degC until shipment to IRMM for further processing The following analytical information was provided by UBA Austria and completed with various screenings

Table 14 ndash Analytical data on compost material received from UBA Austria Inorganic and sum parameters

Parameter Unit Sample fraction used Observed mean B CAT mgl FM Fresh sample lt10mm 61 K CAT mgl FM Fresh sample lt10mm 2624 Mg CAT mgl FM Fresh sample lt10mm 242 P CAT mgl FM Fresh sample lt10mm 49 B CAT DM Fresh sample lt10mm 00017 K CAT DM Fresh sample lt10mm 072 Mg CAT DM Fresh sample lt10mm 007 P CAT DM Fresh sample lt10mm 001 NO3-N mgkg FM Fresh sample lt10mm 35 NH4-N mgkg FM Fresh sample lt10mm 230 Ctotal DM lt45degdry milled 29 Corg DM lt45degdry milled 27 Ntotal DM lt45degdry milled 17 P mgkg DM lt45degdry milled 2596 K mgkg DM lt45degdry milled 11019 K DM lt45degdry milled 110 B mgkg DM lt45degdry milled 60 Cd mgkg DM lt45degdry milled 046 Cr mgkg DM lt45degdry milled 25 Cu mgkg DM lt45degdry milled 46 Hg mgkg DM lt45degdry milled 020 Ni mgkg DM lt45degdry milled 18 Pb mgkg DM lt45degdry milled 45 Zn mgkg DM lt45degdry milled 198 Ca mgkg DM lt45degdry milled 68776 Ca DM lt45degdry milled 69 Mo mgkg DM lt45degdry milled 08 S mgkg DM lt45degdry milled 2137 Fe mgkg DM lt45degdry milled 9959 Mn mgkg DM lt45degdry milled 418 Na mgkg DM lt45degdry milled 742 Co mgkg DM lt45degdry milled 41 AOX mgkg DM lt30deg dry milled 62

Table 15 ndash Analytical data on compost material received from UBA Austria Polycyclic aromatic hydrocarbons

PAH Unit Result Naphthaline microgkg DM 93 Acenaphthylene microgkg DM 86 Acenaphthene microgkg DM 5 Fluorene microgkg DM 80 Phenanthrene microgkg DM 89 Anthracene microgkg DM 27 Fluoranthene microgkg DM 487 Pyrene microgkg DM 380

12

PAH Unit Result Benzo(a)anthracene microgkg DM 278 Chrysene microgkg DM 317 Benzo(b)fluoranthene microgkg DM 365 Benzo(k)fluoranthene microgkg DM 193 Benz(a)pyrene microgkg DM 320 Indeno(123-cd)pyrene microgkg DM 233 Dibenz(ah)anthracene microgkg DM 67 Benzo(ghi)perylene microgkg DM 225 Sum EPA microgkg DM 3013 Sum EPA mgkg DM 30

Table 16 ndash Analytical data on compost material received from UBA Austria Sum PCDDs and PCBs

Parameter

Dioxine TEQ (ITEF) ngkg DM 73 TEQ (WHO) ngkg DM 35 PCB Σ Ballschmiter mgkg DM 005

Table 17 ndash Analytical data on compost material obtained by screening in IRMM

Parameter Result in ngg

PCB 28 2 52 2 101 4 118 3 153 10 105 1 138 8 156 1 180 5 170 lt1 PAH Naphtalene lt10 Acenaphtylene lt10 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene 26 Fluoranthene 611 Pyrene 510 Benz(a)anthracene 888 Chrysene 957 Benz(b)fluoranthene 1531 Benz(k)fluoranthene 547 Benz(a)pyrene 1101 Indeno(123-cd)pyrene 416 Dibenzo(ah)anthracene 81 Benzo(ghi)perylene 295

13

Table 18 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Compost 1

(Vienna)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

402

019

259

nq

023

004

nq

nq

144

174

259

Table 19 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Compost 1

(Vienna) 0058 1426 557

Table 20 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Compost 1 (Vienna) 039 736 319 410 365 127 495 004 079 013 208

Table 21 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Compost 1 (Vienna) 2063 431 617 426 199 249 1602 lt15 10521

Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Compost 1 (Vienna) 035 3496 81 375 79 55 653 60

Table 22 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Compost 1 (Vienna) 017

14

24 Agricultural soil sludge amended soil from Pavia Italy

This sludge-amended soil material was obtained during a monitoring campaign which aimed at a generic description of the over-all soil quality in Pavia Province Italy The material which was collected from the upper horizon originates from a small farm called ldquoCascina Novellordquo During the characterisation of the site the following analytical information was obtained on a pooled sample of a sub-area of the farm of 20 X 20 m2

Table 23 ndash Analytical data on Pavia soil

Parameter Result Al 713 Wgt As 224 mgkg Cd 079 mgkg Cr 59 mgkg Cu 308 mgkg Hg 008 mgkg Ni 344 mgkg Pb 246 mgkg Zn 95 mgkg C 091 Wgt 2378-TCDD 0047 pgg 12378-PeCDD 015 pgg 123478-HxCDD 019 pgg 123678-HxCDD 15 pgg 123789-HxCDD 074 pgg 1234678-HpCDD 26 pgg OCDD 382 pgg 2378-TCDF 068 pgg 12378-PeCDF 053 pgg 23478-PeCDF 071 pgg 123478-HxDF 100 pgg 123678-HxDF 066 pgg 234678-HxDF 16 pgg 123789-HxDF 027 pgg 1234678-HpDF 12 pgg 1234789-HpDF 068 pgg OCDF 33 pgg I-TEQ 20 pgg WHO-TEQ 17 pgg

In addition the screening performed at IRMM did not reveal significant quantities of PCBs and PAHs which were all below the LoDs (1 ngg for PCBs and 10 ngg for PAHs respectively)

Table 24 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 5 (Pavia) 0005 0011 154

15

Table 25 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 5

(Pavia)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

039

nq

nq

008

nq

nd

nd

670

671

Table 26 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 5 (Pavia) 033 184 573 225 426 305 206 200 lt 005 381 878

Table 27 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 5 (Pavia) 6939 129 145 224 425 116 6118 255 1789 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 5 (Pavia) 184 62 38 108 55 66 597 110

Table 28 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 5 (Pavia) 006

16

25 Sludge-amended-soil from Barcelona Spain

The sludge-amended soil material from Barcelona sampled upon indication from the Barcelorsquo- Group in Barcelona

Table 29 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 2 (Lleida T) 0015 0183 1138

Table 30 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 2

(Lleida T)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

159

045

nq

048

160

nq

nq

1000

1004

Table 31 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 2 (Lleida T) 059 141 327 536 405 186 184 224 lt 005 318 111

Table 32 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 2 (Lleida T) 4443 1067 1429 253 344 204 4116 780 3396 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 2 (Lleida T) 064 65 26 125 59 17 547 65

Table 33 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 2 (Lleida T) 010

17

26 Sludge amended soil from Essen Germany

The German sludge-amended soil from Essen which was provided as the three sludge materials by LUA NRW did not feature significant concentrations of the PCB congeners 28 52 101 118 153 105 138 156 180 170 but had detectable amounts of some PAHs

Table 34 ndash Analytical screening data on the German sludge-amended soil

Parameter Concentration(ngg)

Naphtalene lt10 Acenaphtylene lt10 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene lt10 Fluoranthene 28 Pyrene 20 Benz(a)anthracene 24 Chrysene 47 Benz(b)fluoranthene 76 Benz(k)fluoranthene 20 Benz(a)pyrene 35 Indeno(123-cd)pyrene 35 Dibenzo(ah)anthracene 10 Benzo(ghi)perylene 26

Table 35 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 4 (Essen) 0011 0302 055

Table 36 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 4

(Essen)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

nq

nq

nq

nq

nq

nq

128

191

203

18

Table 37 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 4 (Essen) 052 545 261 805 320 403 273 273 lt 005 295 781

Table 38 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 4 (Essen) 7947 442 085 06 086 007 2163 189 2019 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 4 (Essen) 045 19 42 87 683 60 462 61

Table 39 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 4 (Essen) 004

27 Long-term sludge exposed soil from Hohenheim-Stuttgart Germany

Similarly an additional sludge exposed soil was sampled at the University of Hohenheim Stuttgart were a test soil was long-term exposed to elevated concentrations of sewage sludge

Table 40 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 1 (Stuttgart) 0045 0263 1765

Table 41 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 1

(Stuttgart)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

230

006

004

004

nq

nd

nd

498

500

19

Table 42 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 1 (Stuttgart) 069 127 361 262 504 183 252 262 lt 005 266 142

Table 43 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 1 (Stuttgart) 7194 1006 133 186 366 088 7874 275 3571 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 1 (Stuttgart) 123 50 47 212 85 69 991 129

Table 44 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 1 (Stuttgart) 177

18

Annex 3

Statistical calculations

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 47)Mandels h statistics(Sludge 1 - PBD 47)

Sample Sludge 1 NUM

Element PBD 47

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00213 0001 3 -021 005 - - 10L - - NUM46L 00273 0002 4 016 021 - - 46L - - NUM64L 00059 0000 4 -116 002 NUM - 64L - - NUM12L 00188 0000 4 -036 002 - - 12L - - NUM26L 00499 0024 2 157 223 Fail - - 26L - - NUM

Totgem 0025 0005 mgkg 1-level 172 (185) NUM (10L46L64L12L26L) -1Totstd= 0016 0010 5-level 157 (162) 5

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 5 Labs rejected (10L46L64L12L26L)

000 050 100 150 200 250

k-values

10L

46L

64L

12L

26L

Mandels k statistics(Sludge 1 - PBD 47)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

10L

46L

64L

12L

26L

Labo

rato

ries

NUM

-200 -100 000 100 200

h-values

10L

46L

64L

12L

26L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 47)

Sludge 1-PBD 47

Unit mgkg

Mandels k statistics(Soil 3 - PBD 47)Mandels h statistics(Soil 3 - PBD 47)

Sample Soil 3 Soil 3 - PBD 47 -- Mean PARM = 0001 [mgkg]

Element PBD 47

General calcparmT1= 134814E-02T2= 142830E-05T3= 13T4= 45T5= 22767E-06

n= variabelp= 4

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean26L 00007 0000 2 -143 001 00007 00000 2 1 00046L 00010 0001 4 010 181 00010 00008 4 3 00010L 00011 0000 3 049 023 00011 00001 3 2 00012L 00012 0000 4 084 081 00012 00004 4 3 000

Totgem 0001 0000 mgkg 1-level 149 (177) 4 00010 () 4 3Totstd= 0000 0000 5-level 142 (159)

RESULTS Mean = 000100 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000050 --gt 5031 r = 00014Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000050 --gt 5031 R = 00014Remarks none

000 050 100 150 200

k-values

26L

46L

10L

12L

Mandels k statistics(Soil 3 - PBD 47)

00 00 00 00 00 00 00 00 00 00 00

Deviation from Mean

26L

46L

10L

12L

Labo

rato

ries

Soil 3 - PBD 47 -- Mean PARM = 0001 [mgkg]

-200 -100 000 100

h-values

26L

46L

10L

12L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 47)

Soil 3-PBD 47

Unit mgkg

Mandels k statistics(Compost 1 - PBD 99)Mandels h statistics(Compost 1 - PBD 99)

Sample Compost 1 Compost 1 - PBD 99 -- Mean PARM = 0003 [mgkg]

Element PBD 99

General calcparmT1= 492124E-02T2= 148747E-04T3= 17T4= 61T5= 93196E-06

n= variabelp= 5

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00020 0000 4 -137 053 00020 00004 4 3 000

26L 00025 0000 2 -058 024 00025 00002 2 1 00010L 00029 0000 3 012 032 00029 00003 3 2 00046L 00033 0001 4 069 161 00033 00013 4 3 00012L 00036 0001 4 114 140 00036 00011 4 3 000

Totgem 0003 0001 mgkg 1-level 172 (185) 5 00029 () 5 4Totstd= 0001 0001 5-level 157 (162)

RESULTS Mean = 000286 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000088 --gt 3086 r = 00025Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000101 --gt 3525 R = 00028Remarks none

000 050 100 150 200

k-values

4L

26L

10L

46L

12L

Mandels k statistics(Compost 1 - PBD 99)

00 00 00 00 00 00 00 00 00 00

Deviation from Mean

4L

26L

10L

46L

12L

Labo

rato

ries

Compost 1 - PBD 99 -- Mean PARM = 0003 [mgkg]

-200 -100 000 100 200

h-values

4L

26L

10L

46L

12L

Labo

rato

ries

Mandels h statistics(Compost 1 - PBD 99)

Compost 1-PBD 99

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 99)Mandels h statistics(Sludge 1 - PBD 99)

Sample Sludge 1 Sludge 1 - PBD 99 -- Mean PARM = 0024 [mgkg]

Element PBD 99

General calcparmT1= 448050E-01T2= 112113E-02T3= 19T4= 73T5= 32972E-05

n= variabelp= 5

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean64L 00173 0002 4 -118 041 Fail 00173 00019 4 3 -0014L 00183 0002 4 -104 032 00183 00015 4 3 -001

12L 00227 0001 4 -038 022 00227 00010 4 3 00010L 00290 0001 3 055 021 00290 00010 3 2 00146L 00320 0002 4 100 039 00320 00018 4 3 00126L 00323 0011 2 105 234 - - 26L - - 001

Totgem 0025 0003 mgkg 1-level 187 (177) 5 00239 (26L) 5 4Totstd= 0007 0004 5-level 166 (154) 1

RESULTS Mean = 002385 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000153 --gt 643 r = 00043Between lab variance S2L = 000004Reproducibility var S2R = 000004Reproducibility std SR = 000666 --gt 2791 R = 00186Remarks 1 Lab rejected (26L)

000 050 100 150 200 250

k-values

64L

4L

12L

10L

46L

26L

Mandels k statistics(Sludge 1 - PBD 99)

00 00 00 00 00 00 00 00 00 00

Deviation from Mean

64L

4L

12L

10L

46L

26L

Labo

rato

ries

Sludge 1 - PBD 99 -- Mean PARM = 0024 [mgkg]

-200 -100 000 100 200

h-values

64L

4L

12L

10L

46L

26L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 99)

Sludge 1-PBD 99

Unit mgkg

Mandels k statistics(Soil 3 - PBD 99)Mandels h statistics(Soil 3 - PBD 99)

Sample Soil 3 NUM

Element PBD 99

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00017 0000 4 091 068 - - 10L - - NUM46L 00017 0001 4 100 211 - - 46L - - NUM64L 00005 0000 4 -106 023 NUM - 64L - - NUM12L 00012 0000 4 015 014 - - 12L - - NUM26L 00006 0000 2 -101 012 - - 26L - - NUM

Totgem 0001 0000 mgkg 1-level 172 (173) NUM (10L46L64L12L26L) -1Totstd= 0001 0000 5-level 157 (153) 5

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 5 Labs rejected (10L46L64L12L26L)

000 050 100 150 200 250

k-values

10L

46L

64L

12L

26L

Mandels k statistics(Soil 3 - PBD 99)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

10L

46L

64L

12L

26L

Labo

rato

ries

NUM

-200 -100 000 100 200

h-values

10L

46L

64L

12L

26L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 99)

Soil 3-PBD 99

Unit mgkg

Mandels k statistics(Compost 1 - PBD 100)Mandels h statistics(Compost 1 - PBD 100)

Sample Compost 1 Compost 1 - PBD 100 -- Mean PARM = 0001 [mgkg]

Element PBD 100

General calcparmT1= 124272E-02T2= 113129E-05T3= 14T4= 52T5= 46584E-07

n= variabelp= 4

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean26L 00006 0000 2 -131 037 Fail 00006 00001 2 1 00010L 00009 0000 4 003 083 00009 00002 4 3 00046L 00009 0000 4 016 115 00009 00002 4 3 00012L 00011 0000 4 112 136 Fail 00011 00003 4 3 000

Totgem 0001 0000 mgkg 1-level 149 (167) 4 00009 () 4 3Totstd= 0000 0000 5-level 142 (15)

RESULTS Mean = 000085 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000022 --gt 2531 r = 00006Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000025 --gt 2882 R = 00007Remarks none

000 050 100 150

k-values

26L

10L

46L

12L

Mandels k statistics(Compost 1 - PBD 100)

00 00 00 00 00 00 00 00 00 00 00

Deviation from Mean

26L

10L

46L

12L

Labo

rato

ries

Compost 1 - PBD 100 -- Mean PARM = 0001 [mgkg]

-200 -100 000 100 200

h-values

26L

10L

46L

12L

Labo

rato

ries

Mandels h statistics(Compost 1 - PBD 100)

Compost 1-PBD 100

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 100)Mandels h statistics(Sludge 1 - PBD 100)

Sample Sludge 1 Sludge 1 - PBD 100 -- Mean PARM = 0005 [mgkg]

Element PBD 100

General calcparmT1= 852065E-02T2= 412762E-04T3= 18T4= 68T5= 78914E-07

n= variabelp= 5

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00039 0000 4 -042 007 Fail 00039 00002 4 3 000

12L 00044 0000 4 -041 005 Fail 00044 00001 4 3 00010L 00046 0000 4 -041 013 Fail 00046 00003 4 3 00046L 00056 0000 4 -040 012 Fail 00056 00003 4 3 00026L 00059 0000 2 -040 013 Fail 00059 00003 2 1 00038L 02168 0006 4 204 244 Fail - - 38L - - 021

Totgem 0040 0001 mgkg 1-level 187 (177) 5 00049 (38L) 5 4Totstd= 0087 0002 5-level 166 (154) 1

RESULTS Mean = 000486 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000025 --gt 507 r = 00007Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000084 --gt 1731 R = 00024Remarks 1 Lab rejected (38L)

000 050 100 150 200 250

k-values

4L

12L

10L

46L

26L

38L

Mandels k statistics(Sludge 1 - PBD 100)

-01 00 01 01 02 02 03

Deviation from Mean

4L

12L

10L

46L

26L

38L

Labo

rato

ries

Sludge 1 - PBD 100 -- Mean PARM = 0005 [mgkg]

-100 000 100 200 300

h-values

4L

12L

10L

46L

26L

38L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 100)

Sludge 1-PBD 100

Unit mgkg

Mandels k statistics(Soil 3 - PBD 100)Mandels h statistics(Soil 3 - PBD 100)

Sample Soil 3 NUM

Element PBD 100

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00003 0000 4 -050 000 Fail - - 10L - - NUM46L 00003 0000 4 -050 000 Fail NUM - 46L - - NUM3L 305500 2051 2 150 200 Fail - - 3L - - NUM

26L 00005 0000 2 -050 000 Fail - - 26L - - NUM

Totgem 7638 0513 mgkg 1-level 149 (177) NUM (10L46L3L26L) -1Totstd= 15275 1025 5-level 142 (159) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (10L46L3L26L)

000 050 100 150 200

k-values

10L

46L

3L

26L

Mandels k statistics(Soil 3 - PBD 100)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

10L

46L

3L

26L

Labo

rato

ries

NUM

-100 000 100 200

h-values

10L

46L

3L

26L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 100)

Soil 3-PBD 100

Unit mgkg

Mandels k statistics(Compost 1 - PBD 153)Mandels h statistics(Compost 1 - PBD 153)

Sample Compost 1 NUM

Element PBD 153

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean44L 00053 0001 3 150 157 Fail - - 44L - - NUM46L 00007 0000 4 -044 111 Fail - - 46L - - NUM12L 00005 0000 4 -051 055 Fail - - 12L - - NUM26L 00005 0000 2 -054 001 Fail NUM - 26L - - NUM

Totgem 0002 0000 mgkg 1-level 149 (177) NUM (44L46L12L26L) -1Totstd= 0002 0000 5-level 142 (159) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (44L46L12L26L)

000 050 100 150 200

k-values

44L

46L

12L

26L

Mandels k statistics(Compost 1 - PBD 153)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

44L

46L

12L

26L

Labo

rato

ries

NUM

-100 000 100 200

h-values

44L

46L

12L

26L

Labo

rato

ries

Mandels h statistics(Compost 1 - PBD 153)

Compost 1-PBD 153

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 153)Mandels h statistics(Sludge 1 - PBD 153)

Sample Sludge 1 Sludge 1 - PBD 153 -- Mean PARM = 0004 [mgkg]

Element PBD 153

General calcparmT1= 676738E-02T2= 267609E-04T3= 18T4= 68T5= 19626E-05

n= variabelp= 5

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00024 0000 4 -157 017 00024 00002 4 3 000

12L 00038 0002 4 006 154 00038 00018 4 3 00046L 00039 0000 4 011 026 00039 00003 4 3 00026L 00039 0000 2 018 004 00039 00000 2 1 00064L 00049 0002 4 122 159 00049 00018 4 3 000

Totgem 0004 0001 mgkg 1-level 172 (173) 5 00038 () 5 4Totstd= 0001 0001 5-level 157 (153)

RESULTS Mean = 000378 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000123 --gt 3252 r = 00034Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000142 --gt 3754 R = 00040Remarks none

000 050 100 150 200

k-values

4L

12L

46L

26L

64L

Mandels k statistics(Sludge 1 - PBD 153)

00 00 00 00 00 00 00

Deviation from Mean

4L

12L

46L

26L

64L

Labo

rato

ries

Sludge 1 - PBD 153 -- Mean PARM = 0004 [mgkg]

-200 -100 000 100 200

h-values

4L

12L

46L

26L

64L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 153)

Sludge 1-PBD 153

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 154)Mandels h statistics(Sludge 1 - PBD 154)

Sample Sludge 1 NA

Element PBD 154

General calcparmT1= NAT2= NAT3=T4=T5=

n= variabelp=

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00021 0000 3 -100 021 NA - 4L - - NA

46L 00025 0000 4 115 018 NA - 46L - - NA64L 00021 0001 4 -066 179 - - 64L - - NA12L 00023 0000 4 050 085 - - 12L - - NA

Totgem 0002 0000 mgkg 1-level 149 (167) NA (4L46L64L12L) -1Totstd= 0000 0000 5-level 142 (15) 4

RESULTS Mean = NA mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NAReproducibility var S2R = NAReproducibility std SR = NA --gt NA R = NARemarks 4 Labs rejected (4L46L64L12L)

000 050 100 150 200

k-values

4L

46L

64L

12L

Mandels k statistics(Sludge 1 - PBD 154)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

4L

46L

64L

12L

Labo

rato

ries

NA

-100 000 100 200

h-values

4L

46L

64L

12L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 154)

Sludge 1-PBD 154

Unit mgkg

Mandels k statistics(Soil 3 - PBD 154)Mandels h statistics(Soil 3 - PBD 154)

Sample Soil 3 NUM

Element PBD 154

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

4L 00010 - 1 150 Fail - - 4L - - NUM46L 00001 0000 4 -053 096 Fail - - 46L - - NUM64L 00001 0000 4 -056 105 Fail NUM - 64L - - NUM12L 00002 0000 4 -040 099 Fail - - 12L - - NUM

Totgem 000037 0000 mgkg 1-level 149 (164) NUM (4L46L64L12L) -1Totstd= 000042 0000 5-level 142 (153) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (4L46L64L12L)

000 050 100 150

k-values

4L

46L

64L

12L

Mandels k statistics(Soil 3 - PBD 154)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

4L

46L

64L

12L

Labo

rato

ries

NUM

-100 000 100 200

h-values

4L

46L

64L

12L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 154)

Soil 3-PBD 154

Unit mgkg

Mandels k statistics(Compost 1 - PBD 209)Mandels h statistics(Compost 1 - PBD 209)

Sample Compost 1 NUM

Element PBD 209

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00065 0003 2 -049 032 - - 4L - - NUM

44L 00573 0021 4 150 197 Fail - - 44L - - NUM12L 00078 0001 4 -045 011 - - 12L - - NUM26L 00049 0000 2 -056 000 NUM - 26L - - NUM

Totgem 0019 0006 mgkg 1-level 149 (177) NUM (4L44L12L26L) -1Totstd= 0025 0010 5-level 142 (159) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (4L44L12L26L)

000 050 100 150 200

k-values

4L

44L

12L

26L

Mandels k statistics(Compost 1 - PBD 209)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

4L

44L

12L

26L

Labo

rato

ries

NUM

-100 000 100 200

h-values

4L

44L

12L

26L

Labo

rato

ries

Mandels h statistics(Compost 1 - PBD 209)

Compost 1-PBD 209

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 209)Mandels h statistics(Sludge 1 - PBD 209)

Sample Sludge 1 Sludge 1 - PBD 209 -- Mean PARM = 0249 [mgkg]

Element PBD 209

General calcparmT1= 394542E+00T2= 107296E+00T3= 16T4= 56T5= 19723E-02

n= variabelp= 5

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 01550 0055 4 -112 148 Fail 01550 00551 4 3 -009

46L 02050 0007 2 -053 019 02050 00071 2 1 -00412L 02137 0058 4 -042 155 02137 00576 4 3 -00426L 03149 0021 2 078 057 Fail 03149 00210 2 1 00764L 03577 0007 4 129 020 Fail 03577 00074 4 3 011

Totgem 0249 0030 mgkg 1-level 172 (185) 5 02493 () 5 4Totstd= 0084 0025 5-level 157 (162)

RESULTS Mean = 024926 mgkg

Repeatability variance S2r = 000179Repeatability std Sr = 004234 --gt 1699 r = 01186Between lab variance S2L = 000743Reproducibility var S2R = 000922Reproducibility std SR = 009604 --gt 3853 R = 02689Remarks none

000 050 100 150 200

k-values

4L

46L

12L

26L

64L

Mandels k statistics(Sludge 1 - PBD 209)

-01 -01 00 01 01 02

Deviation from Mean

4L

46L

12L

26L

64L

Labo

rato

ries

Sludge 1 - PBD 209 -- Mean PARM = 0249 [mgkg]

-200 -100 000 100 200

h-values

4L

46L

12L

26L

64L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 209)

Sludge 1-PBD 209

Unit mgkg

Mandels k statistics(Soil 3 - PBD 209)Mandels h statistics(Soil 3 - PBD 209)

Sample Soil 3 Soil 3 - PBD 209 -- Mean PARM = 0258 [mgkg]

Element PBD 209

General calcparmT1= 596398E+00T2= 191917E+00T3= 22T4= 84T5= 13249E-02

n= variabelp= 6

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean26L 01162 0021 2 -108 074 Fail 01162 00207 2 1 -0144L 01303 0031 4 -097 111 Fail 01303 00312 4 3 -013

46L 01975 0036 4 -046 128 Fail 01975 00359 4 3 -00644L 02898 0035 4 024 124 Fail 02898 00346 4 3 00312L 03895 0018 4 100 065 Fail 03895 00181 4 3 01364L 04260 0022 4 127 078 Fail 04260 00219 4 3 017

Totgem 0258 0027 mgkg 1-level 187 (177) 6 02582 () 6 5Totstd= 0132 0008 5-level 166 (154)

RESULTS Mean = 025818 mgkg

Repeatability variance S2r = 000083Repeatability std Sr = 002878 --gt 1115 r = 00806Between lab variance S2L = 001640Reproducibility var S2R = 001723Reproducibility std SR = 013127 --gt 5084 R = 03676Remarks none

000 050 100 150

k-values

26L

4L

46L

44L

12L

64L

Mandels k statistics(Soil 3 - PBD 209)

-02 -01 -01 00 01 01 02 02

Deviation from Mean

26L

4L

46L

44L

12L

64L

Labo

rato

ries

Soil 3 - PBD 209 -- Mean PARM = 0258 [mgkg]

-200 -100 000 100 200

h-values

26L

4L

46L

44L

12L

64L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 209)

Soil 3-PBD 209

Unit mgkg

Mandels k statistics(Compost 1 - Sum PBD)Mandels h statistics(Compost 1 - Sum PBD)

Sample Compost 1 Compost 1 - Sum PBD -- Mean PARM = 0009 [mgkg]

Element Sum PBD

General calcparmT1= 154064E-01T2= 169065E-03T3= 18T4= 68T5= 11354E-04

n= variabelp= 5

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00031 0002 4 -067 016 00031 00016 4 3 -0014L 00055 0005 4 -056 048 00055 00047 4 3 000

46L 00085 0003 4 -042 031 00085 00030 4 3 00026L 00123 0000 2 -024 003 00123 00002 2 1 00012L 00154 0002 4 -011 021 00154 00021 4 3 00144L 00613 0023 4 200 237 Fail - - 44L - - 005

Totgem 0018 0006 mgkg 1-level 187 (177) 5 00089 (44L) 5 4Totstd= 0022 0009 5-level 166 (154) 1

RESULTS Mean = 000893 mgkg

Repeatability variance S2r = 000001Repeatability std Sr = 000296 --gt 3308 r = 00083Between lab variance S2L = 000002Reproducibility var S2R = 000003Reproducibility std SR = 000570 --gt 6374 R = 00159Remarks 1 Lab rejected (44L)

000 050 100 150 200 250

k-values

10L

4L

46L

26L

12L

44L

Mandels k statistics(Compost 1 - Sum PBD)

00 00 00 00 00 00 01 01

Deviation from Mean

10L

4L

46L

26L

12L

44L

Labo

rato

ries

Compost 1 - Sum PBD -- Mean PARM = 0009 [mgkg]

-100 000 100 200

h-values

10L

4L

46L

26L

12L

44L

Labo

rato

ries

Mandels h statistics(Compost 1 - Sum PBD)

Compost 1-Sum PBD

Unit mgkg

Mandels k statistics(Sludge 1 - Sum PBD)Mandels h statistics(Sludge 1 - Sum PBD)

Sample Sludge 1 Sludge 1 - Sum PBD -- Mean PARM = 0256 [mgkg]

Element Sum PBD

General calcparmT1= 531806E+00T2= 162188E+00T3= 22T4= 84T5= 25223E-02

n= variabelp= 6

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00423 0025 4 -156 044 Fail 00423 00252 4 3 -02146L 01808 0118 4 -049 205 - - 46L - - -0074L 01810 0056 4 -049 097 01810 00558 4 3 -007

38L 02168 0006 4 -022 010 02168 00059 4 3 -00412L 02890 0065 4 034 113 02890 00647 4 3 00364L 03958 0008 4 116 014 Fail 03958 00079 4 3 01426L 04094 0034 2 126 059 Fail 04094 00337 2 1 015

Totgem 0245 0044 mgkg 1-level 198 (179) 6 02557 (46L) 6 5Totstd= 0130 0039 5-level 171 (155) 1

RESULTS Mean = 025570 mgkg

Repeatability variance S2r = 000158Repeatability std Sr = 003970 --gt 1553 r = 01112Between lab variance S2L = 001807Reproducibility var S2R = 001964Reproducibility std SR = 014015 --gt 5481 R = 03924Remarks 1 Lab rejected (46L)

000 050 100 150 200 250

k-values

10L

46L

4L

38L

12L

64L

26L

Mandels k statistics(Sludge 1 - Sum PBD)

-03 -02 -02 -01 -01 00 01 01 02 02

Deviation from Mean

10L

46L

4L

38L

12L

64L

26L

Labo

rato

ries

Sludge 1 - Sum PBD -- Mean PARM = 0256 [mgkg]

-200 -100 000 100 200

h-values

10L

46L

4L

38L

12L

64L

26L

Labo

rato

ries

Mandels h statistics(Sludge 1 - Sum PBD)

Sludge 1-Sum PBD

Unit mgkg

Mandels k statistics(Soil 3 - Sum PBD)Mandels h statistics(Soil 3 - Sum PBD)

Sample Soil 3 Soil 3 - Sum PBD -- Mean PARM = 0227 [mgkg]

Element Sum PBD

General calcparmT1= 610980E+00T2= 200876E+00T3= 26T4= 100T5= 13106E-02

n= variabelp= 7

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00028 0001 4 -037 000 Fail 00028 00005 4 3 -02226L 01179 0021 2 -036 003 Fail 01179 00208 2 1 -0114L 01305 0031 4 -036 004 Fail 01305 00308 4 3 -010

46L 02065 0035 4 -036 005 Fail 02065 00350 4 3 -00244L 02923 0037 4 -035 005 Fail 02923 00365 4 3 00712L 04051 0015 4 -034 002 Fail 04051 00149 4 3 01864L 04314 0022 4 -033 003 Fail 04314 00223 4 3 0203L 305500 2051 2 247 283 Fail - - 3L - - 3032

Totgem 4017 0276 mgkg 1-level 206 (181) 7 02266 (3L) 7 6Totstd= 10722 0717 5-level 175 (156) 1

RESULTS Mean = 022663 mgkg

Repeatability variance S2r = 000069Repeatability std Sr = 002626 --gt 1159 r = 00735Between lab variance S2L = 002568Reproducibility var S2R = 002637Reproducibility std SR = 016238 --gt 7165 R = 04547Remarks 1 Lab rejected (3L)

000 050 100 150 200 250 300

k-values

10L

26L

4L

46L

44L

12L

64L

3L

Mandels k statistics(Soil 3 - Sum PBD)

-50 00 50 100 150 200 250 300 350

Deviation from Mean

10L

26L

4L

46L

44L

12L

64L

3L

Labo

rato

ries

Soil 3 - Sum PBD -- Mean PARM = 0227 [mgkg]

-100 000 100 200 300

h-values

10L

26L

4L

46L

44L

12L

64L

3L

Labo

rato

ries

Mandels h statistics(Soil 3 - Sum PBD)

Soil 3-Sum PBD

19

Annex 4

Raw data submitted

Sample Compost1 Sample Compost 1 Sample Compost 1Element PBD 99 Element PBD 100 Element PBD 153

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]4L 00021 10L 00008 44L 000504L 00024 10L 00008 44L 000604L 00014 10L 00007 44L 000504L 00020 10L 00011 46L 00004

10L 00029 46L 00007 46L 0001210L 00027 46L 00012 46L 0000410L 00032 46L 00009 46L 0000946L 00025 46L 00007 12L 0000446L 00052 12L 00008 12L 0000846L 00029 12L 00012 12L 0000446L 00026 12L 00008 12L 0000712L 00026 12L 00014 26L 0000512L 00043 26L 00007 26L 0000512L 00026 26L 0000612L 0004726L 0002626L 00024

Sample Compost 1 Sample Compost 1 Sample Compost 1Element PBD 154 Element PBD 183 Element PBD 196

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]4L 00010 46L 00002 46L 00011

46L 00003 46L 00024 46L 0000846L 00007 46L 00021 12L 0000246L 00003 46L 00003 12L 0000346L 00004 12L 00003 12L 0000112L 00003 12L 00011 12L 0000212L 00005 12L 0000312L 00031 12L 0000312L 00006

Sample Compost 1 Sample Compost 1 Sample Compost 1Element PBD 197 Element PBD 203 Element PBD 209

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00002 46L 00010 4L 0004146L 00023 12L 00002 4L 0008946L 00022 12L 00003 44L 0041012L 00004 12L 00002 44L 0084012L 00006 12L 00002 44L 0064012L 00003 44L 0040012L 00004 12L 00079

12L 0007312L 0006512L 0009326L 0004926L 00049

Sample Compost 1Element PBD 47

LAB PARM [mgkg]26L 0003826L 00039

Element PBD 99 Element PBD 47 Element PBD 209LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]

4L 00170 10L 00210 4L 010004L 00200 10L 00220 4L 018004L 00170 10L 00210 4L 012004L 00190 46L 00300 4L 0220010L 00280 46L 00280 46L 0210010L 00300 46L 00250 46L 0200010L 00290 46L 00260 64L 0351846L 00340 64L 00059 64L 0363846L 00330 64L 00057 64L 0364546L 00300 64L 00062 64L 0350846L 00310 64L 00060 12L 0220964L 00194 12L 00191 12L 0177164L 00154 12L 00187 12L 0292264L 00185 12L 00190 12L 0164664L 00159 12L 00186 26L 0329712L 00242 26L 00666 26L 0300012L 00223 26L 0033212L 0022112L 0022226L 0024626L 00400

Element PBD 203 Element PBD 197 Element PBD 196LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00022 46L 00027 46L 0002446L 00014 46L 00024 46L 0002264L 00036 12L 00161 64L 0005864L 00058 12L 00060 64L 0006512L 00063 12L 00061 12L 0004812L 00034 12L 00036 12L 0002512L 00038 12L 0003212L 00027 12L 00022

Element PBD 183 Element PBD 154 Element PBD 153LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00049 4L 00020 4L 0002246L 00035 4L 00022 4L 0002446L 00036 4L 00020 4L 0002246L 00034 46L 00025 4L 0002664L 00027 46L 00025 46L 0004064L 00023 46L 00025 46L 0004264L 00024 46L 00023 46L 0003564L 00020 64L 00034 46L 0003812L 00230 64L 00023 64L 0007412L 00032 64L 00017 64L 0004712L 00031 64L 00011 64L 0004612L 00030 12L 00030 64L 0003026L 00007 12L 00021 12L 0006526L 00008 12L 00021 12L 00029

12L 00021 12L 0003226L 00015 12L 0002926L 00019 26L 00039

26L 00040

Element PBD 100LAB PARM [mgkg]

4L 000384L 000414L 000374L 00038

38L 0219038L 0220038L 0208038L 0220010L 0004410L 0005010L 0004310L 0004646L 0005746L 0005946L 0005346L 0005312L 0004312L 0004512L 0004312L 0004326L 0006226L 00057

Sample Soil 3 Sample Soil 3 Sample Soil 3Element PBD 99 Element PBD 47 Element PBD 100

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]10L 00016 10L 00011 10L 0000310L 00019 10L 00010 10L 0000410L 00013 10L 00012 10L 0000410L 00019 46L 00007 10L 0000246L 00025 46L 00022 46L 0000246L 00025 46L 00005 46L 0000646L 00008 46L 00007 46L 0000246L 00011 12L 00010 46L 0000264L 00005 12L 00017 3L 29100064L 00005 12L 00010 3L 32000064L 00006 12L 00009 26L 0000564L 00007 26L 00007 26L 0000512L 00012 26L 0000712L 0001312L 0001312L 0001226L 0000526L 00006

Sample Soil 3 Sample Soil 3 Sample Soil 3Element PBD 153 Element PBD 154 Element PBD 196

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]44L 00050 4L 00010 46L 0000744L 00050 46L 00001 46L 0001146L 00002 46L 00002 46L 0000846L 00003 46L 00001 46L 0001146L 00002 46L 00002 64L 0002646L 00002 64L 00001 64L 0002664L 00001 64L 00001 64L 0002964L 00001 64L 00001 64L 0003464L 00001 64L 00002 12L 0004564L 00002 12L 00003 12L 00032

12L 00002 12L 0002212L 00002 12L 0002112L 00002

Sample Soil 3 Sample Soil 3 Sample Soil 3Element PBD 197 Element PBD 203 Element PBD 209

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00006 46L 00011 4L 0091046L 00013 46L 00017 4L 0150046L 00011 46L 00015 4L 0120046L 00013 46L 00018 4L 0160012L 00090 64L 00013 44L 0337012L 00056 64L 00014 44L 0281012L 00033 64L 00016 44L 0287012L 00032 64L 00015 44L 02540

12L 00055 46L 0230012L 00041 46L 0220012L 00027 46L 0150012L 00026 46L 01900

64L 0438164L 0401664L 0414464L 0449812L 0367112L 0397812L 0409112L 03838

Sample Soil 3 26L 0102Element PBD 183 26L 0131

LAB PARM [mgkg]46L 0000746L 0000846L 0005846L 0000764L 0000264L 0000364L 0000364L 0000312L 0001512L 0001112L 0000712L 00007

European Commission EUR 23003 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on polybrominated diphenylethers Author(s) E Sobiecka H van der Sloot D Barcelo B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 68 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07403-5 Abstract Project HORIZONTAL is interdisciplinary aiming at a harmonisation and horizontal standardisation of test procedures in particular for sludge soils and biowastes In the context of this standardization project a series of draft technical specification were designed upon an extensive desk study fine-tuned after expert consultations and finally validated in international intercomparisons exercise This report summarises the work performed within the validation study of the draft standard for the determination of polybrominated diphenylethers (PBDE) in soils sludge and treated bio-waste using gas-chromatography method with mass selective detection (GC-MS) It further explains the underlying statistical concept for the calculation of reproducibility and repeatability from intercomparisons data In addition all single values results of the statistical evaluation as well as background information on the validation materials used are described and explained

The mission of the JRC is to provide customer-driven scientific and technical support for the conception development implementation and monitoring of EU policies As a service of the European Commission the JRC functions as a reference centre of science and technology for the Union Close to the policy-making process it serves the common interest of the Member States while being independent of special interests whether private or national

LB

-NA

-23003-EN

-C

5

Introduction to the validation project Project HORIZONTAL is interdisciplinary aiming at a harmonisation and horizontal standardisation of test procedures in particular for sludges soils and biowastes It was created as in response to the European Commission Mandate M 330 given to CEN asking for the development and validation of those standards in support of forthcoming EU Directives such as

o The revision of the Sewage Sludge Directive 86278EEC o The Directive on the biological treatment of biodegradable waste o The initiative on a legal framework for soil monitoring in Europe

This mandate explicitly considers standards for the entire analytical procedure (ie sampling pre-treatment and analytical measurement methods for inorganic organic hygiene and biological parameters) These are grouped into classes according to their physicalchemical properties which in turn determine the methods needed to quantify the potential impact on human and animal health plant uptake soil function and groundwater quality As the materials generally feature a mixture of different types of contaminants it is important to provide an integrated answer covering evaluation of all relevant pollutants In order to fulfil the requirements of the aforementioned mandate the European Commissions Joint Research Centre (JRC) and its Directorate-General for Environment (DG ENV) together with the Technical Committees of the European Standardisation Committee (CEN TCs) concerned designed a pre-normative research initiative called Project HORIZONTAL and presented it to the Commission and the Environmental Authorities in the Member States After an extensive literature research and careful evaluation of the feasibility of a given horizontal standard the standards were drafted and finally validated in an European laboratory intercomparison The underlying statistical concept information about the materials used details about the participants measurement results obtained as well as the derived performance characteristics obtained for the determination of polybrominated diphenylethers (PBDE) are described hereafter

6

11 Statistical concept underlying the validation According to the requirements of the work package concerning data handling amp interpretation of the project HORIZONTAL-ORG the respective validation intercomparisons have to be evaluated according to the principles laid down in ISO standard 5725-21994 In particular repeatability and reproducibility of the draft standard methods have to be determined The determination of trueness would require the availability of independent reference values for the materials investigated This however is not possible and was not requested in the frame of this work In the following the approach chosen is explained

111 Introduction to the statistical model The statistical model used in ISO 5725 for estimation of accuracy of a measurement method assumes that every test result is the sum of three components

eBmy ++= y test result m general mean B laboratory component of bias under repeatability conditions e random error occurring in every measurement under repeatability conditions

In the workprogram the quantification of term e is explicitly asked for (ie repeatability and reproducibility) The repeatability variance is measured directly as the variance of the error term e but the reproducibility depends on the sum of the repeatability variance and the between-laboratory variance

( )er var=σ 22rLR σσσ += with ( )BL var=σ

However soil biowaste and sludge are multi-phase materials ie they contain two or more distinct types of particles which are fundamentally different in their properties and composition As a consequence this introduces an important source of variation for the intercomparison exercise which needs to be considered ie the inherent heterogeneity of the materials Thus a contribution of variation between samples H is introduced to the general statistical model

HeBmy +++= Using ANOVA techniques the different variances are calculated and separated for the evaluation

7

112 Requirements for precision experiment

Layout of the experiment A suite of 10 to 12 different materials (soil sludge and biowaste) has been made available for the intercomparison exercise For each parameter investigated at least 10 to laboratories should be nominated to participate The same laboratories should be used for different parameters as far as possible Due to the complexity of analysis and the respective workload to the laboratories it was decided to propose three materials for the validation of the PBDE draft standard Each laboratory received two bottles of each material and was be requested to perform 4 independent analyses per material1 (2 per bottle) using the respective draft standard methods The 4 analysis per material should be carried out under repeatability conditions (ie same operator2 same equipment within a short period of time) As far as possible also the different materials should be measured under repeatability conditions however changes of eg operator or equipment are permitted but must be reported Likewise different materials can be analysed on different days if necessary Equipment used in the experiment needed to be checked prior to the experiment according to the requirements of the draft standard The results of these checks have to be documented Similarly date and time of each measurement had to be recorded for verification of repeatability conditions An appropriate timeframe for the entire exercise has been set and was to be respected

Recruitment of the laboratories Each sub-workpackage leader of HORIZONTAL was asked to select the laboratories using the information from section 52 of ISO 5725-21994 and provide the signed questionnaires (see also Annex 1) The workpackage leaders were responsible for providing the laboratories with the draft standard method and explaining the context of this exercise

Preparation and use of the materials Materials used for the exercise were prepared according to the general requirements for reference materials as laid down in ISO Guide 34 Materials were accompanied by instructions for use

Reporting of results Online submissions of results using an internet-based IT platform as well as XLS-Spreadsheets were used In case of online data submission the participating laboratories received a unique and confidential login and password in due time enabling them to

1 Independent analysis means analysis of independent test portions applying the entire analytical scheme to this test portion from eg extraction to quantification For instance it does not mean replicate injections of aliquots into a GC-MS instrument 2 Operator in this context may also consist of a fixed team of persons eg one person performing extraction one clean-up one quantification

8

enter their data in a structured form For authentication purposes a signed printout had to be submitted by mail The online data submission included a detailed questionnaire for additional information on the measurements

113 Statistical analysis Statistical analysis of data followed the requirements of ISO 5725-21994 and ISO 5725-51998 Appropriate tests for the homogeneity of variance detection of outliers and normal distribution were applied Statistical evaluation was done using an Excel Macro developed tested and successfully applied in other occasion by ECN Evaluation was executed jointly by JRC and ECN

12 Validation exercise for PBDE

121 Compounds to be measured The following compound were selected for the validation exercise Tetra-BDE-47 Penta-BDE-100 Penta-BDE-99 Hexa-BDE-154 Hexa-BDE-153 Hepta-BDE-183 Octa-BDE-196 Octa-BDE-197 Octa-BDE-203 Deca-BDE-209

122 Samples dispatched for the validation of PBDE After a preliminary rough screening the following materials were used for the validation round of PBDE

bull Compost 1 A pollutant loaded compost material from Vienna bull Sewage Sludge 1 A mixed sewage sludge from Essen bull Soil 3 A sludge amended soil from Barcelona

A more detailed description of background concentrations can be found in Annex 2 to this report The samples were dispatched simultaneously to all participants using a private courier service

123 Draft standards to be followed The draft standards to be followed could be downloaded following this link which is situated on the website of the Project HORIZONTAL httpwwwecnnldocssocietyhorizontalBFR_Standard_for_validationpdf

124 Analytical programm Of each of the three materials 2 bottles had to be analysed and each bottle had to analysed independently twice As mentioned above analyses were to be done under repeatability conditions Results were to be reported referring to DRY MATTER content The choice how to apply dm correction was free for each participant

9

125 Timing and Submission of data Dispatch of samples was done on the 18th of October 2006 For users of the Online data submission system (MILC) User Registration was possible from 14th of November 2006 with opening of the MILC Data Submission on 1st of December 2006 The deadline for submission of results has been set for PBDE to the 12th of January 2007 but was extended to the end of the same months After that no further submission was possible Alternatively the participants were allowed to submit data electronically as Excel sheet using simply Email All data were treated in a confidential way Any presentation hereafter will refer only to numerical data and it will not be possible to identify the originating laboratory Lab Codes displayed are NOT related to the order of laboratories hereafter In addition to the information provide an Helpdesk was implemented in order to give quick and individual response to the participants during and immediately after the validation study In case of doubt and suspected transcription errors further enquires were conducted by JRC

10

126 Participants The following table lists the participating organisations and entities in the validation exercise for the horizontal PBDE standard

bull Austria o Umweltbundesamt

bull Czech Republic o Povodi Labe statni podnik - OVHL Laboratory

bull France o CIRSEE o CTC Environnement o INERIS

bull Germany o Federal Environmental Agency Section III 34 Laboratory Methods for

the Surveillance of Waste and Wastewater (UBA) bull Italy

o European Commission DG JRC IES bull Spain

o Consejo Superior de Investigaciones Cientificas (CSIC)

bull Sweden o ALCONTROL AB

11

13 Summary results and derived performance characteristics The result of the various statistical evaluation including outlier tests calculation of repeatability and reproducibility standard deviation for the congeners of interest can be found in Annex 3 of this report In addition all data submitted by the participants as well as those considered for the calculation of the performance characteristics are listed in Annex 3 to this report Based on these calculations the following results were obtained in the validation round upon statistical evaluation according to ISO 5725-2 The average values the repeatability standard deviation (sr) and the reproducibility standard deviation (sR) were obtained (Table1) The repeatability is determined as an interval around a measurement result (ie repeatability limit) This interval corresponds to the maximum difference that can be expected (with a 95 statistical confidence) between one test result and another both test results being obtained under the following conditions The tests are performed in accordance with all the requirements of the present standard by the same laboratory using its own facilities and testing laboratory samples obtained from the same primary field sample and prepared under identical procedures The repeatability limit was calculated using the relationship r test = f radic2 s rtest with the critical range factor f = 2 The reproducibility like repeatability is also determined as an interval around a measurement result (ie reproducibility limit) This interval corresponds to the maximum difference that can be expected (with a 95 statistical confidence) between one test result and another test result obtained by another laboratory both test results being obtained under the following conditions The tests are performed in accordance with all the requirements of the present standard by two different laboratories using their own facilities and testing laboratory samples obtained from the same primary field sample and prepared under identical procedures The reproducibility limit was calculated using the relationship R = f radic2 sR with the critical range factor f = 2

12

Table 1 - Results of the interlaboratory comparison studies of the determination of selected polybrominated diphenyl ethers (PBDE) by gaschromatography with mass spectrometric detection (GC-MS) in soil sludge and treated biowaste All concentrations are expressed in mgkg dm

Matrix Parameter Mean sr sR r R p Outliers Used No of data

No of data reported below

detection

Total no of data

Sludge 1 PBD 47 00181 461 4 15 5 20 Compost 1 00039 94 3 12 0 12 Soil 3 00010 50 50 00014 00014 4 0 13 10 23 Sludge 1 PBD 99 00239 64 28 00043 00186 5 1 19 0 23 Compost 1 00029 31 35 00025 00028 5 0 17 4 21 Soil 3 00013 499 4 16 8 24 Sludge 1 PBD 100 00049 51 17 00007 00024 5 1 18 2 24 Compost 1 00009 25 29 00006 00007 4 0 14 7 21 Soil 3 61103 211 3 10 15 25 Sludge 1 PBD 153 00038 33 38 00034 0004 5 0 18 0 18 Compost 1 00019 116 3 11 3 14 Soil 3 00011 177 2 10 10 20 Sludge 1 PBD 154 00023 234 4 15 2 17 Compost 1 00008 1118 3 9 5 14

13

Matrix Parameter Mean sr sR r R p Outliers Used No of data

No of data reported below

detection

Total no of data

Soil 3 00002 1049 4 13 6 19 Sludge 1 PBD 183 00048 1217 3 12 2 14 Compost 1 00009 1048 2 8 5 13 Soil 3 00011 1395 3 12 6 18 Sludge 1 PBD 196 00037 470 2 8 7 15 Compost 1 00004 950 2 6 4 10 Soil 3 00023 519 3 12 2 14 Sludge 1 PBD 197 00062 834 2 6 8 14 Compost 1 00009 1001 2 7 7 14 Soil 3 00032 904 2 8 6 14 Sludge 1 PBD 203 00037 461 2 8 4 12 Compost 1 00004 978 2 5 3 8 Soil 3 00022 598 3 12 0 12 Sludge 1 PBD 209 02493 170 39 01186 02689 5 0 16 2 18 Compost 1 00273 104 3 10 5 15 Soil 3 02582 1115 51 00806 03676 6 0 22 0 22

14

Matrix Parameter Mean sr sR r R p Outliers Used No of data

No of data reported below

detection

Total no of data

Sludge 1 Sum PBD 0256 155 548 0111 0392 6 1 22 Compost 1 0009 331 637 0008 0016 5 1 18 Soil 3 0227 116 717 0074 0455 7 1 26 Abbreviations sr Repeatability standard deviation SR Reproducibility standard deviation r Repeatability limit (comparing two measurements) R Reproducibility limit (comparing two measurements) p Number of labs determination not possible

15

14 Annexes Annex 1 Model questionnaire to be filled by the participating laboratories Annex 3 Report on the validation materials used Annex 2 Statistical calculations Annex 3 Data submitted

16

Annex 1

Model questionnaire to be filled by the participating laboratories

Model questionnaire to be filled by the participating laboratories Name of laboratory Contact person Contact details email Phone Fax Mail address of lab Dispatch address of lab for shipment of samples (no PO boxes) Title of measurement method (copy attached) Our laboratory is willing to participate in the precision experiment for this draft standard method

Yes No As participant we understand that

bull All essential apparatus chemicals and other requirements specified in the method must be available in our laboratory when the programme begins

bull Specified timing requirements such as starting and finishing date of the programme must be rigidly met

bull The method must be strictly adhered to bull Samples must be handled in accordance with instructions bull A qualified operator must perform the measurements

Having studied the method and having made a fair appraisal of our capabilities and facilities we feel that we will be adequately prepared for cooperative testing of this method Comments helliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphellip Signature Date

17

Annex 2

Report on the validation materials used

VI

Abstract This report gives an overview on the available analytical information on the following raw materials to be used for the production of validation materials of the so-called Project HORIZONTAL

bull Four sludge materials from Duumlsseldorf Germany

bull An agricultural soil material from Reading United Kingdom

bull A compost material from Vienna Austria

bull A compost material from Korschenbroich Germany

bull A sludge-amended agricultural soil from Pavia Province Italy

bull A sludge-amended soil from Barcelona Spain

bull A sludge-amended soil from Essen Germany

bull A long-term sludge exposed soil from Hohenheim Germany

VII

List of Abbreviations Throughout this report the following abbreviations are used

AOX absorbable organic halogens

Corg organic carbon content

Ctotal total carbon content

CAT cation exchangeable

CDD chlorinated dibenzodioxin

CDF chlorinated dibenzofuran

DEHP di(2-ethylhexyl)phthalate

DM dry matter

EPA Environment Protection Agency

EU European Union

FM fresh matter

Hp hepta

Hx hexa

IES Institute for Environment and Sustainability

IRMM Institute for Reference Materials and Measurements

JRC Joint Research Centre

LAS linear alkylsulfonates

LoD limit of detection

LUA Landesumweltamt

Ntotal total nitrogen content

NH4-N Ammonium nitrogen

NO3-N Nitrate nitrogen

NP nonylphenol

NRW North Rhine Westphalia

O octa

P poly

PAH polycyclic aromatic hydrocarbon

PCB polychlorinated biphenyl

Pe penta

T tetra

TEQ toxicity equivalent

UBA Umweltbundesamt

WHO World Health Organization

WWTP waste water treatment plant

6

1 Introduction This report gives an overview on the available analytical information on the following raw materials to be used for the production of validation materials of the so-called Project HORIZONTAL

bull Four sludge materials from Duumlsseldorf Germany

bull An agricultural soil material from Reading United Kingdom

bull A compost material from Vienna Austria

bull A compost material from Korschenbroich Germany

bull A sludge-amended agricultural soil from Pavia Province Italy

bull A sludge-amended soil from Barcelona Spain

bull A sludge-amended soil from Essen Germany

bull A long-term sludge exposed soil from Hohenheim Germany

The following analytical information was gathered partly before and during the sampling of the raw materials to be used for the production of the HORIZONTAL validation materials The material were sampled by IES and shipped to IRMM in the course of the year 2005 The information gathered was then completed by various analytical screenings for PAHs and PCBs done by the Institute for Reference Materials and Measurements Geel Belgium for phthalates done by UBA Berlin Germany for PBDE done by IIQAB-CSIC Barcelona Spain for trace elements and some selected major and minor elements by the Institute for Environment and Sustainability Ispra Italy

The work compiled hereafter is based on the numerous additional efforts of the scientists working at various members of the consortium Project HORIZONTAL-Org and contributing organisations

This work is gratefully acknowledged

2 Overview on property values

21 Sludge materials from Duumlsseldorf Germany

The various sewage sludge materials originate from various installations in the North Rhine Westphalia and were produced and sampled by staff from the Landesumweltamt (LUA) NRW under the responsibility from Dr K Furtmann

In total four sludge materials (Sludge A and D from a major municipal WWTP Sludge B from a municipal WWTP with industrial input and Sludge C from a municipal WWTP with high PCB-Content) were obtained and will be blended to two final materials Before sampling the following analytical data for a typical sample were received

7

Table 1 ndash Analytical data obtained on an average sludge sample in LUA NRW (with courtesy of K Furtmann LUA Duumlsseldorf)

Parameter Concentration PCB 120 ugkg DEHP 110 mgkg PAH 5 mgkg (EPA) PCDDF 15 ng TEkg PBDE 400 ugkg NP 40 mgkg LAS 3 gkg AOX 300 mgkg

Subsequent screening led to the information displayed hereafter It should be stressed that the data were obtained as SCREENING information on the UNTREATED or partially treated raw materials Therefore the final target values which are relevant for the validation intercomparison can be different

Table 2 ndash Analytical data obtained on a first screening on the sludge samples from LUA NRW

Sewage sludge A

Dusseldorf

sewage sludge D

Dusseldorf PCB (ngg) 28 62 35 52 101 65 101 31 38 118 49 40 153 30 33 105 24 11 138 46 38 156 lt1 lt1 180 34 23 170 23 19 PAH (ngg) Naphtalene 34 381 Acenaphtylene 15 43 Acenaphthene 81 108 Fluorene 94 1167 Phenantrene 3440 Anthracene 22 344 Flouranthene 316 4817 Pyrene 235 3011 Benz(a)anthracene 473 791 Chrysene 691 1078 Benz(b)fluoranthene 538 1688 Benz(k)fluoranthene 228 635 Benz(a)pyrene 383 1114 Indeno(123-cd)pyrene 92 229 Dibenzo(ah)anthracene 71 70 Benzo(ghi)perylene 80 185

8

Table 3 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Sludge D (1) 0135 41474 385 Sludge B (2) 0538 0034 30634 547 Sludge A (3) 0184 0037 31399 146 Sludge C (4) 0354 1528 6678 229

Table 4 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Sludge 2

(B)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

554

959

694

591

772

509

nq

nq

970

2216

2379

Table 5 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena IES Ispra Spain) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Sludge 1 (D) 265 290 533 359 1231 338 784 438 lt 005 232 786 Sludge 2 (B) 119 311 626 202 278 299 722 251 lt 005 118 625 Sludge 3 (A) 168 360 621 332 847 416 119 451 lt 005 116 1237 Sludge 4 (C) 563 198 116 273 726 511 473 618 lt 005 444 2015

Table 6 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Sludge 1 (D) 2154 58 844 099 103 101 4367 lt15 50448 Sludge 2 (B) 1067 366 692 046 1491 077 5217 lt15 57633 Sludge 3 (A) 731 663 684 035 1287 068 3733 lt15 60369 Sludge 4 (C) 4379 965 527 163 522 107 5628 lt15 23945

Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM)Sludge 1 (D) 03 2403 101 1002 350 15 1944 132Sludge 2 (B) 031 315 97 879 172 12 514 180Sludge 3 (A) 031 1281 153 1567 265 16 1440 168Sludge 4 (C) 055 231 628 2625 371 81 1101 244

9

22 Agricultural soil material from Reading United Kingdom

The material was proposed by the University of Reading (S Nortcliff) and was sampled from a site called ldquoFrogmore Farmrdquo which was featured in the ldquoMetalsrdquo Report for HORIZONTAL This site is close to Reading with soils developed on flintyloamy periglacial materials over Chalk has a long and well documented history of sludge application The focus of the work of Nortcliff et al undertook at this site and the monitoring and control at the site (by Thames Water and the subsequent subsidiary bodies dealing with sludge application to soil) was on metals (and metal loads) with no analysis or indeed any form of investigation in to organics in the broadest sense

The analytical information produced in the context of the screening of the raw material is displayed below

Table 7 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 3

(Reading) 0032 0119 669

Table 8 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 3 (Reading) 015 706 279 138 152 901 267 300 lt 005 258 931

Table 9 ndash Analytical data obtained on a first screening on the sludge-amended soil from Reading (courtesy of IRMM)

Parameter Concentration

PCB ngg 28 lt1 52 lt1 101 lt1 118 lt1 153 lt1 105 lt1 138 lt1 156 lt1 180 lt1 170 lt1 PAH ngg Naphtalene lt10 Acenaphtylene 21 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene lt10 Flouranthene 818 Pyrene 776 Benz(a)anthracene 565

10

Parameter Concentration

Chrysene 608 Benz(b)fluoranthene 824 Benz(k)fluoranthene 329 Benz(a)pyrene 799 Indeno(123-cd)pyrene

779

Dibenzo(ah)anthracene 118 Benzo(ghi)perylene 394

Table 10 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 3

(Reading)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

103

003

nq

nq

nq

nd

nd

272

273

Table 11 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 3 (Reading) 015 706 279 138 152 901 267 300 lt 005 258 931

Table 12 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 3 (Reading) 7936 477 112 096 194 017 4107 443 2102 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 3 (Reading) 042 13 45 69 69 69 216 92

Table 13 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 3 (Reading) 012

11

23 Compost from Vienna Austria

The fresh compost material was obtained from the Austrian Federal Environment Agency (UBA Vienna) which had used a sub-batch of the raw material for national intercomparson The remainder of the material was stored at 4degC until shipment to IRMM for further processing The following analytical information was provided by UBA Austria and completed with various screenings

Table 14 ndash Analytical data on compost material received from UBA Austria Inorganic and sum parameters

Parameter Unit Sample fraction used Observed mean B CAT mgl FM Fresh sample lt10mm 61 K CAT mgl FM Fresh sample lt10mm 2624 Mg CAT mgl FM Fresh sample lt10mm 242 P CAT mgl FM Fresh sample lt10mm 49 B CAT DM Fresh sample lt10mm 00017 K CAT DM Fresh sample lt10mm 072 Mg CAT DM Fresh sample lt10mm 007 P CAT DM Fresh sample lt10mm 001 NO3-N mgkg FM Fresh sample lt10mm 35 NH4-N mgkg FM Fresh sample lt10mm 230 Ctotal DM lt45degdry milled 29 Corg DM lt45degdry milled 27 Ntotal DM lt45degdry milled 17 P mgkg DM lt45degdry milled 2596 K mgkg DM lt45degdry milled 11019 K DM lt45degdry milled 110 B mgkg DM lt45degdry milled 60 Cd mgkg DM lt45degdry milled 046 Cr mgkg DM lt45degdry milled 25 Cu mgkg DM lt45degdry milled 46 Hg mgkg DM lt45degdry milled 020 Ni mgkg DM lt45degdry milled 18 Pb mgkg DM lt45degdry milled 45 Zn mgkg DM lt45degdry milled 198 Ca mgkg DM lt45degdry milled 68776 Ca DM lt45degdry milled 69 Mo mgkg DM lt45degdry milled 08 S mgkg DM lt45degdry milled 2137 Fe mgkg DM lt45degdry milled 9959 Mn mgkg DM lt45degdry milled 418 Na mgkg DM lt45degdry milled 742 Co mgkg DM lt45degdry milled 41 AOX mgkg DM lt30deg dry milled 62

Table 15 ndash Analytical data on compost material received from UBA Austria Polycyclic aromatic hydrocarbons

PAH Unit Result Naphthaline microgkg DM 93 Acenaphthylene microgkg DM 86 Acenaphthene microgkg DM 5 Fluorene microgkg DM 80 Phenanthrene microgkg DM 89 Anthracene microgkg DM 27 Fluoranthene microgkg DM 487 Pyrene microgkg DM 380

12

PAH Unit Result Benzo(a)anthracene microgkg DM 278 Chrysene microgkg DM 317 Benzo(b)fluoranthene microgkg DM 365 Benzo(k)fluoranthene microgkg DM 193 Benz(a)pyrene microgkg DM 320 Indeno(123-cd)pyrene microgkg DM 233 Dibenz(ah)anthracene microgkg DM 67 Benzo(ghi)perylene microgkg DM 225 Sum EPA microgkg DM 3013 Sum EPA mgkg DM 30

Table 16 ndash Analytical data on compost material received from UBA Austria Sum PCDDs and PCBs

Parameter

Dioxine TEQ (ITEF) ngkg DM 73 TEQ (WHO) ngkg DM 35 PCB Σ Ballschmiter mgkg DM 005

Table 17 ndash Analytical data on compost material obtained by screening in IRMM

Parameter Result in ngg

PCB 28 2 52 2 101 4 118 3 153 10 105 1 138 8 156 1 180 5 170 lt1 PAH Naphtalene lt10 Acenaphtylene lt10 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene 26 Fluoranthene 611 Pyrene 510 Benz(a)anthracene 888 Chrysene 957 Benz(b)fluoranthene 1531 Benz(k)fluoranthene 547 Benz(a)pyrene 1101 Indeno(123-cd)pyrene 416 Dibenzo(ah)anthracene 81 Benzo(ghi)perylene 295

13

Table 18 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Compost 1

(Vienna)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

402

019

259

nq

023

004

nq

nq

144

174

259

Table 19 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Compost 1

(Vienna) 0058 1426 557

Table 20 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Compost 1 (Vienna) 039 736 319 410 365 127 495 004 079 013 208

Table 21 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Compost 1 (Vienna) 2063 431 617 426 199 249 1602 lt15 10521

Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Compost 1 (Vienna) 035 3496 81 375 79 55 653 60

Table 22 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Compost 1 (Vienna) 017

14

24 Agricultural soil sludge amended soil from Pavia Italy

This sludge-amended soil material was obtained during a monitoring campaign which aimed at a generic description of the over-all soil quality in Pavia Province Italy The material which was collected from the upper horizon originates from a small farm called ldquoCascina Novellordquo During the characterisation of the site the following analytical information was obtained on a pooled sample of a sub-area of the farm of 20 X 20 m2

Table 23 ndash Analytical data on Pavia soil

Parameter Result Al 713 Wgt As 224 mgkg Cd 079 mgkg Cr 59 mgkg Cu 308 mgkg Hg 008 mgkg Ni 344 mgkg Pb 246 mgkg Zn 95 mgkg C 091 Wgt 2378-TCDD 0047 pgg 12378-PeCDD 015 pgg 123478-HxCDD 019 pgg 123678-HxCDD 15 pgg 123789-HxCDD 074 pgg 1234678-HpCDD 26 pgg OCDD 382 pgg 2378-TCDF 068 pgg 12378-PeCDF 053 pgg 23478-PeCDF 071 pgg 123478-HxDF 100 pgg 123678-HxDF 066 pgg 234678-HxDF 16 pgg 123789-HxDF 027 pgg 1234678-HpDF 12 pgg 1234789-HpDF 068 pgg OCDF 33 pgg I-TEQ 20 pgg WHO-TEQ 17 pgg

In addition the screening performed at IRMM did not reveal significant quantities of PCBs and PAHs which were all below the LoDs (1 ngg for PCBs and 10 ngg for PAHs respectively)

Table 24 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 5 (Pavia) 0005 0011 154

15

Table 25 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 5

(Pavia)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

039

nq

nq

008

nq

nd

nd

670

671

Table 26 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 5 (Pavia) 033 184 573 225 426 305 206 200 lt 005 381 878

Table 27 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 5 (Pavia) 6939 129 145 224 425 116 6118 255 1789 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 5 (Pavia) 184 62 38 108 55 66 597 110

Table 28 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 5 (Pavia) 006

16

25 Sludge-amended-soil from Barcelona Spain

The sludge-amended soil material from Barcelona sampled upon indication from the Barcelorsquo- Group in Barcelona

Table 29 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 2 (Lleida T) 0015 0183 1138

Table 30 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 2

(Lleida T)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

159

045

nq

048

160

nq

nq

1000

1004

Table 31 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 2 (Lleida T) 059 141 327 536 405 186 184 224 lt 005 318 111

Table 32 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 2 (Lleida T) 4443 1067 1429 253 344 204 4116 780 3396 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 2 (Lleida T) 064 65 26 125 59 17 547 65

Table 33 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 2 (Lleida T) 010

17

26 Sludge amended soil from Essen Germany

The German sludge-amended soil from Essen which was provided as the three sludge materials by LUA NRW did not feature significant concentrations of the PCB congeners 28 52 101 118 153 105 138 156 180 170 but had detectable amounts of some PAHs

Table 34 ndash Analytical screening data on the German sludge-amended soil

Parameter Concentration(ngg)

Naphtalene lt10 Acenaphtylene lt10 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene lt10 Fluoranthene 28 Pyrene 20 Benz(a)anthracene 24 Chrysene 47 Benz(b)fluoranthene 76 Benz(k)fluoranthene 20 Benz(a)pyrene 35 Indeno(123-cd)pyrene 35 Dibenzo(ah)anthracene 10 Benzo(ghi)perylene 26

Table 35 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 4 (Essen) 0011 0302 055

Table 36 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 4

(Essen)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

nq

nq

nq

nq

nq

nq

128

191

203

18

Table 37 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 4 (Essen) 052 545 261 805 320 403 273 273 lt 005 295 781

Table 38 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 4 (Essen) 7947 442 085 06 086 007 2163 189 2019 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 4 (Essen) 045 19 42 87 683 60 462 61

Table 39 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 4 (Essen) 004

27 Long-term sludge exposed soil from Hohenheim-Stuttgart Germany

Similarly an additional sludge exposed soil was sampled at the University of Hohenheim Stuttgart were a test soil was long-term exposed to elevated concentrations of sewage sludge

Table 40 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 1 (Stuttgart) 0045 0263 1765

Table 41 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 1

(Stuttgart)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

230

006

004

004

nq

nd

nd

498

500

19

Table 42 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 1 (Stuttgart) 069 127 361 262 504 183 252 262 lt 005 266 142

Table 43 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 1 (Stuttgart) 7194 1006 133 186 366 088 7874 275 3571 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 1 (Stuttgart) 123 50 47 212 85 69 991 129

Table 44 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 1 (Stuttgart) 177

18

Annex 3

Statistical calculations

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 47)Mandels h statistics(Sludge 1 - PBD 47)

Sample Sludge 1 NUM

Element PBD 47

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00213 0001 3 -021 005 - - 10L - - NUM46L 00273 0002 4 016 021 - - 46L - - NUM64L 00059 0000 4 -116 002 NUM - 64L - - NUM12L 00188 0000 4 -036 002 - - 12L - - NUM26L 00499 0024 2 157 223 Fail - - 26L - - NUM

Totgem 0025 0005 mgkg 1-level 172 (185) NUM (10L46L64L12L26L) -1Totstd= 0016 0010 5-level 157 (162) 5

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 5 Labs rejected (10L46L64L12L26L)

000 050 100 150 200 250

k-values

10L

46L

64L

12L

26L

Mandels k statistics(Sludge 1 - PBD 47)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

10L

46L

64L

12L

26L

Labo

rato

ries

NUM

-200 -100 000 100 200

h-values

10L

46L

64L

12L

26L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 47)

Sludge 1-PBD 47

Unit mgkg

Mandels k statistics(Soil 3 - PBD 47)Mandels h statistics(Soil 3 - PBD 47)

Sample Soil 3 Soil 3 - PBD 47 -- Mean PARM = 0001 [mgkg]

Element PBD 47

General calcparmT1= 134814E-02T2= 142830E-05T3= 13T4= 45T5= 22767E-06

n= variabelp= 4

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean26L 00007 0000 2 -143 001 00007 00000 2 1 00046L 00010 0001 4 010 181 00010 00008 4 3 00010L 00011 0000 3 049 023 00011 00001 3 2 00012L 00012 0000 4 084 081 00012 00004 4 3 000

Totgem 0001 0000 mgkg 1-level 149 (177) 4 00010 () 4 3Totstd= 0000 0000 5-level 142 (159)

RESULTS Mean = 000100 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000050 --gt 5031 r = 00014Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000050 --gt 5031 R = 00014Remarks none

000 050 100 150 200

k-values

26L

46L

10L

12L

Mandels k statistics(Soil 3 - PBD 47)

00 00 00 00 00 00 00 00 00 00 00

Deviation from Mean

26L

46L

10L

12L

Labo

rato

ries

Soil 3 - PBD 47 -- Mean PARM = 0001 [mgkg]

-200 -100 000 100

h-values

26L

46L

10L

12L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 47)

Soil 3-PBD 47

Unit mgkg

Mandels k statistics(Compost 1 - PBD 99)Mandels h statistics(Compost 1 - PBD 99)

Sample Compost 1 Compost 1 - PBD 99 -- Mean PARM = 0003 [mgkg]

Element PBD 99

General calcparmT1= 492124E-02T2= 148747E-04T3= 17T4= 61T5= 93196E-06

n= variabelp= 5

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00020 0000 4 -137 053 00020 00004 4 3 000

26L 00025 0000 2 -058 024 00025 00002 2 1 00010L 00029 0000 3 012 032 00029 00003 3 2 00046L 00033 0001 4 069 161 00033 00013 4 3 00012L 00036 0001 4 114 140 00036 00011 4 3 000

Totgem 0003 0001 mgkg 1-level 172 (185) 5 00029 () 5 4Totstd= 0001 0001 5-level 157 (162)

RESULTS Mean = 000286 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000088 --gt 3086 r = 00025Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000101 --gt 3525 R = 00028Remarks none

000 050 100 150 200

k-values

4L

26L

10L

46L

12L

Mandels k statistics(Compost 1 - PBD 99)

00 00 00 00 00 00 00 00 00 00

Deviation from Mean

4L

26L

10L

46L

12L

Labo

rato

ries

Compost 1 - PBD 99 -- Mean PARM = 0003 [mgkg]

-200 -100 000 100 200

h-values

4L

26L

10L

46L

12L

Labo

rato

ries

Mandels h statistics(Compost 1 - PBD 99)

Compost 1-PBD 99

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 99)Mandels h statistics(Sludge 1 - PBD 99)

Sample Sludge 1 Sludge 1 - PBD 99 -- Mean PARM = 0024 [mgkg]

Element PBD 99

General calcparmT1= 448050E-01T2= 112113E-02T3= 19T4= 73T5= 32972E-05

n= variabelp= 5

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean64L 00173 0002 4 -118 041 Fail 00173 00019 4 3 -0014L 00183 0002 4 -104 032 00183 00015 4 3 -001

12L 00227 0001 4 -038 022 00227 00010 4 3 00010L 00290 0001 3 055 021 00290 00010 3 2 00146L 00320 0002 4 100 039 00320 00018 4 3 00126L 00323 0011 2 105 234 - - 26L - - 001

Totgem 0025 0003 mgkg 1-level 187 (177) 5 00239 (26L) 5 4Totstd= 0007 0004 5-level 166 (154) 1

RESULTS Mean = 002385 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000153 --gt 643 r = 00043Between lab variance S2L = 000004Reproducibility var S2R = 000004Reproducibility std SR = 000666 --gt 2791 R = 00186Remarks 1 Lab rejected (26L)

000 050 100 150 200 250

k-values

64L

4L

12L

10L

46L

26L

Mandels k statistics(Sludge 1 - PBD 99)

00 00 00 00 00 00 00 00 00 00

Deviation from Mean

64L

4L

12L

10L

46L

26L

Labo

rato

ries

Sludge 1 - PBD 99 -- Mean PARM = 0024 [mgkg]

-200 -100 000 100 200

h-values

64L

4L

12L

10L

46L

26L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 99)

Sludge 1-PBD 99

Unit mgkg

Mandels k statistics(Soil 3 - PBD 99)Mandels h statistics(Soil 3 - PBD 99)

Sample Soil 3 NUM

Element PBD 99

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00017 0000 4 091 068 - - 10L - - NUM46L 00017 0001 4 100 211 - - 46L - - NUM64L 00005 0000 4 -106 023 NUM - 64L - - NUM12L 00012 0000 4 015 014 - - 12L - - NUM26L 00006 0000 2 -101 012 - - 26L - - NUM

Totgem 0001 0000 mgkg 1-level 172 (173) NUM (10L46L64L12L26L) -1Totstd= 0001 0000 5-level 157 (153) 5

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 5 Labs rejected (10L46L64L12L26L)

000 050 100 150 200 250

k-values

10L

46L

64L

12L

26L

Mandels k statistics(Soil 3 - PBD 99)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

10L

46L

64L

12L

26L

Labo

rato

ries

NUM

-200 -100 000 100 200

h-values

10L

46L

64L

12L

26L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 99)

Soil 3-PBD 99

Unit mgkg

Mandels k statistics(Compost 1 - PBD 100)Mandels h statistics(Compost 1 - PBD 100)

Sample Compost 1 Compost 1 - PBD 100 -- Mean PARM = 0001 [mgkg]

Element PBD 100

General calcparmT1= 124272E-02T2= 113129E-05T3= 14T4= 52T5= 46584E-07

n= variabelp= 4

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean26L 00006 0000 2 -131 037 Fail 00006 00001 2 1 00010L 00009 0000 4 003 083 00009 00002 4 3 00046L 00009 0000 4 016 115 00009 00002 4 3 00012L 00011 0000 4 112 136 Fail 00011 00003 4 3 000

Totgem 0001 0000 mgkg 1-level 149 (167) 4 00009 () 4 3Totstd= 0000 0000 5-level 142 (15)

RESULTS Mean = 000085 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000022 --gt 2531 r = 00006Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000025 --gt 2882 R = 00007Remarks none

000 050 100 150

k-values

26L

10L

46L

12L

Mandels k statistics(Compost 1 - PBD 100)

00 00 00 00 00 00 00 00 00 00 00

Deviation from Mean

26L

10L

46L

12L

Labo

rato

ries

Compost 1 - PBD 100 -- Mean PARM = 0001 [mgkg]

-200 -100 000 100 200

h-values

26L

10L

46L

12L

Labo

rato

ries

Mandels h statistics(Compost 1 - PBD 100)

Compost 1-PBD 100

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 100)Mandels h statistics(Sludge 1 - PBD 100)

Sample Sludge 1 Sludge 1 - PBD 100 -- Mean PARM = 0005 [mgkg]

Element PBD 100

General calcparmT1= 852065E-02T2= 412762E-04T3= 18T4= 68T5= 78914E-07

n= variabelp= 5

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00039 0000 4 -042 007 Fail 00039 00002 4 3 000

12L 00044 0000 4 -041 005 Fail 00044 00001 4 3 00010L 00046 0000 4 -041 013 Fail 00046 00003 4 3 00046L 00056 0000 4 -040 012 Fail 00056 00003 4 3 00026L 00059 0000 2 -040 013 Fail 00059 00003 2 1 00038L 02168 0006 4 204 244 Fail - - 38L - - 021

Totgem 0040 0001 mgkg 1-level 187 (177) 5 00049 (38L) 5 4Totstd= 0087 0002 5-level 166 (154) 1

RESULTS Mean = 000486 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000025 --gt 507 r = 00007Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000084 --gt 1731 R = 00024Remarks 1 Lab rejected (38L)

000 050 100 150 200 250

k-values

4L

12L

10L

46L

26L

38L

Mandels k statistics(Sludge 1 - PBD 100)

-01 00 01 01 02 02 03

Deviation from Mean

4L

12L

10L

46L

26L

38L

Labo

rato

ries

Sludge 1 - PBD 100 -- Mean PARM = 0005 [mgkg]

-100 000 100 200 300

h-values

4L

12L

10L

46L

26L

38L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 100)

Sludge 1-PBD 100

Unit mgkg

Mandels k statistics(Soil 3 - PBD 100)Mandels h statistics(Soil 3 - PBD 100)

Sample Soil 3 NUM

Element PBD 100

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00003 0000 4 -050 000 Fail - - 10L - - NUM46L 00003 0000 4 -050 000 Fail NUM - 46L - - NUM3L 305500 2051 2 150 200 Fail - - 3L - - NUM

26L 00005 0000 2 -050 000 Fail - - 26L - - NUM

Totgem 7638 0513 mgkg 1-level 149 (177) NUM (10L46L3L26L) -1Totstd= 15275 1025 5-level 142 (159) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (10L46L3L26L)

000 050 100 150 200

k-values

10L

46L

3L

26L

Mandels k statistics(Soil 3 - PBD 100)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

10L

46L

3L

26L

Labo

rato

ries

NUM

-100 000 100 200

h-values

10L

46L

3L

26L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 100)

Soil 3-PBD 100

Unit mgkg

Mandels k statistics(Compost 1 - PBD 153)Mandels h statistics(Compost 1 - PBD 153)

Sample Compost 1 NUM

Element PBD 153

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean44L 00053 0001 3 150 157 Fail - - 44L - - NUM46L 00007 0000 4 -044 111 Fail - - 46L - - NUM12L 00005 0000 4 -051 055 Fail - - 12L - - NUM26L 00005 0000 2 -054 001 Fail NUM - 26L - - NUM

Totgem 0002 0000 mgkg 1-level 149 (177) NUM (44L46L12L26L) -1Totstd= 0002 0000 5-level 142 (159) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (44L46L12L26L)

000 050 100 150 200

k-values

44L

46L

12L

26L

Mandels k statistics(Compost 1 - PBD 153)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

44L

46L

12L

26L

Labo

rato

ries

NUM

-100 000 100 200

h-values

44L

46L

12L

26L

Labo

rato

ries

Mandels h statistics(Compost 1 - PBD 153)

Compost 1-PBD 153

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 153)Mandels h statistics(Sludge 1 - PBD 153)

Sample Sludge 1 Sludge 1 - PBD 153 -- Mean PARM = 0004 [mgkg]

Element PBD 153

General calcparmT1= 676738E-02T2= 267609E-04T3= 18T4= 68T5= 19626E-05

n= variabelp= 5

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00024 0000 4 -157 017 00024 00002 4 3 000

12L 00038 0002 4 006 154 00038 00018 4 3 00046L 00039 0000 4 011 026 00039 00003 4 3 00026L 00039 0000 2 018 004 00039 00000 2 1 00064L 00049 0002 4 122 159 00049 00018 4 3 000

Totgem 0004 0001 mgkg 1-level 172 (173) 5 00038 () 5 4Totstd= 0001 0001 5-level 157 (153)

RESULTS Mean = 000378 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000123 --gt 3252 r = 00034Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000142 --gt 3754 R = 00040Remarks none

000 050 100 150 200

k-values

4L

12L

46L

26L

64L

Mandels k statistics(Sludge 1 - PBD 153)

00 00 00 00 00 00 00

Deviation from Mean

4L

12L

46L

26L

64L

Labo

rato

ries

Sludge 1 - PBD 153 -- Mean PARM = 0004 [mgkg]

-200 -100 000 100 200

h-values

4L

12L

46L

26L

64L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 153)

Sludge 1-PBD 153

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 154)Mandels h statistics(Sludge 1 - PBD 154)

Sample Sludge 1 NA

Element PBD 154

General calcparmT1= NAT2= NAT3=T4=T5=

n= variabelp=

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00021 0000 3 -100 021 NA - 4L - - NA

46L 00025 0000 4 115 018 NA - 46L - - NA64L 00021 0001 4 -066 179 - - 64L - - NA12L 00023 0000 4 050 085 - - 12L - - NA

Totgem 0002 0000 mgkg 1-level 149 (167) NA (4L46L64L12L) -1Totstd= 0000 0000 5-level 142 (15) 4

RESULTS Mean = NA mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NAReproducibility var S2R = NAReproducibility std SR = NA --gt NA R = NARemarks 4 Labs rejected (4L46L64L12L)

000 050 100 150 200

k-values

4L

46L

64L

12L

Mandels k statistics(Sludge 1 - PBD 154)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

4L

46L

64L

12L

Labo

rato

ries

NA

-100 000 100 200

h-values

4L

46L

64L

12L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 154)

Sludge 1-PBD 154

Unit mgkg

Mandels k statistics(Soil 3 - PBD 154)Mandels h statistics(Soil 3 - PBD 154)

Sample Soil 3 NUM

Element PBD 154

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

4L 00010 - 1 150 Fail - - 4L - - NUM46L 00001 0000 4 -053 096 Fail - - 46L - - NUM64L 00001 0000 4 -056 105 Fail NUM - 64L - - NUM12L 00002 0000 4 -040 099 Fail - - 12L - - NUM

Totgem 000037 0000 mgkg 1-level 149 (164) NUM (4L46L64L12L) -1Totstd= 000042 0000 5-level 142 (153) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (4L46L64L12L)

000 050 100 150

k-values

4L

46L

64L

12L

Mandels k statistics(Soil 3 - PBD 154)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

4L

46L

64L

12L

Labo

rato

ries

NUM

-100 000 100 200

h-values

4L

46L

64L

12L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 154)

Soil 3-PBD 154

Unit mgkg

Mandels k statistics(Compost 1 - PBD 209)Mandels h statistics(Compost 1 - PBD 209)

Sample Compost 1 NUM

Element PBD 209

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00065 0003 2 -049 032 - - 4L - - NUM

44L 00573 0021 4 150 197 Fail - - 44L - - NUM12L 00078 0001 4 -045 011 - - 12L - - NUM26L 00049 0000 2 -056 000 NUM - 26L - - NUM

Totgem 0019 0006 mgkg 1-level 149 (177) NUM (4L44L12L26L) -1Totstd= 0025 0010 5-level 142 (159) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (4L44L12L26L)

000 050 100 150 200

k-values

4L

44L

12L

26L

Mandels k statistics(Compost 1 - PBD 209)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

4L

44L

12L

26L

Labo

rato

ries

NUM

-100 000 100 200

h-values

4L

44L

12L

26L

Labo

rato

ries

Mandels h statistics(Compost 1 - PBD 209)

Compost 1-PBD 209

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 209)Mandels h statistics(Sludge 1 - PBD 209)

Sample Sludge 1 Sludge 1 - PBD 209 -- Mean PARM = 0249 [mgkg]

Element PBD 209

General calcparmT1= 394542E+00T2= 107296E+00T3= 16T4= 56T5= 19723E-02

n= variabelp= 5

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 01550 0055 4 -112 148 Fail 01550 00551 4 3 -009

46L 02050 0007 2 -053 019 02050 00071 2 1 -00412L 02137 0058 4 -042 155 02137 00576 4 3 -00426L 03149 0021 2 078 057 Fail 03149 00210 2 1 00764L 03577 0007 4 129 020 Fail 03577 00074 4 3 011

Totgem 0249 0030 mgkg 1-level 172 (185) 5 02493 () 5 4Totstd= 0084 0025 5-level 157 (162)

RESULTS Mean = 024926 mgkg

Repeatability variance S2r = 000179Repeatability std Sr = 004234 --gt 1699 r = 01186Between lab variance S2L = 000743Reproducibility var S2R = 000922Reproducibility std SR = 009604 --gt 3853 R = 02689Remarks none

000 050 100 150 200

k-values

4L

46L

12L

26L

64L

Mandels k statistics(Sludge 1 - PBD 209)

-01 -01 00 01 01 02

Deviation from Mean

4L

46L

12L

26L

64L

Labo

rato

ries

Sludge 1 - PBD 209 -- Mean PARM = 0249 [mgkg]

-200 -100 000 100 200

h-values

4L

46L

12L

26L

64L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 209)

Sludge 1-PBD 209

Unit mgkg

Mandels k statistics(Soil 3 - PBD 209)Mandels h statistics(Soil 3 - PBD 209)

Sample Soil 3 Soil 3 - PBD 209 -- Mean PARM = 0258 [mgkg]

Element PBD 209

General calcparmT1= 596398E+00T2= 191917E+00T3= 22T4= 84T5= 13249E-02

n= variabelp= 6

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean26L 01162 0021 2 -108 074 Fail 01162 00207 2 1 -0144L 01303 0031 4 -097 111 Fail 01303 00312 4 3 -013

46L 01975 0036 4 -046 128 Fail 01975 00359 4 3 -00644L 02898 0035 4 024 124 Fail 02898 00346 4 3 00312L 03895 0018 4 100 065 Fail 03895 00181 4 3 01364L 04260 0022 4 127 078 Fail 04260 00219 4 3 017

Totgem 0258 0027 mgkg 1-level 187 (177) 6 02582 () 6 5Totstd= 0132 0008 5-level 166 (154)

RESULTS Mean = 025818 mgkg

Repeatability variance S2r = 000083Repeatability std Sr = 002878 --gt 1115 r = 00806Between lab variance S2L = 001640Reproducibility var S2R = 001723Reproducibility std SR = 013127 --gt 5084 R = 03676Remarks none

000 050 100 150

k-values

26L

4L

46L

44L

12L

64L

Mandels k statistics(Soil 3 - PBD 209)

-02 -01 -01 00 01 01 02 02

Deviation from Mean

26L

4L

46L

44L

12L

64L

Labo

rato

ries

Soil 3 - PBD 209 -- Mean PARM = 0258 [mgkg]

-200 -100 000 100 200

h-values

26L

4L

46L

44L

12L

64L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 209)

Soil 3-PBD 209

Unit mgkg

Mandels k statistics(Compost 1 - Sum PBD)Mandels h statistics(Compost 1 - Sum PBD)

Sample Compost 1 Compost 1 - Sum PBD -- Mean PARM = 0009 [mgkg]

Element Sum PBD

General calcparmT1= 154064E-01T2= 169065E-03T3= 18T4= 68T5= 11354E-04

n= variabelp= 5

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00031 0002 4 -067 016 00031 00016 4 3 -0014L 00055 0005 4 -056 048 00055 00047 4 3 000

46L 00085 0003 4 -042 031 00085 00030 4 3 00026L 00123 0000 2 -024 003 00123 00002 2 1 00012L 00154 0002 4 -011 021 00154 00021 4 3 00144L 00613 0023 4 200 237 Fail - - 44L - - 005

Totgem 0018 0006 mgkg 1-level 187 (177) 5 00089 (44L) 5 4Totstd= 0022 0009 5-level 166 (154) 1

RESULTS Mean = 000893 mgkg

Repeatability variance S2r = 000001Repeatability std Sr = 000296 --gt 3308 r = 00083Between lab variance S2L = 000002Reproducibility var S2R = 000003Reproducibility std SR = 000570 --gt 6374 R = 00159Remarks 1 Lab rejected (44L)

000 050 100 150 200 250

k-values

10L

4L

46L

26L

12L

44L

Mandels k statistics(Compost 1 - Sum PBD)

00 00 00 00 00 00 01 01

Deviation from Mean

10L

4L

46L

26L

12L

44L

Labo

rato

ries

Compost 1 - Sum PBD -- Mean PARM = 0009 [mgkg]

-100 000 100 200

h-values

10L

4L

46L

26L

12L

44L

Labo

rato

ries

Mandels h statistics(Compost 1 - Sum PBD)

Compost 1-Sum PBD

Unit mgkg

Mandels k statistics(Sludge 1 - Sum PBD)Mandels h statistics(Sludge 1 - Sum PBD)

Sample Sludge 1 Sludge 1 - Sum PBD -- Mean PARM = 0256 [mgkg]

Element Sum PBD

General calcparmT1= 531806E+00T2= 162188E+00T3= 22T4= 84T5= 25223E-02

n= variabelp= 6

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00423 0025 4 -156 044 Fail 00423 00252 4 3 -02146L 01808 0118 4 -049 205 - - 46L - - -0074L 01810 0056 4 -049 097 01810 00558 4 3 -007

38L 02168 0006 4 -022 010 02168 00059 4 3 -00412L 02890 0065 4 034 113 02890 00647 4 3 00364L 03958 0008 4 116 014 Fail 03958 00079 4 3 01426L 04094 0034 2 126 059 Fail 04094 00337 2 1 015

Totgem 0245 0044 mgkg 1-level 198 (179) 6 02557 (46L) 6 5Totstd= 0130 0039 5-level 171 (155) 1

RESULTS Mean = 025570 mgkg

Repeatability variance S2r = 000158Repeatability std Sr = 003970 --gt 1553 r = 01112Between lab variance S2L = 001807Reproducibility var S2R = 001964Reproducibility std SR = 014015 --gt 5481 R = 03924Remarks 1 Lab rejected (46L)

000 050 100 150 200 250

k-values

10L

46L

4L

38L

12L

64L

26L

Mandels k statistics(Sludge 1 - Sum PBD)

-03 -02 -02 -01 -01 00 01 01 02 02

Deviation from Mean

10L

46L

4L

38L

12L

64L

26L

Labo

rato

ries

Sludge 1 - Sum PBD -- Mean PARM = 0256 [mgkg]

-200 -100 000 100 200

h-values

10L

46L

4L

38L

12L

64L

26L

Labo

rato

ries

Mandels h statistics(Sludge 1 - Sum PBD)

Sludge 1-Sum PBD

Unit mgkg

Mandels k statistics(Soil 3 - Sum PBD)Mandels h statistics(Soil 3 - Sum PBD)

Sample Soil 3 Soil 3 - Sum PBD -- Mean PARM = 0227 [mgkg]

Element Sum PBD

General calcparmT1= 610980E+00T2= 200876E+00T3= 26T4= 100T5= 13106E-02

n= variabelp= 7

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00028 0001 4 -037 000 Fail 00028 00005 4 3 -02226L 01179 0021 2 -036 003 Fail 01179 00208 2 1 -0114L 01305 0031 4 -036 004 Fail 01305 00308 4 3 -010

46L 02065 0035 4 -036 005 Fail 02065 00350 4 3 -00244L 02923 0037 4 -035 005 Fail 02923 00365 4 3 00712L 04051 0015 4 -034 002 Fail 04051 00149 4 3 01864L 04314 0022 4 -033 003 Fail 04314 00223 4 3 0203L 305500 2051 2 247 283 Fail - - 3L - - 3032

Totgem 4017 0276 mgkg 1-level 206 (181) 7 02266 (3L) 7 6Totstd= 10722 0717 5-level 175 (156) 1

RESULTS Mean = 022663 mgkg

Repeatability variance S2r = 000069Repeatability std Sr = 002626 --gt 1159 r = 00735Between lab variance S2L = 002568Reproducibility var S2R = 002637Reproducibility std SR = 016238 --gt 7165 R = 04547Remarks 1 Lab rejected (3L)

000 050 100 150 200 250 300

k-values

10L

26L

4L

46L

44L

12L

64L

3L

Mandels k statistics(Soil 3 - Sum PBD)

-50 00 50 100 150 200 250 300 350

Deviation from Mean

10L

26L

4L

46L

44L

12L

64L

3L

Labo

rato

ries

Soil 3 - Sum PBD -- Mean PARM = 0227 [mgkg]

-100 000 100 200 300

h-values

10L

26L

4L

46L

44L

12L

64L

3L

Labo

rato

ries

Mandels h statistics(Soil 3 - Sum PBD)

Soil 3-Sum PBD

19

Annex 4

Raw data submitted

Sample Compost1 Sample Compost 1 Sample Compost 1Element PBD 99 Element PBD 100 Element PBD 153

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]4L 00021 10L 00008 44L 000504L 00024 10L 00008 44L 000604L 00014 10L 00007 44L 000504L 00020 10L 00011 46L 00004

10L 00029 46L 00007 46L 0001210L 00027 46L 00012 46L 0000410L 00032 46L 00009 46L 0000946L 00025 46L 00007 12L 0000446L 00052 12L 00008 12L 0000846L 00029 12L 00012 12L 0000446L 00026 12L 00008 12L 0000712L 00026 12L 00014 26L 0000512L 00043 26L 00007 26L 0000512L 00026 26L 0000612L 0004726L 0002626L 00024

Sample Compost 1 Sample Compost 1 Sample Compost 1Element PBD 154 Element PBD 183 Element PBD 196

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]4L 00010 46L 00002 46L 00011

46L 00003 46L 00024 46L 0000846L 00007 46L 00021 12L 0000246L 00003 46L 00003 12L 0000346L 00004 12L 00003 12L 0000112L 00003 12L 00011 12L 0000212L 00005 12L 0000312L 00031 12L 0000312L 00006

Sample Compost 1 Sample Compost 1 Sample Compost 1Element PBD 197 Element PBD 203 Element PBD 209

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00002 46L 00010 4L 0004146L 00023 12L 00002 4L 0008946L 00022 12L 00003 44L 0041012L 00004 12L 00002 44L 0084012L 00006 12L 00002 44L 0064012L 00003 44L 0040012L 00004 12L 00079

12L 0007312L 0006512L 0009326L 0004926L 00049

Sample Compost 1Element PBD 47

LAB PARM [mgkg]26L 0003826L 00039

Element PBD 99 Element PBD 47 Element PBD 209LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]

4L 00170 10L 00210 4L 010004L 00200 10L 00220 4L 018004L 00170 10L 00210 4L 012004L 00190 46L 00300 4L 0220010L 00280 46L 00280 46L 0210010L 00300 46L 00250 46L 0200010L 00290 46L 00260 64L 0351846L 00340 64L 00059 64L 0363846L 00330 64L 00057 64L 0364546L 00300 64L 00062 64L 0350846L 00310 64L 00060 12L 0220964L 00194 12L 00191 12L 0177164L 00154 12L 00187 12L 0292264L 00185 12L 00190 12L 0164664L 00159 12L 00186 26L 0329712L 00242 26L 00666 26L 0300012L 00223 26L 0033212L 0022112L 0022226L 0024626L 00400

Element PBD 203 Element PBD 197 Element PBD 196LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00022 46L 00027 46L 0002446L 00014 46L 00024 46L 0002264L 00036 12L 00161 64L 0005864L 00058 12L 00060 64L 0006512L 00063 12L 00061 12L 0004812L 00034 12L 00036 12L 0002512L 00038 12L 0003212L 00027 12L 00022

Element PBD 183 Element PBD 154 Element PBD 153LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00049 4L 00020 4L 0002246L 00035 4L 00022 4L 0002446L 00036 4L 00020 4L 0002246L 00034 46L 00025 4L 0002664L 00027 46L 00025 46L 0004064L 00023 46L 00025 46L 0004264L 00024 46L 00023 46L 0003564L 00020 64L 00034 46L 0003812L 00230 64L 00023 64L 0007412L 00032 64L 00017 64L 0004712L 00031 64L 00011 64L 0004612L 00030 12L 00030 64L 0003026L 00007 12L 00021 12L 0006526L 00008 12L 00021 12L 00029

12L 00021 12L 0003226L 00015 12L 0002926L 00019 26L 00039

26L 00040

Element PBD 100LAB PARM [mgkg]

4L 000384L 000414L 000374L 00038

38L 0219038L 0220038L 0208038L 0220010L 0004410L 0005010L 0004310L 0004646L 0005746L 0005946L 0005346L 0005312L 0004312L 0004512L 0004312L 0004326L 0006226L 00057

Sample Soil 3 Sample Soil 3 Sample Soil 3Element PBD 99 Element PBD 47 Element PBD 100

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]10L 00016 10L 00011 10L 0000310L 00019 10L 00010 10L 0000410L 00013 10L 00012 10L 0000410L 00019 46L 00007 10L 0000246L 00025 46L 00022 46L 0000246L 00025 46L 00005 46L 0000646L 00008 46L 00007 46L 0000246L 00011 12L 00010 46L 0000264L 00005 12L 00017 3L 29100064L 00005 12L 00010 3L 32000064L 00006 12L 00009 26L 0000564L 00007 26L 00007 26L 0000512L 00012 26L 0000712L 0001312L 0001312L 0001226L 0000526L 00006

Sample Soil 3 Sample Soil 3 Sample Soil 3Element PBD 153 Element PBD 154 Element PBD 196

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]44L 00050 4L 00010 46L 0000744L 00050 46L 00001 46L 0001146L 00002 46L 00002 46L 0000846L 00003 46L 00001 46L 0001146L 00002 46L 00002 64L 0002646L 00002 64L 00001 64L 0002664L 00001 64L 00001 64L 0002964L 00001 64L 00001 64L 0003464L 00001 64L 00002 12L 0004564L 00002 12L 00003 12L 00032

12L 00002 12L 0002212L 00002 12L 0002112L 00002

Sample Soil 3 Sample Soil 3 Sample Soil 3Element PBD 197 Element PBD 203 Element PBD 209

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00006 46L 00011 4L 0091046L 00013 46L 00017 4L 0150046L 00011 46L 00015 4L 0120046L 00013 46L 00018 4L 0160012L 00090 64L 00013 44L 0337012L 00056 64L 00014 44L 0281012L 00033 64L 00016 44L 0287012L 00032 64L 00015 44L 02540

12L 00055 46L 0230012L 00041 46L 0220012L 00027 46L 0150012L 00026 46L 01900

64L 0438164L 0401664L 0414464L 0449812L 0367112L 0397812L 0409112L 03838

Sample Soil 3 26L 0102Element PBD 183 26L 0131

LAB PARM [mgkg]46L 0000746L 0000846L 0005846L 0000764L 0000264L 0000364L 0000364L 0000312L 0001512L 0001112L 0000712L 00007

European Commission EUR 23003 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on polybrominated diphenylethers Author(s) E Sobiecka H van der Sloot D Barcelo B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 68 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07403-5 Abstract Project HORIZONTAL is interdisciplinary aiming at a harmonisation and horizontal standardisation of test procedures in particular for sludge soils and biowastes In the context of this standardization project a series of draft technical specification were designed upon an extensive desk study fine-tuned after expert consultations and finally validated in international intercomparisons exercise This report summarises the work performed within the validation study of the draft standard for the determination of polybrominated diphenylethers (PBDE) in soils sludge and treated bio-waste using gas-chromatography method with mass selective detection (GC-MS) It further explains the underlying statistical concept for the calculation of reproducibility and repeatability from intercomparisons data In addition all single values results of the statistical evaluation as well as background information on the validation materials used are described and explained

The mission of the JRC is to provide customer-driven scientific and technical support for the conception development implementation and monitoring of EU policies As a service of the European Commission the JRC functions as a reference centre of science and technology for the Union Close to the policy-making process it serves the common interest of the Member States while being independent of special interests whether private or national

LB

-NA

-23003-EN

-C

6

11 Statistical concept underlying the validation According to the requirements of the work package concerning data handling amp interpretation of the project HORIZONTAL-ORG the respective validation intercomparisons have to be evaluated according to the principles laid down in ISO standard 5725-21994 In particular repeatability and reproducibility of the draft standard methods have to be determined The determination of trueness would require the availability of independent reference values for the materials investigated This however is not possible and was not requested in the frame of this work In the following the approach chosen is explained

111 Introduction to the statistical model The statistical model used in ISO 5725 for estimation of accuracy of a measurement method assumes that every test result is the sum of three components

eBmy ++= y test result m general mean B laboratory component of bias under repeatability conditions e random error occurring in every measurement under repeatability conditions

In the workprogram the quantification of term e is explicitly asked for (ie repeatability and reproducibility) The repeatability variance is measured directly as the variance of the error term e but the reproducibility depends on the sum of the repeatability variance and the between-laboratory variance

( )er var=σ 22rLR σσσ += with ( )BL var=σ

However soil biowaste and sludge are multi-phase materials ie they contain two or more distinct types of particles which are fundamentally different in their properties and composition As a consequence this introduces an important source of variation for the intercomparison exercise which needs to be considered ie the inherent heterogeneity of the materials Thus a contribution of variation between samples H is introduced to the general statistical model

HeBmy +++= Using ANOVA techniques the different variances are calculated and separated for the evaluation

7

112 Requirements for precision experiment

Layout of the experiment A suite of 10 to 12 different materials (soil sludge and biowaste) has been made available for the intercomparison exercise For each parameter investigated at least 10 to laboratories should be nominated to participate The same laboratories should be used for different parameters as far as possible Due to the complexity of analysis and the respective workload to the laboratories it was decided to propose three materials for the validation of the PBDE draft standard Each laboratory received two bottles of each material and was be requested to perform 4 independent analyses per material1 (2 per bottle) using the respective draft standard methods The 4 analysis per material should be carried out under repeatability conditions (ie same operator2 same equipment within a short period of time) As far as possible also the different materials should be measured under repeatability conditions however changes of eg operator or equipment are permitted but must be reported Likewise different materials can be analysed on different days if necessary Equipment used in the experiment needed to be checked prior to the experiment according to the requirements of the draft standard The results of these checks have to be documented Similarly date and time of each measurement had to be recorded for verification of repeatability conditions An appropriate timeframe for the entire exercise has been set and was to be respected

Recruitment of the laboratories Each sub-workpackage leader of HORIZONTAL was asked to select the laboratories using the information from section 52 of ISO 5725-21994 and provide the signed questionnaires (see also Annex 1) The workpackage leaders were responsible for providing the laboratories with the draft standard method and explaining the context of this exercise

Preparation and use of the materials Materials used for the exercise were prepared according to the general requirements for reference materials as laid down in ISO Guide 34 Materials were accompanied by instructions for use

Reporting of results Online submissions of results using an internet-based IT platform as well as XLS-Spreadsheets were used In case of online data submission the participating laboratories received a unique and confidential login and password in due time enabling them to

1 Independent analysis means analysis of independent test portions applying the entire analytical scheme to this test portion from eg extraction to quantification For instance it does not mean replicate injections of aliquots into a GC-MS instrument 2 Operator in this context may also consist of a fixed team of persons eg one person performing extraction one clean-up one quantification

8

enter their data in a structured form For authentication purposes a signed printout had to be submitted by mail The online data submission included a detailed questionnaire for additional information on the measurements

113 Statistical analysis Statistical analysis of data followed the requirements of ISO 5725-21994 and ISO 5725-51998 Appropriate tests for the homogeneity of variance detection of outliers and normal distribution were applied Statistical evaluation was done using an Excel Macro developed tested and successfully applied in other occasion by ECN Evaluation was executed jointly by JRC and ECN

12 Validation exercise for PBDE

121 Compounds to be measured The following compound were selected for the validation exercise Tetra-BDE-47 Penta-BDE-100 Penta-BDE-99 Hexa-BDE-154 Hexa-BDE-153 Hepta-BDE-183 Octa-BDE-196 Octa-BDE-197 Octa-BDE-203 Deca-BDE-209

122 Samples dispatched for the validation of PBDE After a preliminary rough screening the following materials were used for the validation round of PBDE

bull Compost 1 A pollutant loaded compost material from Vienna bull Sewage Sludge 1 A mixed sewage sludge from Essen bull Soil 3 A sludge amended soil from Barcelona

A more detailed description of background concentrations can be found in Annex 2 to this report The samples were dispatched simultaneously to all participants using a private courier service

123 Draft standards to be followed The draft standards to be followed could be downloaded following this link which is situated on the website of the Project HORIZONTAL httpwwwecnnldocssocietyhorizontalBFR_Standard_for_validationpdf

124 Analytical programm Of each of the three materials 2 bottles had to be analysed and each bottle had to analysed independently twice As mentioned above analyses were to be done under repeatability conditions Results were to be reported referring to DRY MATTER content The choice how to apply dm correction was free for each participant

9

125 Timing and Submission of data Dispatch of samples was done on the 18th of October 2006 For users of the Online data submission system (MILC) User Registration was possible from 14th of November 2006 with opening of the MILC Data Submission on 1st of December 2006 The deadline for submission of results has been set for PBDE to the 12th of January 2007 but was extended to the end of the same months After that no further submission was possible Alternatively the participants were allowed to submit data electronically as Excel sheet using simply Email All data were treated in a confidential way Any presentation hereafter will refer only to numerical data and it will not be possible to identify the originating laboratory Lab Codes displayed are NOT related to the order of laboratories hereafter In addition to the information provide an Helpdesk was implemented in order to give quick and individual response to the participants during and immediately after the validation study In case of doubt and suspected transcription errors further enquires were conducted by JRC

10

126 Participants The following table lists the participating organisations and entities in the validation exercise for the horizontal PBDE standard

bull Austria o Umweltbundesamt

bull Czech Republic o Povodi Labe statni podnik - OVHL Laboratory

bull France o CIRSEE o CTC Environnement o INERIS

bull Germany o Federal Environmental Agency Section III 34 Laboratory Methods for

the Surveillance of Waste and Wastewater (UBA) bull Italy

o European Commission DG JRC IES bull Spain

o Consejo Superior de Investigaciones Cientificas (CSIC)

bull Sweden o ALCONTROL AB

11

13 Summary results and derived performance characteristics The result of the various statistical evaluation including outlier tests calculation of repeatability and reproducibility standard deviation for the congeners of interest can be found in Annex 3 of this report In addition all data submitted by the participants as well as those considered for the calculation of the performance characteristics are listed in Annex 3 to this report Based on these calculations the following results were obtained in the validation round upon statistical evaluation according to ISO 5725-2 The average values the repeatability standard deviation (sr) and the reproducibility standard deviation (sR) were obtained (Table1) The repeatability is determined as an interval around a measurement result (ie repeatability limit) This interval corresponds to the maximum difference that can be expected (with a 95 statistical confidence) between one test result and another both test results being obtained under the following conditions The tests are performed in accordance with all the requirements of the present standard by the same laboratory using its own facilities and testing laboratory samples obtained from the same primary field sample and prepared under identical procedures The repeatability limit was calculated using the relationship r test = f radic2 s rtest with the critical range factor f = 2 The reproducibility like repeatability is also determined as an interval around a measurement result (ie reproducibility limit) This interval corresponds to the maximum difference that can be expected (with a 95 statistical confidence) between one test result and another test result obtained by another laboratory both test results being obtained under the following conditions The tests are performed in accordance with all the requirements of the present standard by two different laboratories using their own facilities and testing laboratory samples obtained from the same primary field sample and prepared under identical procedures The reproducibility limit was calculated using the relationship R = f radic2 sR with the critical range factor f = 2

12

Table 1 - Results of the interlaboratory comparison studies of the determination of selected polybrominated diphenyl ethers (PBDE) by gaschromatography with mass spectrometric detection (GC-MS) in soil sludge and treated biowaste All concentrations are expressed in mgkg dm

Matrix Parameter Mean sr sR r R p Outliers Used No of data

No of data reported below

detection

Total no of data

Sludge 1 PBD 47 00181 461 4 15 5 20 Compost 1 00039 94 3 12 0 12 Soil 3 00010 50 50 00014 00014 4 0 13 10 23 Sludge 1 PBD 99 00239 64 28 00043 00186 5 1 19 0 23 Compost 1 00029 31 35 00025 00028 5 0 17 4 21 Soil 3 00013 499 4 16 8 24 Sludge 1 PBD 100 00049 51 17 00007 00024 5 1 18 2 24 Compost 1 00009 25 29 00006 00007 4 0 14 7 21 Soil 3 61103 211 3 10 15 25 Sludge 1 PBD 153 00038 33 38 00034 0004 5 0 18 0 18 Compost 1 00019 116 3 11 3 14 Soil 3 00011 177 2 10 10 20 Sludge 1 PBD 154 00023 234 4 15 2 17 Compost 1 00008 1118 3 9 5 14

13

Matrix Parameter Mean sr sR r R p Outliers Used No of data

No of data reported below

detection

Total no of data

Soil 3 00002 1049 4 13 6 19 Sludge 1 PBD 183 00048 1217 3 12 2 14 Compost 1 00009 1048 2 8 5 13 Soil 3 00011 1395 3 12 6 18 Sludge 1 PBD 196 00037 470 2 8 7 15 Compost 1 00004 950 2 6 4 10 Soil 3 00023 519 3 12 2 14 Sludge 1 PBD 197 00062 834 2 6 8 14 Compost 1 00009 1001 2 7 7 14 Soil 3 00032 904 2 8 6 14 Sludge 1 PBD 203 00037 461 2 8 4 12 Compost 1 00004 978 2 5 3 8 Soil 3 00022 598 3 12 0 12 Sludge 1 PBD 209 02493 170 39 01186 02689 5 0 16 2 18 Compost 1 00273 104 3 10 5 15 Soil 3 02582 1115 51 00806 03676 6 0 22 0 22

14

Matrix Parameter Mean sr sR r R p Outliers Used No of data

No of data reported below

detection

Total no of data

Sludge 1 Sum PBD 0256 155 548 0111 0392 6 1 22 Compost 1 0009 331 637 0008 0016 5 1 18 Soil 3 0227 116 717 0074 0455 7 1 26 Abbreviations sr Repeatability standard deviation SR Reproducibility standard deviation r Repeatability limit (comparing two measurements) R Reproducibility limit (comparing two measurements) p Number of labs determination not possible

15

14 Annexes Annex 1 Model questionnaire to be filled by the participating laboratories Annex 3 Report on the validation materials used Annex 2 Statistical calculations Annex 3 Data submitted

16

Annex 1

Model questionnaire to be filled by the participating laboratories

Model questionnaire to be filled by the participating laboratories Name of laboratory Contact person Contact details email Phone Fax Mail address of lab Dispatch address of lab for shipment of samples (no PO boxes) Title of measurement method (copy attached) Our laboratory is willing to participate in the precision experiment for this draft standard method

Yes No As participant we understand that

bull All essential apparatus chemicals and other requirements specified in the method must be available in our laboratory when the programme begins

bull Specified timing requirements such as starting and finishing date of the programme must be rigidly met

bull The method must be strictly adhered to bull Samples must be handled in accordance with instructions bull A qualified operator must perform the measurements

Having studied the method and having made a fair appraisal of our capabilities and facilities we feel that we will be adequately prepared for cooperative testing of this method Comments helliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphellip Signature Date

17

Annex 2

Report on the validation materials used

VI

Abstract This report gives an overview on the available analytical information on the following raw materials to be used for the production of validation materials of the so-called Project HORIZONTAL

bull Four sludge materials from Duumlsseldorf Germany

bull An agricultural soil material from Reading United Kingdom

bull A compost material from Vienna Austria

bull A compost material from Korschenbroich Germany

bull A sludge-amended agricultural soil from Pavia Province Italy

bull A sludge-amended soil from Barcelona Spain

bull A sludge-amended soil from Essen Germany

bull A long-term sludge exposed soil from Hohenheim Germany

VII

List of Abbreviations Throughout this report the following abbreviations are used

AOX absorbable organic halogens

Corg organic carbon content

Ctotal total carbon content

CAT cation exchangeable

CDD chlorinated dibenzodioxin

CDF chlorinated dibenzofuran

DEHP di(2-ethylhexyl)phthalate

DM dry matter

EPA Environment Protection Agency

EU European Union

FM fresh matter

Hp hepta

Hx hexa

IES Institute for Environment and Sustainability

IRMM Institute for Reference Materials and Measurements

JRC Joint Research Centre

LAS linear alkylsulfonates

LoD limit of detection

LUA Landesumweltamt

Ntotal total nitrogen content

NH4-N Ammonium nitrogen

NO3-N Nitrate nitrogen

NP nonylphenol

NRW North Rhine Westphalia

O octa

P poly

PAH polycyclic aromatic hydrocarbon

PCB polychlorinated biphenyl

Pe penta

T tetra

TEQ toxicity equivalent

UBA Umweltbundesamt

WHO World Health Organization

WWTP waste water treatment plant

6

1 Introduction This report gives an overview on the available analytical information on the following raw materials to be used for the production of validation materials of the so-called Project HORIZONTAL

bull Four sludge materials from Duumlsseldorf Germany

bull An agricultural soil material from Reading United Kingdom

bull A compost material from Vienna Austria

bull A compost material from Korschenbroich Germany

bull A sludge-amended agricultural soil from Pavia Province Italy

bull A sludge-amended soil from Barcelona Spain

bull A sludge-amended soil from Essen Germany

bull A long-term sludge exposed soil from Hohenheim Germany

The following analytical information was gathered partly before and during the sampling of the raw materials to be used for the production of the HORIZONTAL validation materials The material were sampled by IES and shipped to IRMM in the course of the year 2005 The information gathered was then completed by various analytical screenings for PAHs and PCBs done by the Institute for Reference Materials and Measurements Geel Belgium for phthalates done by UBA Berlin Germany for PBDE done by IIQAB-CSIC Barcelona Spain for trace elements and some selected major and minor elements by the Institute for Environment and Sustainability Ispra Italy

The work compiled hereafter is based on the numerous additional efforts of the scientists working at various members of the consortium Project HORIZONTAL-Org and contributing organisations

This work is gratefully acknowledged

2 Overview on property values

21 Sludge materials from Duumlsseldorf Germany

The various sewage sludge materials originate from various installations in the North Rhine Westphalia and were produced and sampled by staff from the Landesumweltamt (LUA) NRW under the responsibility from Dr K Furtmann

In total four sludge materials (Sludge A and D from a major municipal WWTP Sludge B from a municipal WWTP with industrial input and Sludge C from a municipal WWTP with high PCB-Content) were obtained and will be blended to two final materials Before sampling the following analytical data for a typical sample were received

7

Table 1 ndash Analytical data obtained on an average sludge sample in LUA NRW (with courtesy of K Furtmann LUA Duumlsseldorf)

Parameter Concentration PCB 120 ugkg DEHP 110 mgkg PAH 5 mgkg (EPA) PCDDF 15 ng TEkg PBDE 400 ugkg NP 40 mgkg LAS 3 gkg AOX 300 mgkg

Subsequent screening led to the information displayed hereafter It should be stressed that the data were obtained as SCREENING information on the UNTREATED or partially treated raw materials Therefore the final target values which are relevant for the validation intercomparison can be different

Table 2 ndash Analytical data obtained on a first screening on the sludge samples from LUA NRW

Sewage sludge A

Dusseldorf

sewage sludge D

Dusseldorf PCB (ngg) 28 62 35 52 101 65 101 31 38 118 49 40 153 30 33 105 24 11 138 46 38 156 lt1 lt1 180 34 23 170 23 19 PAH (ngg) Naphtalene 34 381 Acenaphtylene 15 43 Acenaphthene 81 108 Fluorene 94 1167 Phenantrene 3440 Anthracene 22 344 Flouranthene 316 4817 Pyrene 235 3011 Benz(a)anthracene 473 791 Chrysene 691 1078 Benz(b)fluoranthene 538 1688 Benz(k)fluoranthene 228 635 Benz(a)pyrene 383 1114 Indeno(123-cd)pyrene 92 229 Dibenzo(ah)anthracene 71 70 Benzo(ghi)perylene 80 185

8

Table 3 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Sludge D (1) 0135 41474 385 Sludge B (2) 0538 0034 30634 547 Sludge A (3) 0184 0037 31399 146 Sludge C (4) 0354 1528 6678 229

Table 4 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Sludge 2

(B)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

554

959

694

591

772

509

nq

nq

970

2216

2379

Table 5 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena IES Ispra Spain) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Sludge 1 (D) 265 290 533 359 1231 338 784 438 lt 005 232 786 Sludge 2 (B) 119 311 626 202 278 299 722 251 lt 005 118 625 Sludge 3 (A) 168 360 621 332 847 416 119 451 lt 005 116 1237 Sludge 4 (C) 563 198 116 273 726 511 473 618 lt 005 444 2015

Table 6 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Sludge 1 (D) 2154 58 844 099 103 101 4367 lt15 50448 Sludge 2 (B) 1067 366 692 046 1491 077 5217 lt15 57633 Sludge 3 (A) 731 663 684 035 1287 068 3733 lt15 60369 Sludge 4 (C) 4379 965 527 163 522 107 5628 lt15 23945

Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM)Sludge 1 (D) 03 2403 101 1002 350 15 1944 132Sludge 2 (B) 031 315 97 879 172 12 514 180Sludge 3 (A) 031 1281 153 1567 265 16 1440 168Sludge 4 (C) 055 231 628 2625 371 81 1101 244

9

22 Agricultural soil material from Reading United Kingdom

The material was proposed by the University of Reading (S Nortcliff) and was sampled from a site called ldquoFrogmore Farmrdquo which was featured in the ldquoMetalsrdquo Report for HORIZONTAL This site is close to Reading with soils developed on flintyloamy periglacial materials over Chalk has a long and well documented history of sludge application The focus of the work of Nortcliff et al undertook at this site and the monitoring and control at the site (by Thames Water and the subsequent subsidiary bodies dealing with sludge application to soil) was on metals (and metal loads) with no analysis or indeed any form of investigation in to organics in the broadest sense

The analytical information produced in the context of the screening of the raw material is displayed below

Table 7 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 3

(Reading) 0032 0119 669

Table 8 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 3 (Reading) 015 706 279 138 152 901 267 300 lt 005 258 931

Table 9 ndash Analytical data obtained on a first screening on the sludge-amended soil from Reading (courtesy of IRMM)

Parameter Concentration

PCB ngg 28 lt1 52 lt1 101 lt1 118 lt1 153 lt1 105 lt1 138 lt1 156 lt1 180 lt1 170 lt1 PAH ngg Naphtalene lt10 Acenaphtylene 21 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene lt10 Flouranthene 818 Pyrene 776 Benz(a)anthracene 565

10

Parameter Concentration

Chrysene 608 Benz(b)fluoranthene 824 Benz(k)fluoranthene 329 Benz(a)pyrene 799 Indeno(123-cd)pyrene

779

Dibenzo(ah)anthracene 118 Benzo(ghi)perylene 394

Table 10 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 3

(Reading)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

103

003

nq

nq

nq

nd

nd

272

273

Table 11 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 3 (Reading) 015 706 279 138 152 901 267 300 lt 005 258 931

Table 12 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 3 (Reading) 7936 477 112 096 194 017 4107 443 2102 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 3 (Reading) 042 13 45 69 69 69 216 92

Table 13 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 3 (Reading) 012

11

23 Compost from Vienna Austria

The fresh compost material was obtained from the Austrian Federal Environment Agency (UBA Vienna) which had used a sub-batch of the raw material for national intercomparson The remainder of the material was stored at 4degC until shipment to IRMM for further processing The following analytical information was provided by UBA Austria and completed with various screenings

Table 14 ndash Analytical data on compost material received from UBA Austria Inorganic and sum parameters

Parameter Unit Sample fraction used Observed mean B CAT mgl FM Fresh sample lt10mm 61 K CAT mgl FM Fresh sample lt10mm 2624 Mg CAT mgl FM Fresh sample lt10mm 242 P CAT mgl FM Fresh sample lt10mm 49 B CAT DM Fresh sample lt10mm 00017 K CAT DM Fresh sample lt10mm 072 Mg CAT DM Fresh sample lt10mm 007 P CAT DM Fresh sample lt10mm 001 NO3-N mgkg FM Fresh sample lt10mm 35 NH4-N mgkg FM Fresh sample lt10mm 230 Ctotal DM lt45degdry milled 29 Corg DM lt45degdry milled 27 Ntotal DM lt45degdry milled 17 P mgkg DM lt45degdry milled 2596 K mgkg DM lt45degdry milled 11019 K DM lt45degdry milled 110 B mgkg DM lt45degdry milled 60 Cd mgkg DM lt45degdry milled 046 Cr mgkg DM lt45degdry milled 25 Cu mgkg DM lt45degdry milled 46 Hg mgkg DM lt45degdry milled 020 Ni mgkg DM lt45degdry milled 18 Pb mgkg DM lt45degdry milled 45 Zn mgkg DM lt45degdry milled 198 Ca mgkg DM lt45degdry milled 68776 Ca DM lt45degdry milled 69 Mo mgkg DM lt45degdry milled 08 S mgkg DM lt45degdry milled 2137 Fe mgkg DM lt45degdry milled 9959 Mn mgkg DM lt45degdry milled 418 Na mgkg DM lt45degdry milled 742 Co mgkg DM lt45degdry milled 41 AOX mgkg DM lt30deg dry milled 62

Table 15 ndash Analytical data on compost material received from UBA Austria Polycyclic aromatic hydrocarbons

PAH Unit Result Naphthaline microgkg DM 93 Acenaphthylene microgkg DM 86 Acenaphthene microgkg DM 5 Fluorene microgkg DM 80 Phenanthrene microgkg DM 89 Anthracene microgkg DM 27 Fluoranthene microgkg DM 487 Pyrene microgkg DM 380

12

PAH Unit Result Benzo(a)anthracene microgkg DM 278 Chrysene microgkg DM 317 Benzo(b)fluoranthene microgkg DM 365 Benzo(k)fluoranthene microgkg DM 193 Benz(a)pyrene microgkg DM 320 Indeno(123-cd)pyrene microgkg DM 233 Dibenz(ah)anthracene microgkg DM 67 Benzo(ghi)perylene microgkg DM 225 Sum EPA microgkg DM 3013 Sum EPA mgkg DM 30

Table 16 ndash Analytical data on compost material received from UBA Austria Sum PCDDs and PCBs

Parameter

Dioxine TEQ (ITEF) ngkg DM 73 TEQ (WHO) ngkg DM 35 PCB Σ Ballschmiter mgkg DM 005

Table 17 ndash Analytical data on compost material obtained by screening in IRMM

Parameter Result in ngg

PCB 28 2 52 2 101 4 118 3 153 10 105 1 138 8 156 1 180 5 170 lt1 PAH Naphtalene lt10 Acenaphtylene lt10 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene 26 Fluoranthene 611 Pyrene 510 Benz(a)anthracene 888 Chrysene 957 Benz(b)fluoranthene 1531 Benz(k)fluoranthene 547 Benz(a)pyrene 1101 Indeno(123-cd)pyrene 416 Dibenzo(ah)anthracene 81 Benzo(ghi)perylene 295

13

Table 18 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Compost 1

(Vienna)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

402

019

259

nq

023

004

nq

nq

144

174

259

Table 19 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Compost 1

(Vienna) 0058 1426 557

Table 20 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Compost 1 (Vienna) 039 736 319 410 365 127 495 004 079 013 208

Table 21 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Compost 1 (Vienna) 2063 431 617 426 199 249 1602 lt15 10521

Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Compost 1 (Vienna) 035 3496 81 375 79 55 653 60

Table 22 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Compost 1 (Vienna) 017

14

24 Agricultural soil sludge amended soil from Pavia Italy

This sludge-amended soil material was obtained during a monitoring campaign which aimed at a generic description of the over-all soil quality in Pavia Province Italy The material which was collected from the upper horizon originates from a small farm called ldquoCascina Novellordquo During the characterisation of the site the following analytical information was obtained on a pooled sample of a sub-area of the farm of 20 X 20 m2

Table 23 ndash Analytical data on Pavia soil

Parameter Result Al 713 Wgt As 224 mgkg Cd 079 mgkg Cr 59 mgkg Cu 308 mgkg Hg 008 mgkg Ni 344 mgkg Pb 246 mgkg Zn 95 mgkg C 091 Wgt 2378-TCDD 0047 pgg 12378-PeCDD 015 pgg 123478-HxCDD 019 pgg 123678-HxCDD 15 pgg 123789-HxCDD 074 pgg 1234678-HpCDD 26 pgg OCDD 382 pgg 2378-TCDF 068 pgg 12378-PeCDF 053 pgg 23478-PeCDF 071 pgg 123478-HxDF 100 pgg 123678-HxDF 066 pgg 234678-HxDF 16 pgg 123789-HxDF 027 pgg 1234678-HpDF 12 pgg 1234789-HpDF 068 pgg OCDF 33 pgg I-TEQ 20 pgg WHO-TEQ 17 pgg

In addition the screening performed at IRMM did not reveal significant quantities of PCBs and PAHs which were all below the LoDs (1 ngg for PCBs and 10 ngg for PAHs respectively)

Table 24 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 5 (Pavia) 0005 0011 154

15

Table 25 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 5

(Pavia)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

039

nq

nq

008

nq

nd

nd

670

671

Table 26 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 5 (Pavia) 033 184 573 225 426 305 206 200 lt 005 381 878

Table 27 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 5 (Pavia) 6939 129 145 224 425 116 6118 255 1789 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 5 (Pavia) 184 62 38 108 55 66 597 110

Table 28 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 5 (Pavia) 006

16

25 Sludge-amended-soil from Barcelona Spain

The sludge-amended soil material from Barcelona sampled upon indication from the Barcelorsquo- Group in Barcelona

Table 29 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 2 (Lleida T) 0015 0183 1138

Table 30 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 2

(Lleida T)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

159

045

nq

048

160

nq

nq

1000

1004

Table 31 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 2 (Lleida T) 059 141 327 536 405 186 184 224 lt 005 318 111

Table 32 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 2 (Lleida T) 4443 1067 1429 253 344 204 4116 780 3396 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 2 (Lleida T) 064 65 26 125 59 17 547 65

Table 33 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 2 (Lleida T) 010

17

26 Sludge amended soil from Essen Germany

The German sludge-amended soil from Essen which was provided as the three sludge materials by LUA NRW did not feature significant concentrations of the PCB congeners 28 52 101 118 153 105 138 156 180 170 but had detectable amounts of some PAHs

Table 34 ndash Analytical screening data on the German sludge-amended soil

Parameter Concentration(ngg)

Naphtalene lt10 Acenaphtylene lt10 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene lt10 Fluoranthene 28 Pyrene 20 Benz(a)anthracene 24 Chrysene 47 Benz(b)fluoranthene 76 Benz(k)fluoranthene 20 Benz(a)pyrene 35 Indeno(123-cd)pyrene 35 Dibenzo(ah)anthracene 10 Benzo(ghi)perylene 26

Table 35 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 4 (Essen) 0011 0302 055

Table 36 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 4

(Essen)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

nq

nq

nq

nq

nq

nq

128

191

203

18

Table 37 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 4 (Essen) 052 545 261 805 320 403 273 273 lt 005 295 781

Table 38 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 4 (Essen) 7947 442 085 06 086 007 2163 189 2019 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 4 (Essen) 045 19 42 87 683 60 462 61

Table 39 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 4 (Essen) 004

27 Long-term sludge exposed soil from Hohenheim-Stuttgart Germany

Similarly an additional sludge exposed soil was sampled at the University of Hohenheim Stuttgart were a test soil was long-term exposed to elevated concentrations of sewage sludge

Table 40 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 1 (Stuttgart) 0045 0263 1765

Table 41 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 1

(Stuttgart)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

230

006

004

004

nq

nd

nd

498

500

19

Table 42 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 1 (Stuttgart) 069 127 361 262 504 183 252 262 lt 005 266 142

Table 43 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 1 (Stuttgart) 7194 1006 133 186 366 088 7874 275 3571 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 1 (Stuttgart) 123 50 47 212 85 69 991 129

Table 44 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 1 (Stuttgart) 177

18

Annex 3

Statistical calculations

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 47)Mandels h statistics(Sludge 1 - PBD 47)

Sample Sludge 1 NUM

Element PBD 47

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00213 0001 3 -021 005 - - 10L - - NUM46L 00273 0002 4 016 021 - - 46L - - NUM64L 00059 0000 4 -116 002 NUM - 64L - - NUM12L 00188 0000 4 -036 002 - - 12L - - NUM26L 00499 0024 2 157 223 Fail - - 26L - - NUM

Totgem 0025 0005 mgkg 1-level 172 (185) NUM (10L46L64L12L26L) -1Totstd= 0016 0010 5-level 157 (162) 5

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 5 Labs rejected (10L46L64L12L26L)

000 050 100 150 200 250

k-values

10L

46L

64L

12L

26L

Mandels k statistics(Sludge 1 - PBD 47)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

10L

46L

64L

12L

26L

Labo

rato

ries

NUM

-200 -100 000 100 200

h-values

10L

46L

64L

12L

26L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 47)

Sludge 1-PBD 47

Unit mgkg

Mandels k statistics(Soil 3 - PBD 47)Mandels h statistics(Soil 3 - PBD 47)

Sample Soil 3 Soil 3 - PBD 47 -- Mean PARM = 0001 [mgkg]

Element PBD 47

General calcparmT1= 134814E-02T2= 142830E-05T3= 13T4= 45T5= 22767E-06

n= variabelp= 4

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean26L 00007 0000 2 -143 001 00007 00000 2 1 00046L 00010 0001 4 010 181 00010 00008 4 3 00010L 00011 0000 3 049 023 00011 00001 3 2 00012L 00012 0000 4 084 081 00012 00004 4 3 000

Totgem 0001 0000 mgkg 1-level 149 (177) 4 00010 () 4 3Totstd= 0000 0000 5-level 142 (159)

RESULTS Mean = 000100 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000050 --gt 5031 r = 00014Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000050 --gt 5031 R = 00014Remarks none

000 050 100 150 200

k-values

26L

46L

10L

12L

Mandels k statistics(Soil 3 - PBD 47)

00 00 00 00 00 00 00 00 00 00 00

Deviation from Mean

26L

46L

10L

12L

Labo

rato

ries

Soil 3 - PBD 47 -- Mean PARM = 0001 [mgkg]

-200 -100 000 100

h-values

26L

46L

10L

12L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 47)

Soil 3-PBD 47

Unit mgkg

Mandels k statistics(Compost 1 - PBD 99)Mandels h statistics(Compost 1 - PBD 99)

Sample Compost 1 Compost 1 - PBD 99 -- Mean PARM = 0003 [mgkg]

Element PBD 99

General calcparmT1= 492124E-02T2= 148747E-04T3= 17T4= 61T5= 93196E-06

n= variabelp= 5

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00020 0000 4 -137 053 00020 00004 4 3 000

26L 00025 0000 2 -058 024 00025 00002 2 1 00010L 00029 0000 3 012 032 00029 00003 3 2 00046L 00033 0001 4 069 161 00033 00013 4 3 00012L 00036 0001 4 114 140 00036 00011 4 3 000

Totgem 0003 0001 mgkg 1-level 172 (185) 5 00029 () 5 4Totstd= 0001 0001 5-level 157 (162)

RESULTS Mean = 000286 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000088 --gt 3086 r = 00025Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000101 --gt 3525 R = 00028Remarks none

000 050 100 150 200

k-values

4L

26L

10L

46L

12L

Mandels k statistics(Compost 1 - PBD 99)

00 00 00 00 00 00 00 00 00 00

Deviation from Mean

4L

26L

10L

46L

12L

Labo

rato

ries

Compost 1 - PBD 99 -- Mean PARM = 0003 [mgkg]

-200 -100 000 100 200

h-values

4L

26L

10L

46L

12L

Labo

rato

ries

Mandels h statistics(Compost 1 - PBD 99)

Compost 1-PBD 99

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 99)Mandels h statistics(Sludge 1 - PBD 99)

Sample Sludge 1 Sludge 1 - PBD 99 -- Mean PARM = 0024 [mgkg]

Element PBD 99

General calcparmT1= 448050E-01T2= 112113E-02T3= 19T4= 73T5= 32972E-05

n= variabelp= 5

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean64L 00173 0002 4 -118 041 Fail 00173 00019 4 3 -0014L 00183 0002 4 -104 032 00183 00015 4 3 -001

12L 00227 0001 4 -038 022 00227 00010 4 3 00010L 00290 0001 3 055 021 00290 00010 3 2 00146L 00320 0002 4 100 039 00320 00018 4 3 00126L 00323 0011 2 105 234 - - 26L - - 001

Totgem 0025 0003 mgkg 1-level 187 (177) 5 00239 (26L) 5 4Totstd= 0007 0004 5-level 166 (154) 1

RESULTS Mean = 002385 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000153 --gt 643 r = 00043Between lab variance S2L = 000004Reproducibility var S2R = 000004Reproducibility std SR = 000666 --gt 2791 R = 00186Remarks 1 Lab rejected (26L)

000 050 100 150 200 250

k-values

64L

4L

12L

10L

46L

26L

Mandels k statistics(Sludge 1 - PBD 99)

00 00 00 00 00 00 00 00 00 00

Deviation from Mean

64L

4L

12L

10L

46L

26L

Labo

rato

ries

Sludge 1 - PBD 99 -- Mean PARM = 0024 [mgkg]

-200 -100 000 100 200

h-values

64L

4L

12L

10L

46L

26L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 99)

Sludge 1-PBD 99

Unit mgkg

Mandels k statistics(Soil 3 - PBD 99)Mandels h statistics(Soil 3 - PBD 99)

Sample Soil 3 NUM

Element PBD 99

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00017 0000 4 091 068 - - 10L - - NUM46L 00017 0001 4 100 211 - - 46L - - NUM64L 00005 0000 4 -106 023 NUM - 64L - - NUM12L 00012 0000 4 015 014 - - 12L - - NUM26L 00006 0000 2 -101 012 - - 26L - - NUM

Totgem 0001 0000 mgkg 1-level 172 (173) NUM (10L46L64L12L26L) -1Totstd= 0001 0000 5-level 157 (153) 5

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 5 Labs rejected (10L46L64L12L26L)

000 050 100 150 200 250

k-values

10L

46L

64L

12L

26L

Mandels k statistics(Soil 3 - PBD 99)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

10L

46L

64L

12L

26L

Labo

rato

ries

NUM

-200 -100 000 100 200

h-values

10L

46L

64L

12L

26L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 99)

Soil 3-PBD 99

Unit mgkg

Mandels k statistics(Compost 1 - PBD 100)Mandels h statistics(Compost 1 - PBD 100)

Sample Compost 1 Compost 1 - PBD 100 -- Mean PARM = 0001 [mgkg]

Element PBD 100

General calcparmT1= 124272E-02T2= 113129E-05T3= 14T4= 52T5= 46584E-07

n= variabelp= 4

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean26L 00006 0000 2 -131 037 Fail 00006 00001 2 1 00010L 00009 0000 4 003 083 00009 00002 4 3 00046L 00009 0000 4 016 115 00009 00002 4 3 00012L 00011 0000 4 112 136 Fail 00011 00003 4 3 000

Totgem 0001 0000 mgkg 1-level 149 (167) 4 00009 () 4 3Totstd= 0000 0000 5-level 142 (15)

RESULTS Mean = 000085 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000022 --gt 2531 r = 00006Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000025 --gt 2882 R = 00007Remarks none

000 050 100 150

k-values

26L

10L

46L

12L

Mandels k statistics(Compost 1 - PBD 100)

00 00 00 00 00 00 00 00 00 00 00

Deviation from Mean

26L

10L

46L

12L

Labo

rato

ries

Compost 1 - PBD 100 -- Mean PARM = 0001 [mgkg]

-200 -100 000 100 200

h-values

26L

10L

46L

12L

Labo

rato

ries

Mandels h statistics(Compost 1 - PBD 100)

Compost 1-PBD 100

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 100)Mandels h statistics(Sludge 1 - PBD 100)

Sample Sludge 1 Sludge 1 - PBD 100 -- Mean PARM = 0005 [mgkg]

Element PBD 100

General calcparmT1= 852065E-02T2= 412762E-04T3= 18T4= 68T5= 78914E-07

n= variabelp= 5

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00039 0000 4 -042 007 Fail 00039 00002 4 3 000

12L 00044 0000 4 -041 005 Fail 00044 00001 4 3 00010L 00046 0000 4 -041 013 Fail 00046 00003 4 3 00046L 00056 0000 4 -040 012 Fail 00056 00003 4 3 00026L 00059 0000 2 -040 013 Fail 00059 00003 2 1 00038L 02168 0006 4 204 244 Fail - - 38L - - 021

Totgem 0040 0001 mgkg 1-level 187 (177) 5 00049 (38L) 5 4Totstd= 0087 0002 5-level 166 (154) 1

RESULTS Mean = 000486 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000025 --gt 507 r = 00007Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000084 --gt 1731 R = 00024Remarks 1 Lab rejected (38L)

000 050 100 150 200 250

k-values

4L

12L

10L

46L

26L

38L

Mandels k statistics(Sludge 1 - PBD 100)

-01 00 01 01 02 02 03

Deviation from Mean

4L

12L

10L

46L

26L

38L

Labo

rato

ries

Sludge 1 - PBD 100 -- Mean PARM = 0005 [mgkg]

-100 000 100 200 300

h-values

4L

12L

10L

46L

26L

38L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 100)

Sludge 1-PBD 100

Unit mgkg

Mandels k statistics(Soil 3 - PBD 100)Mandels h statistics(Soil 3 - PBD 100)

Sample Soil 3 NUM

Element PBD 100

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00003 0000 4 -050 000 Fail - - 10L - - NUM46L 00003 0000 4 -050 000 Fail NUM - 46L - - NUM3L 305500 2051 2 150 200 Fail - - 3L - - NUM

26L 00005 0000 2 -050 000 Fail - - 26L - - NUM

Totgem 7638 0513 mgkg 1-level 149 (177) NUM (10L46L3L26L) -1Totstd= 15275 1025 5-level 142 (159) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (10L46L3L26L)

000 050 100 150 200

k-values

10L

46L

3L

26L

Mandels k statistics(Soil 3 - PBD 100)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

10L

46L

3L

26L

Labo

rato

ries

NUM

-100 000 100 200

h-values

10L

46L

3L

26L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 100)

Soil 3-PBD 100

Unit mgkg

Mandels k statistics(Compost 1 - PBD 153)Mandels h statistics(Compost 1 - PBD 153)

Sample Compost 1 NUM

Element PBD 153

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean44L 00053 0001 3 150 157 Fail - - 44L - - NUM46L 00007 0000 4 -044 111 Fail - - 46L - - NUM12L 00005 0000 4 -051 055 Fail - - 12L - - NUM26L 00005 0000 2 -054 001 Fail NUM - 26L - - NUM

Totgem 0002 0000 mgkg 1-level 149 (177) NUM (44L46L12L26L) -1Totstd= 0002 0000 5-level 142 (159) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (44L46L12L26L)

000 050 100 150 200

k-values

44L

46L

12L

26L

Mandels k statistics(Compost 1 - PBD 153)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

44L

46L

12L

26L

Labo

rato

ries

NUM

-100 000 100 200

h-values

44L

46L

12L

26L

Labo

rato

ries

Mandels h statistics(Compost 1 - PBD 153)

Compost 1-PBD 153

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 153)Mandels h statistics(Sludge 1 - PBD 153)

Sample Sludge 1 Sludge 1 - PBD 153 -- Mean PARM = 0004 [mgkg]

Element PBD 153

General calcparmT1= 676738E-02T2= 267609E-04T3= 18T4= 68T5= 19626E-05

n= variabelp= 5

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00024 0000 4 -157 017 00024 00002 4 3 000

12L 00038 0002 4 006 154 00038 00018 4 3 00046L 00039 0000 4 011 026 00039 00003 4 3 00026L 00039 0000 2 018 004 00039 00000 2 1 00064L 00049 0002 4 122 159 00049 00018 4 3 000

Totgem 0004 0001 mgkg 1-level 172 (173) 5 00038 () 5 4Totstd= 0001 0001 5-level 157 (153)

RESULTS Mean = 000378 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000123 --gt 3252 r = 00034Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000142 --gt 3754 R = 00040Remarks none

000 050 100 150 200

k-values

4L

12L

46L

26L

64L

Mandels k statistics(Sludge 1 - PBD 153)

00 00 00 00 00 00 00

Deviation from Mean

4L

12L

46L

26L

64L

Labo

rato

ries

Sludge 1 - PBD 153 -- Mean PARM = 0004 [mgkg]

-200 -100 000 100 200

h-values

4L

12L

46L

26L

64L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 153)

Sludge 1-PBD 153

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 154)Mandels h statistics(Sludge 1 - PBD 154)

Sample Sludge 1 NA

Element PBD 154

General calcparmT1= NAT2= NAT3=T4=T5=

n= variabelp=

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00021 0000 3 -100 021 NA - 4L - - NA

46L 00025 0000 4 115 018 NA - 46L - - NA64L 00021 0001 4 -066 179 - - 64L - - NA12L 00023 0000 4 050 085 - - 12L - - NA

Totgem 0002 0000 mgkg 1-level 149 (167) NA (4L46L64L12L) -1Totstd= 0000 0000 5-level 142 (15) 4

RESULTS Mean = NA mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NAReproducibility var S2R = NAReproducibility std SR = NA --gt NA R = NARemarks 4 Labs rejected (4L46L64L12L)

000 050 100 150 200

k-values

4L

46L

64L

12L

Mandels k statistics(Sludge 1 - PBD 154)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

4L

46L

64L

12L

Labo

rato

ries

NA

-100 000 100 200

h-values

4L

46L

64L

12L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 154)

Sludge 1-PBD 154

Unit mgkg

Mandels k statistics(Soil 3 - PBD 154)Mandels h statistics(Soil 3 - PBD 154)

Sample Soil 3 NUM

Element PBD 154

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

4L 00010 - 1 150 Fail - - 4L - - NUM46L 00001 0000 4 -053 096 Fail - - 46L - - NUM64L 00001 0000 4 -056 105 Fail NUM - 64L - - NUM12L 00002 0000 4 -040 099 Fail - - 12L - - NUM

Totgem 000037 0000 mgkg 1-level 149 (164) NUM (4L46L64L12L) -1Totstd= 000042 0000 5-level 142 (153) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (4L46L64L12L)

000 050 100 150

k-values

4L

46L

64L

12L

Mandels k statistics(Soil 3 - PBD 154)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

4L

46L

64L

12L

Labo

rato

ries

NUM

-100 000 100 200

h-values

4L

46L

64L

12L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 154)

Soil 3-PBD 154

Unit mgkg

Mandels k statistics(Compost 1 - PBD 209)Mandels h statistics(Compost 1 - PBD 209)

Sample Compost 1 NUM

Element PBD 209

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00065 0003 2 -049 032 - - 4L - - NUM

44L 00573 0021 4 150 197 Fail - - 44L - - NUM12L 00078 0001 4 -045 011 - - 12L - - NUM26L 00049 0000 2 -056 000 NUM - 26L - - NUM

Totgem 0019 0006 mgkg 1-level 149 (177) NUM (4L44L12L26L) -1Totstd= 0025 0010 5-level 142 (159) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (4L44L12L26L)

000 050 100 150 200

k-values

4L

44L

12L

26L

Mandels k statistics(Compost 1 - PBD 209)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

4L

44L

12L

26L

Labo

rato

ries

NUM

-100 000 100 200

h-values

4L

44L

12L

26L

Labo

rato

ries

Mandels h statistics(Compost 1 - PBD 209)

Compost 1-PBD 209

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 209)Mandels h statistics(Sludge 1 - PBD 209)

Sample Sludge 1 Sludge 1 - PBD 209 -- Mean PARM = 0249 [mgkg]

Element PBD 209

General calcparmT1= 394542E+00T2= 107296E+00T3= 16T4= 56T5= 19723E-02

n= variabelp= 5

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 01550 0055 4 -112 148 Fail 01550 00551 4 3 -009

46L 02050 0007 2 -053 019 02050 00071 2 1 -00412L 02137 0058 4 -042 155 02137 00576 4 3 -00426L 03149 0021 2 078 057 Fail 03149 00210 2 1 00764L 03577 0007 4 129 020 Fail 03577 00074 4 3 011

Totgem 0249 0030 mgkg 1-level 172 (185) 5 02493 () 5 4Totstd= 0084 0025 5-level 157 (162)

RESULTS Mean = 024926 mgkg

Repeatability variance S2r = 000179Repeatability std Sr = 004234 --gt 1699 r = 01186Between lab variance S2L = 000743Reproducibility var S2R = 000922Reproducibility std SR = 009604 --gt 3853 R = 02689Remarks none

000 050 100 150 200

k-values

4L

46L

12L

26L

64L

Mandels k statistics(Sludge 1 - PBD 209)

-01 -01 00 01 01 02

Deviation from Mean

4L

46L

12L

26L

64L

Labo

rato

ries

Sludge 1 - PBD 209 -- Mean PARM = 0249 [mgkg]

-200 -100 000 100 200

h-values

4L

46L

12L

26L

64L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 209)

Sludge 1-PBD 209

Unit mgkg

Mandels k statistics(Soil 3 - PBD 209)Mandels h statistics(Soil 3 - PBD 209)

Sample Soil 3 Soil 3 - PBD 209 -- Mean PARM = 0258 [mgkg]

Element PBD 209

General calcparmT1= 596398E+00T2= 191917E+00T3= 22T4= 84T5= 13249E-02

n= variabelp= 6

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean26L 01162 0021 2 -108 074 Fail 01162 00207 2 1 -0144L 01303 0031 4 -097 111 Fail 01303 00312 4 3 -013

46L 01975 0036 4 -046 128 Fail 01975 00359 4 3 -00644L 02898 0035 4 024 124 Fail 02898 00346 4 3 00312L 03895 0018 4 100 065 Fail 03895 00181 4 3 01364L 04260 0022 4 127 078 Fail 04260 00219 4 3 017

Totgem 0258 0027 mgkg 1-level 187 (177) 6 02582 () 6 5Totstd= 0132 0008 5-level 166 (154)

RESULTS Mean = 025818 mgkg

Repeatability variance S2r = 000083Repeatability std Sr = 002878 --gt 1115 r = 00806Between lab variance S2L = 001640Reproducibility var S2R = 001723Reproducibility std SR = 013127 --gt 5084 R = 03676Remarks none

000 050 100 150

k-values

26L

4L

46L

44L

12L

64L

Mandels k statistics(Soil 3 - PBD 209)

-02 -01 -01 00 01 01 02 02

Deviation from Mean

26L

4L

46L

44L

12L

64L

Labo

rato

ries

Soil 3 - PBD 209 -- Mean PARM = 0258 [mgkg]

-200 -100 000 100 200

h-values

26L

4L

46L

44L

12L

64L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 209)

Soil 3-PBD 209

Unit mgkg

Mandels k statistics(Compost 1 - Sum PBD)Mandels h statistics(Compost 1 - Sum PBD)

Sample Compost 1 Compost 1 - Sum PBD -- Mean PARM = 0009 [mgkg]

Element Sum PBD

General calcparmT1= 154064E-01T2= 169065E-03T3= 18T4= 68T5= 11354E-04

n= variabelp= 5

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00031 0002 4 -067 016 00031 00016 4 3 -0014L 00055 0005 4 -056 048 00055 00047 4 3 000

46L 00085 0003 4 -042 031 00085 00030 4 3 00026L 00123 0000 2 -024 003 00123 00002 2 1 00012L 00154 0002 4 -011 021 00154 00021 4 3 00144L 00613 0023 4 200 237 Fail - - 44L - - 005

Totgem 0018 0006 mgkg 1-level 187 (177) 5 00089 (44L) 5 4Totstd= 0022 0009 5-level 166 (154) 1

RESULTS Mean = 000893 mgkg

Repeatability variance S2r = 000001Repeatability std Sr = 000296 --gt 3308 r = 00083Between lab variance S2L = 000002Reproducibility var S2R = 000003Reproducibility std SR = 000570 --gt 6374 R = 00159Remarks 1 Lab rejected (44L)

000 050 100 150 200 250

k-values

10L

4L

46L

26L

12L

44L

Mandels k statistics(Compost 1 - Sum PBD)

00 00 00 00 00 00 01 01

Deviation from Mean

10L

4L

46L

26L

12L

44L

Labo

rato

ries

Compost 1 - Sum PBD -- Mean PARM = 0009 [mgkg]

-100 000 100 200

h-values

10L

4L

46L

26L

12L

44L

Labo

rato

ries

Mandels h statistics(Compost 1 - Sum PBD)

Compost 1-Sum PBD

Unit mgkg

Mandels k statistics(Sludge 1 - Sum PBD)Mandels h statistics(Sludge 1 - Sum PBD)

Sample Sludge 1 Sludge 1 - Sum PBD -- Mean PARM = 0256 [mgkg]

Element Sum PBD

General calcparmT1= 531806E+00T2= 162188E+00T3= 22T4= 84T5= 25223E-02

n= variabelp= 6

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00423 0025 4 -156 044 Fail 00423 00252 4 3 -02146L 01808 0118 4 -049 205 - - 46L - - -0074L 01810 0056 4 -049 097 01810 00558 4 3 -007

38L 02168 0006 4 -022 010 02168 00059 4 3 -00412L 02890 0065 4 034 113 02890 00647 4 3 00364L 03958 0008 4 116 014 Fail 03958 00079 4 3 01426L 04094 0034 2 126 059 Fail 04094 00337 2 1 015

Totgem 0245 0044 mgkg 1-level 198 (179) 6 02557 (46L) 6 5Totstd= 0130 0039 5-level 171 (155) 1

RESULTS Mean = 025570 mgkg

Repeatability variance S2r = 000158Repeatability std Sr = 003970 --gt 1553 r = 01112Between lab variance S2L = 001807Reproducibility var S2R = 001964Reproducibility std SR = 014015 --gt 5481 R = 03924Remarks 1 Lab rejected (46L)

000 050 100 150 200 250

k-values

10L

46L

4L

38L

12L

64L

26L

Mandels k statistics(Sludge 1 - Sum PBD)

-03 -02 -02 -01 -01 00 01 01 02 02

Deviation from Mean

10L

46L

4L

38L

12L

64L

26L

Labo

rato

ries

Sludge 1 - Sum PBD -- Mean PARM = 0256 [mgkg]

-200 -100 000 100 200

h-values

10L

46L

4L

38L

12L

64L

26L

Labo

rato

ries

Mandels h statistics(Sludge 1 - Sum PBD)

Sludge 1-Sum PBD

Unit mgkg

Mandels k statistics(Soil 3 - Sum PBD)Mandels h statistics(Soil 3 - Sum PBD)

Sample Soil 3 Soil 3 - Sum PBD -- Mean PARM = 0227 [mgkg]

Element Sum PBD

General calcparmT1= 610980E+00T2= 200876E+00T3= 26T4= 100T5= 13106E-02

n= variabelp= 7

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00028 0001 4 -037 000 Fail 00028 00005 4 3 -02226L 01179 0021 2 -036 003 Fail 01179 00208 2 1 -0114L 01305 0031 4 -036 004 Fail 01305 00308 4 3 -010

46L 02065 0035 4 -036 005 Fail 02065 00350 4 3 -00244L 02923 0037 4 -035 005 Fail 02923 00365 4 3 00712L 04051 0015 4 -034 002 Fail 04051 00149 4 3 01864L 04314 0022 4 -033 003 Fail 04314 00223 4 3 0203L 305500 2051 2 247 283 Fail - - 3L - - 3032

Totgem 4017 0276 mgkg 1-level 206 (181) 7 02266 (3L) 7 6Totstd= 10722 0717 5-level 175 (156) 1

RESULTS Mean = 022663 mgkg

Repeatability variance S2r = 000069Repeatability std Sr = 002626 --gt 1159 r = 00735Between lab variance S2L = 002568Reproducibility var S2R = 002637Reproducibility std SR = 016238 --gt 7165 R = 04547Remarks 1 Lab rejected (3L)

000 050 100 150 200 250 300

k-values

10L

26L

4L

46L

44L

12L

64L

3L

Mandels k statistics(Soil 3 - Sum PBD)

-50 00 50 100 150 200 250 300 350

Deviation from Mean

10L

26L

4L

46L

44L

12L

64L

3L

Labo

rato

ries

Soil 3 - Sum PBD -- Mean PARM = 0227 [mgkg]

-100 000 100 200 300

h-values

10L

26L

4L

46L

44L

12L

64L

3L

Labo

rato

ries

Mandels h statistics(Soil 3 - Sum PBD)

Soil 3-Sum PBD

19

Annex 4

Raw data submitted

Sample Compost1 Sample Compost 1 Sample Compost 1Element PBD 99 Element PBD 100 Element PBD 153

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]4L 00021 10L 00008 44L 000504L 00024 10L 00008 44L 000604L 00014 10L 00007 44L 000504L 00020 10L 00011 46L 00004

10L 00029 46L 00007 46L 0001210L 00027 46L 00012 46L 0000410L 00032 46L 00009 46L 0000946L 00025 46L 00007 12L 0000446L 00052 12L 00008 12L 0000846L 00029 12L 00012 12L 0000446L 00026 12L 00008 12L 0000712L 00026 12L 00014 26L 0000512L 00043 26L 00007 26L 0000512L 00026 26L 0000612L 0004726L 0002626L 00024

Sample Compost 1 Sample Compost 1 Sample Compost 1Element PBD 154 Element PBD 183 Element PBD 196

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]4L 00010 46L 00002 46L 00011

46L 00003 46L 00024 46L 0000846L 00007 46L 00021 12L 0000246L 00003 46L 00003 12L 0000346L 00004 12L 00003 12L 0000112L 00003 12L 00011 12L 0000212L 00005 12L 0000312L 00031 12L 0000312L 00006

Sample Compost 1 Sample Compost 1 Sample Compost 1Element PBD 197 Element PBD 203 Element PBD 209

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00002 46L 00010 4L 0004146L 00023 12L 00002 4L 0008946L 00022 12L 00003 44L 0041012L 00004 12L 00002 44L 0084012L 00006 12L 00002 44L 0064012L 00003 44L 0040012L 00004 12L 00079

12L 0007312L 0006512L 0009326L 0004926L 00049

Sample Compost 1Element PBD 47

LAB PARM [mgkg]26L 0003826L 00039

Element PBD 99 Element PBD 47 Element PBD 209LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]

4L 00170 10L 00210 4L 010004L 00200 10L 00220 4L 018004L 00170 10L 00210 4L 012004L 00190 46L 00300 4L 0220010L 00280 46L 00280 46L 0210010L 00300 46L 00250 46L 0200010L 00290 46L 00260 64L 0351846L 00340 64L 00059 64L 0363846L 00330 64L 00057 64L 0364546L 00300 64L 00062 64L 0350846L 00310 64L 00060 12L 0220964L 00194 12L 00191 12L 0177164L 00154 12L 00187 12L 0292264L 00185 12L 00190 12L 0164664L 00159 12L 00186 26L 0329712L 00242 26L 00666 26L 0300012L 00223 26L 0033212L 0022112L 0022226L 0024626L 00400

Element PBD 203 Element PBD 197 Element PBD 196LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00022 46L 00027 46L 0002446L 00014 46L 00024 46L 0002264L 00036 12L 00161 64L 0005864L 00058 12L 00060 64L 0006512L 00063 12L 00061 12L 0004812L 00034 12L 00036 12L 0002512L 00038 12L 0003212L 00027 12L 00022

Element PBD 183 Element PBD 154 Element PBD 153LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00049 4L 00020 4L 0002246L 00035 4L 00022 4L 0002446L 00036 4L 00020 4L 0002246L 00034 46L 00025 4L 0002664L 00027 46L 00025 46L 0004064L 00023 46L 00025 46L 0004264L 00024 46L 00023 46L 0003564L 00020 64L 00034 46L 0003812L 00230 64L 00023 64L 0007412L 00032 64L 00017 64L 0004712L 00031 64L 00011 64L 0004612L 00030 12L 00030 64L 0003026L 00007 12L 00021 12L 0006526L 00008 12L 00021 12L 00029

12L 00021 12L 0003226L 00015 12L 0002926L 00019 26L 00039

26L 00040

Element PBD 100LAB PARM [mgkg]

4L 000384L 000414L 000374L 00038

38L 0219038L 0220038L 0208038L 0220010L 0004410L 0005010L 0004310L 0004646L 0005746L 0005946L 0005346L 0005312L 0004312L 0004512L 0004312L 0004326L 0006226L 00057

Sample Soil 3 Sample Soil 3 Sample Soil 3Element PBD 99 Element PBD 47 Element PBD 100

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]10L 00016 10L 00011 10L 0000310L 00019 10L 00010 10L 0000410L 00013 10L 00012 10L 0000410L 00019 46L 00007 10L 0000246L 00025 46L 00022 46L 0000246L 00025 46L 00005 46L 0000646L 00008 46L 00007 46L 0000246L 00011 12L 00010 46L 0000264L 00005 12L 00017 3L 29100064L 00005 12L 00010 3L 32000064L 00006 12L 00009 26L 0000564L 00007 26L 00007 26L 0000512L 00012 26L 0000712L 0001312L 0001312L 0001226L 0000526L 00006

Sample Soil 3 Sample Soil 3 Sample Soil 3Element PBD 153 Element PBD 154 Element PBD 196

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]44L 00050 4L 00010 46L 0000744L 00050 46L 00001 46L 0001146L 00002 46L 00002 46L 0000846L 00003 46L 00001 46L 0001146L 00002 46L 00002 64L 0002646L 00002 64L 00001 64L 0002664L 00001 64L 00001 64L 0002964L 00001 64L 00001 64L 0003464L 00001 64L 00002 12L 0004564L 00002 12L 00003 12L 00032

12L 00002 12L 0002212L 00002 12L 0002112L 00002

Sample Soil 3 Sample Soil 3 Sample Soil 3Element PBD 197 Element PBD 203 Element PBD 209

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00006 46L 00011 4L 0091046L 00013 46L 00017 4L 0150046L 00011 46L 00015 4L 0120046L 00013 46L 00018 4L 0160012L 00090 64L 00013 44L 0337012L 00056 64L 00014 44L 0281012L 00033 64L 00016 44L 0287012L 00032 64L 00015 44L 02540

12L 00055 46L 0230012L 00041 46L 0220012L 00027 46L 0150012L 00026 46L 01900

64L 0438164L 0401664L 0414464L 0449812L 0367112L 0397812L 0409112L 03838

Sample Soil 3 26L 0102Element PBD 183 26L 0131

LAB PARM [mgkg]46L 0000746L 0000846L 0005846L 0000764L 0000264L 0000364L 0000364L 0000312L 0001512L 0001112L 0000712L 00007

European Commission EUR 23003 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on polybrominated diphenylethers Author(s) E Sobiecka H van der Sloot D Barcelo B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 68 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07403-5 Abstract Project HORIZONTAL is interdisciplinary aiming at a harmonisation and horizontal standardisation of test procedures in particular for sludge soils and biowastes In the context of this standardization project a series of draft technical specification were designed upon an extensive desk study fine-tuned after expert consultations and finally validated in international intercomparisons exercise This report summarises the work performed within the validation study of the draft standard for the determination of polybrominated diphenylethers (PBDE) in soils sludge and treated bio-waste using gas-chromatography method with mass selective detection (GC-MS) It further explains the underlying statistical concept for the calculation of reproducibility and repeatability from intercomparisons data In addition all single values results of the statistical evaluation as well as background information on the validation materials used are described and explained

The mission of the JRC is to provide customer-driven scientific and technical support for the conception development implementation and monitoring of EU policies As a service of the European Commission the JRC functions as a reference centre of science and technology for the Union Close to the policy-making process it serves the common interest of the Member States while being independent of special interests whether private or national

LB

-NA

-23003-EN

-C

7

112 Requirements for precision experiment

Layout of the experiment A suite of 10 to 12 different materials (soil sludge and biowaste) has been made available for the intercomparison exercise For each parameter investigated at least 10 to laboratories should be nominated to participate The same laboratories should be used for different parameters as far as possible Due to the complexity of analysis and the respective workload to the laboratories it was decided to propose three materials for the validation of the PBDE draft standard Each laboratory received two bottles of each material and was be requested to perform 4 independent analyses per material1 (2 per bottle) using the respective draft standard methods The 4 analysis per material should be carried out under repeatability conditions (ie same operator2 same equipment within a short period of time) As far as possible also the different materials should be measured under repeatability conditions however changes of eg operator or equipment are permitted but must be reported Likewise different materials can be analysed on different days if necessary Equipment used in the experiment needed to be checked prior to the experiment according to the requirements of the draft standard The results of these checks have to be documented Similarly date and time of each measurement had to be recorded for verification of repeatability conditions An appropriate timeframe for the entire exercise has been set and was to be respected

Recruitment of the laboratories Each sub-workpackage leader of HORIZONTAL was asked to select the laboratories using the information from section 52 of ISO 5725-21994 and provide the signed questionnaires (see also Annex 1) The workpackage leaders were responsible for providing the laboratories with the draft standard method and explaining the context of this exercise

Preparation and use of the materials Materials used for the exercise were prepared according to the general requirements for reference materials as laid down in ISO Guide 34 Materials were accompanied by instructions for use

Reporting of results Online submissions of results using an internet-based IT platform as well as XLS-Spreadsheets were used In case of online data submission the participating laboratories received a unique and confidential login and password in due time enabling them to

1 Independent analysis means analysis of independent test portions applying the entire analytical scheme to this test portion from eg extraction to quantification For instance it does not mean replicate injections of aliquots into a GC-MS instrument 2 Operator in this context may also consist of a fixed team of persons eg one person performing extraction one clean-up one quantification

8

enter their data in a structured form For authentication purposes a signed printout had to be submitted by mail The online data submission included a detailed questionnaire for additional information on the measurements

113 Statistical analysis Statistical analysis of data followed the requirements of ISO 5725-21994 and ISO 5725-51998 Appropriate tests for the homogeneity of variance detection of outliers and normal distribution were applied Statistical evaluation was done using an Excel Macro developed tested and successfully applied in other occasion by ECN Evaluation was executed jointly by JRC and ECN

12 Validation exercise for PBDE

121 Compounds to be measured The following compound were selected for the validation exercise Tetra-BDE-47 Penta-BDE-100 Penta-BDE-99 Hexa-BDE-154 Hexa-BDE-153 Hepta-BDE-183 Octa-BDE-196 Octa-BDE-197 Octa-BDE-203 Deca-BDE-209

122 Samples dispatched for the validation of PBDE After a preliminary rough screening the following materials were used for the validation round of PBDE

bull Compost 1 A pollutant loaded compost material from Vienna bull Sewage Sludge 1 A mixed sewage sludge from Essen bull Soil 3 A sludge amended soil from Barcelona

A more detailed description of background concentrations can be found in Annex 2 to this report The samples were dispatched simultaneously to all participants using a private courier service

123 Draft standards to be followed The draft standards to be followed could be downloaded following this link which is situated on the website of the Project HORIZONTAL httpwwwecnnldocssocietyhorizontalBFR_Standard_for_validationpdf

124 Analytical programm Of each of the three materials 2 bottles had to be analysed and each bottle had to analysed independently twice As mentioned above analyses were to be done under repeatability conditions Results were to be reported referring to DRY MATTER content The choice how to apply dm correction was free for each participant

9

125 Timing and Submission of data Dispatch of samples was done on the 18th of October 2006 For users of the Online data submission system (MILC) User Registration was possible from 14th of November 2006 with opening of the MILC Data Submission on 1st of December 2006 The deadline for submission of results has been set for PBDE to the 12th of January 2007 but was extended to the end of the same months After that no further submission was possible Alternatively the participants were allowed to submit data electronically as Excel sheet using simply Email All data were treated in a confidential way Any presentation hereafter will refer only to numerical data and it will not be possible to identify the originating laboratory Lab Codes displayed are NOT related to the order of laboratories hereafter In addition to the information provide an Helpdesk was implemented in order to give quick and individual response to the participants during and immediately after the validation study In case of doubt and suspected transcription errors further enquires were conducted by JRC

10

126 Participants The following table lists the participating organisations and entities in the validation exercise for the horizontal PBDE standard

bull Austria o Umweltbundesamt

bull Czech Republic o Povodi Labe statni podnik - OVHL Laboratory

bull France o CIRSEE o CTC Environnement o INERIS

bull Germany o Federal Environmental Agency Section III 34 Laboratory Methods for

the Surveillance of Waste and Wastewater (UBA) bull Italy

o European Commission DG JRC IES bull Spain

o Consejo Superior de Investigaciones Cientificas (CSIC)

bull Sweden o ALCONTROL AB

11

13 Summary results and derived performance characteristics The result of the various statistical evaluation including outlier tests calculation of repeatability and reproducibility standard deviation for the congeners of interest can be found in Annex 3 of this report In addition all data submitted by the participants as well as those considered for the calculation of the performance characteristics are listed in Annex 3 to this report Based on these calculations the following results were obtained in the validation round upon statistical evaluation according to ISO 5725-2 The average values the repeatability standard deviation (sr) and the reproducibility standard deviation (sR) were obtained (Table1) The repeatability is determined as an interval around a measurement result (ie repeatability limit) This interval corresponds to the maximum difference that can be expected (with a 95 statistical confidence) between one test result and another both test results being obtained under the following conditions The tests are performed in accordance with all the requirements of the present standard by the same laboratory using its own facilities and testing laboratory samples obtained from the same primary field sample and prepared under identical procedures The repeatability limit was calculated using the relationship r test = f radic2 s rtest with the critical range factor f = 2 The reproducibility like repeatability is also determined as an interval around a measurement result (ie reproducibility limit) This interval corresponds to the maximum difference that can be expected (with a 95 statistical confidence) between one test result and another test result obtained by another laboratory both test results being obtained under the following conditions The tests are performed in accordance with all the requirements of the present standard by two different laboratories using their own facilities and testing laboratory samples obtained from the same primary field sample and prepared under identical procedures The reproducibility limit was calculated using the relationship R = f radic2 sR with the critical range factor f = 2

12

Table 1 - Results of the interlaboratory comparison studies of the determination of selected polybrominated diphenyl ethers (PBDE) by gaschromatography with mass spectrometric detection (GC-MS) in soil sludge and treated biowaste All concentrations are expressed in mgkg dm

Matrix Parameter Mean sr sR r R p Outliers Used No of data

No of data reported below

detection

Total no of data

Sludge 1 PBD 47 00181 461 4 15 5 20 Compost 1 00039 94 3 12 0 12 Soil 3 00010 50 50 00014 00014 4 0 13 10 23 Sludge 1 PBD 99 00239 64 28 00043 00186 5 1 19 0 23 Compost 1 00029 31 35 00025 00028 5 0 17 4 21 Soil 3 00013 499 4 16 8 24 Sludge 1 PBD 100 00049 51 17 00007 00024 5 1 18 2 24 Compost 1 00009 25 29 00006 00007 4 0 14 7 21 Soil 3 61103 211 3 10 15 25 Sludge 1 PBD 153 00038 33 38 00034 0004 5 0 18 0 18 Compost 1 00019 116 3 11 3 14 Soil 3 00011 177 2 10 10 20 Sludge 1 PBD 154 00023 234 4 15 2 17 Compost 1 00008 1118 3 9 5 14

13

Matrix Parameter Mean sr sR r R p Outliers Used No of data

No of data reported below

detection

Total no of data

Soil 3 00002 1049 4 13 6 19 Sludge 1 PBD 183 00048 1217 3 12 2 14 Compost 1 00009 1048 2 8 5 13 Soil 3 00011 1395 3 12 6 18 Sludge 1 PBD 196 00037 470 2 8 7 15 Compost 1 00004 950 2 6 4 10 Soil 3 00023 519 3 12 2 14 Sludge 1 PBD 197 00062 834 2 6 8 14 Compost 1 00009 1001 2 7 7 14 Soil 3 00032 904 2 8 6 14 Sludge 1 PBD 203 00037 461 2 8 4 12 Compost 1 00004 978 2 5 3 8 Soil 3 00022 598 3 12 0 12 Sludge 1 PBD 209 02493 170 39 01186 02689 5 0 16 2 18 Compost 1 00273 104 3 10 5 15 Soil 3 02582 1115 51 00806 03676 6 0 22 0 22

14

Matrix Parameter Mean sr sR r R p Outliers Used No of data

No of data reported below

detection

Total no of data

Sludge 1 Sum PBD 0256 155 548 0111 0392 6 1 22 Compost 1 0009 331 637 0008 0016 5 1 18 Soil 3 0227 116 717 0074 0455 7 1 26 Abbreviations sr Repeatability standard deviation SR Reproducibility standard deviation r Repeatability limit (comparing two measurements) R Reproducibility limit (comparing two measurements) p Number of labs determination not possible

15

14 Annexes Annex 1 Model questionnaire to be filled by the participating laboratories Annex 3 Report on the validation materials used Annex 2 Statistical calculations Annex 3 Data submitted

16

Annex 1

Model questionnaire to be filled by the participating laboratories

Model questionnaire to be filled by the participating laboratories Name of laboratory Contact person Contact details email Phone Fax Mail address of lab Dispatch address of lab for shipment of samples (no PO boxes) Title of measurement method (copy attached) Our laboratory is willing to participate in the precision experiment for this draft standard method

Yes No As participant we understand that

bull All essential apparatus chemicals and other requirements specified in the method must be available in our laboratory when the programme begins

bull Specified timing requirements such as starting and finishing date of the programme must be rigidly met

bull The method must be strictly adhered to bull Samples must be handled in accordance with instructions bull A qualified operator must perform the measurements

Having studied the method and having made a fair appraisal of our capabilities and facilities we feel that we will be adequately prepared for cooperative testing of this method Comments helliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphellip Signature Date

17

Annex 2

Report on the validation materials used

VI

Abstract This report gives an overview on the available analytical information on the following raw materials to be used for the production of validation materials of the so-called Project HORIZONTAL

bull Four sludge materials from Duumlsseldorf Germany

bull An agricultural soil material from Reading United Kingdom

bull A compost material from Vienna Austria

bull A compost material from Korschenbroich Germany

bull A sludge-amended agricultural soil from Pavia Province Italy

bull A sludge-amended soil from Barcelona Spain

bull A sludge-amended soil from Essen Germany

bull A long-term sludge exposed soil from Hohenheim Germany

VII

List of Abbreviations Throughout this report the following abbreviations are used

AOX absorbable organic halogens

Corg organic carbon content

Ctotal total carbon content

CAT cation exchangeable

CDD chlorinated dibenzodioxin

CDF chlorinated dibenzofuran

DEHP di(2-ethylhexyl)phthalate

DM dry matter

EPA Environment Protection Agency

EU European Union

FM fresh matter

Hp hepta

Hx hexa

IES Institute for Environment and Sustainability

IRMM Institute for Reference Materials and Measurements

JRC Joint Research Centre

LAS linear alkylsulfonates

LoD limit of detection

LUA Landesumweltamt

Ntotal total nitrogen content

NH4-N Ammonium nitrogen

NO3-N Nitrate nitrogen

NP nonylphenol

NRW North Rhine Westphalia

O octa

P poly

PAH polycyclic aromatic hydrocarbon

PCB polychlorinated biphenyl

Pe penta

T tetra

TEQ toxicity equivalent

UBA Umweltbundesamt

WHO World Health Organization

WWTP waste water treatment plant

6

1 Introduction This report gives an overview on the available analytical information on the following raw materials to be used for the production of validation materials of the so-called Project HORIZONTAL

bull Four sludge materials from Duumlsseldorf Germany

bull An agricultural soil material from Reading United Kingdom

bull A compost material from Vienna Austria

bull A compost material from Korschenbroich Germany

bull A sludge-amended agricultural soil from Pavia Province Italy

bull A sludge-amended soil from Barcelona Spain

bull A sludge-amended soil from Essen Germany

bull A long-term sludge exposed soil from Hohenheim Germany

The following analytical information was gathered partly before and during the sampling of the raw materials to be used for the production of the HORIZONTAL validation materials The material were sampled by IES and shipped to IRMM in the course of the year 2005 The information gathered was then completed by various analytical screenings for PAHs and PCBs done by the Institute for Reference Materials and Measurements Geel Belgium for phthalates done by UBA Berlin Germany for PBDE done by IIQAB-CSIC Barcelona Spain for trace elements and some selected major and minor elements by the Institute for Environment and Sustainability Ispra Italy

The work compiled hereafter is based on the numerous additional efforts of the scientists working at various members of the consortium Project HORIZONTAL-Org and contributing organisations

This work is gratefully acknowledged

2 Overview on property values

21 Sludge materials from Duumlsseldorf Germany

The various sewage sludge materials originate from various installations in the North Rhine Westphalia and were produced and sampled by staff from the Landesumweltamt (LUA) NRW under the responsibility from Dr K Furtmann

In total four sludge materials (Sludge A and D from a major municipal WWTP Sludge B from a municipal WWTP with industrial input and Sludge C from a municipal WWTP with high PCB-Content) were obtained and will be blended to two final materials Before sampling the following analytical data for a typical sample were received

7

Table 1 ndash Analytical data obtained on an average sludge sample in LUA NRW (with courtesy of K Furtmann LUA Duumlsseldorf)

Parameter Concentration PCB 120 ugkg DEHP 110 mgkg PAH 5 mgkg (EPA) PCDDF 15 ng TEkg PBDE 400 ugkg NP 40 mgkg LAS 3 gkg AOX 300 mgkg

Subsequent screening led to the information displayed hereafter It should be stressed that the data were obtained as SCREENING information on the UNTREATED or partially treated raw materials Therefore the final target values which are relevant for the validation intercomparison can be different

Table 2 ndash Analytical data obtained on a first screening on the sludge samples from LUA NRW

Sewage sludge A

Dusseldorf

sewage sludge D

Dusseldorf PCB (ngg) 28 62 35 52 101 65 101 31 38 118 49 40 153 30 33 105 24 11 138 46 38 156 lt1 lt1 180 34 23 170 23 19 PAH (ngg) Naphtalene 34 381 Acenaphtylene 15 43 Acenaphthene 81 108 Fluorene 94 1167 Phenantrene 3440 Anthracene 22 344 Flouranthene 316 4817 Pyrene 235 3011 Benz(a)anthracene 473 791 Chrysene 691 1078 Benz(b)fluoranthene 538 1688 Benz(k)fluoranthene 228 635 Benz(a)pyrene 383 1114 Indeno(123-cd)pyrene 92 229 Dibenzo(ah)anthracene 71 70 Benzo(ghi)perylene 80 185

8

Table 3 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Sludge D (1) 0135 41474 385 Sludge B (2) 0538 0034 30634 547 Sludge A (3) 0184 0037 31399 146 Sludge C (4) 0354 1528 6678 229

Table 4 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Sludge 2

(B)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

554

959

694

591

772

509

nq

nq

970

2216

2379

Table 5 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena IES Ispra Spain) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Sludge 1 (D) 265 290 533 359 1231 338 784 438 lt 005 232 786 Sludge 2 (B) 119 311 626 202 278 299 722 251 lt 005 118 625 Sludge 3 (A) 168 360 621 332 847 416 119 451 lt 005 116 1237 Sludge 4 (C) 563 198 116 273 726 511 473 618 lt 005 444 2015

Table 6 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Sludge 1 (D) 2154 58 844 099 103 101 4367 lt15 50448 Sludge 2 (B) 1067 366 692 046 1491 077 5217 lt15 57633 Sludge 3 (A) 731 663 684 035 1287 068 3733 lt15 60369 Sludge 4 (C) 4379 965 527 163 522 107 5628 lt15 23945

Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM)Sludge 1 (D) 03 2403 101 1002 350 15 1944 132Sludge 2 (B) 031 315 97 879 172 12 514 180Sludge 3 (A) 031 1281 153 1567 265 16 1440 168Sludge 4 (C) 055 231 628 2625 371 81 1101 244

9

22 Agricultural soil material from Reading United Kingdom

The material was proposed by the University of Reading (S Nortcliff) and was sampled from a site called ldquoFrogmore Farmrdquo which was featured in the ldquoMetalsrdquo Report for HORIZONTAL This site is close to Reading with soils developed on flintyloamy periglacial materials over Chalk has a long and well documented history of sludge application The focus of the work of Nortcliff et al undertook at this site and the monitoring and control at the site (by Thames Water and the subsequent subsidiary bodies dealing with sludge application to soil) was on metals (and metal loads) with no analysis or indeed any form of investigation in to organics in the broadest sense

The analytical information produced in the context of the screening of the raw material is displayed below

Table 7 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 3

(Reading) 0032 0119 669

Table 8 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 3 (Reading) 015 706 279 138 152 901 267 300 lt 005 258 931

Table 9 ndash Analytical data obtained on a first screening on the sludge-amended soil from Reading (courtesy of IRMM)

Parameter Concentration

PCB ngg 28 lt1 52 lt1 101 lt1 118 lt1 153 lt1 105 lt1 138 lt1 156 lt1 180 lt1 170 lt1 PAH ngg Naphtalene lt10 Acenaphtylene 21 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene lt10 Flouranthene 818 Pyrene 776 Benz(a)anthracene 565

10

Parameter Concentration

Chrysene 608 Benz(b)fluoranthene 824 Benz(k)fluoranthene 329 Benz(a)pyrene 799 Indeno(123-cd)pyrene

779

Dibenzo(ah)anthracene 118 Benzo(ghi)perylene 394

Table 10 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 3

(Reading)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

103

003

nq

nq

nq

nd

nd

272

273

Table 11 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 3 (Reading) 015 706 279 138 152 901 267 300 lt 005 258 931

Table 12 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 3 (Reading) 7936 477 112 096 194 017 4107 443 2102 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 3 (Reading) 042 13 45 69 69 69 216 92

Table 13 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 3 (Reading) 012

11

23 Compost from Vienna Austria

The fresh compost material was obtained from the Austrian Federal Environment Agency (UBA Vienna) which had used a sub-batch of the raw material for national intercomparson The remainder of the material was stored at 4degC until shipment to IRMM for further processing The following analytical information was provided by UBA Austria and completed with various screenings

Table 14 ndash Analytical data on compost material received from UBA Austria Inorganic and sum parameters

Parameter Unit Sample fraction used Observed mean B CAT mgl FM Fresh sample lt10mm 61 K CAT mgl FM Fresh sample lt10mm 2624 Mg CAT mgl FM Fresh sample lt10mm 242 P CAT mgl FM Fresh sample lt10mm 49 B CAT DM Fresh sample lt10mm 00017 K CAT DM Fresh sample lt10mm 072 Mg CAT DM Fresh sample lt10mm 007 P CAT DM Fresh sample lt10mm 001 NO3-N mgkg FM Fresh sample lt10mm 35 NH4-N mgkg FM Fresh sample lt10mm 230 Ctotal DM lt45degdry milled 29 Corg DM lt45degdry milled 27 Ntotal DM lt45degdry milled 17 P mgkg DM lt45degdry milled 2596 K mgkg DM lt45degdry milled 11019 K DM lt45degdry milled 110 B mgkg DM lt45degdry milled 60 Cd mgkg DM lt45degdry milled 046 Cr mgkg DM lt45degdry milled 25 Cu mgkg DM lt45degdry milled 46 Hg mgkg DM lt45degdry milled 020 Ni mgkg DM lt45degdry milled 18 Pb mgkg DM lt45degdry milled 45 Zn mgkg DM lt45degdry milled 198 Ca mgkg DM lt45degdry milled 68776 Ca DM lt45degdry milled 69 Mo mgkg DM lt45degdry milled 08 S mgkg DM lt45degdry milled 2137 Fe mgkg DM lt45degdry milled 9959 Mn mgkg DM lt45degdry milled 418 Na mgkg DM lt45degdry milled 742 Co mgkg DM lt45degdry milled 41 AOX mgkg DM lt30deg dry milled 62

Table 15 ndash Analytical data on compost material received from UBA Austria Polycyclic aromatic hydrocarbons

PAH Unit Result Naphthaline microgkg DM 93 Acenaphthylene microgkg DM 86 Acenaphthene microgkg DM 5 Fluorene microgkg DM 80 Phenanthrene microgkg DM 89 Anthracene microgkg DM 27 Fluoranthene microgkg DM 487 Pyrene microgkg DM 380

12

PAH Unit Result Benzo(a)anthracene microgkg DM 278 Chrysene microgkg DM 317 Benzo(b)fluoranthene microgkg DM 365 Benzo(k)fluoranthene microgkg DM 193 Benz(a)pyrene microgkg DM 320 Indeno(123-cd)pyrene microgkg DM 233 Dibenz(ah)anthracene microgkg DM 67 Benzo(ghi)perylene microgkg DM 225 Sum EPA microgkg DM 3013 Sum EPA mgkg DM 30

Table 16 ndash Analytical data on compost material received from UBA Austria Sum PCDDs and PCBs

Parameter

Dioxine TEQ (ITEF) ngkg DM 73 TEQ (WHO) ngkg DM 35 PCB Σ Ballschmiter mgkg DM 005

Table 17 ndash Analytical data on compost material obtained by screening in IRMM

Parameter Result in ngg

PCB 28 2 52 2 101 4 118 3 153 10 105 1 138 8 156 1 180 5 170 lt1 PAH Naphtalene lt10 Acenaphtylene lt10 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene 26 Fluoranthene 611 Pyrene 510 Benz(a)anthracene 888 Chrysene 957 Benz(b)fluoranthene 1531 Benz(k)fluoranthene 547 Benz(a)pyrene 1101 Indeno(123-cd)pyrene 416 Dibenzo(ah)anthracene 81 Benzo(ghi)perylene 295

13

Table 18 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Compost 1

(Vienna)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

402

019

259

nq

023

004

nq

nq

144

174

259

Table 19 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Compost 1

(Vienna) 0058 1426 557

Table 20 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Compost 1 (Vienna) 039 736 319 410 365 127 495 004 079 013 208

Table 21 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Compost 1 (Vienna) 2063 431 617 426 199 249 1602 lt15 10521

Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Compost 1 (Vienna) 035 3496 81 375 79 55 653 60

Table 22 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Compost 1 (Vienna) 017

14

24 Agricultural soil sludge amended soil from Pavia Italy

This sludge-amended soil material was obtained during a monitoring campaign which aimed at a generic description of the over-all soil quality in Pavia Province Italy The material which was collected from the upper horizon originates from a small farm called ldquoCascina Novellordquo During the characterisation of the site the following analytical information was obtained on a pooled sample of a sub-area of the farm of 20 X 20 m2

Table 23 ndash Analytical data on Pavia soil

Parameter Result Al 713 Wgt As 224 mgkg Cd 079 mgkg Cr 59 mgkg Cu 308 mgkg Hg 008 mgkg Ni 344 mgkg Pb 246 mgkg Zn 95 mgkg C 091 Wgt 2378-TCDD 0047 pgg 12378-PeCDD 015 pgg 123478-HxCDD 019 pgg 123678-HxCDD 15 pgg 123789-HxCDD 074 pgg 1234678-HpCDD 26 pgg OCDD 382 pgg 2378-TCDF 068 pgg 12378-PeCDF 053 pgg 23478-PeCDF 071 pgg 123478-HxDF 100 pgg 123678-HxDF 066 pgg 234678-HxDF 16 pgg 123789-HxDF 027 pgg 1234678-HpDF 12 pgg 1234789-HpDF 068 pgg OCDF 33 pgg I-TEQ 20 pgg WHO-TEQ 17 pgg

In addition the screening performed at IRMM did not reveal significant quantities of PCBs and PAHs which were all below the LoDs (1 ngg for PCBs and 10 ngg for PAHs respectively)

Table 24 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 5 (Pavia) 0005 0011 154

15

Table 25 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 5

(Pavia)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

039

nq

nq

008

nq

nd

nd

670

671

Table 26 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 5 (Pavia) 033 184 573 225 426 305 206 200 lt 005 381 878

Table 27 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 5 (Pavia) 6939 129 145 224 425 116 6118 255 1789 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 5 (Pavia) 184 62 38 108 55 66 597 110

Table 28 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 5 (Pavia) 006

16

25 Sludge-amended-soil from Barcelona Spain

The sludge-amended soil material from Barcelona sampled upon indication from the Barcelorsquo- Group in Barcelona

Table 29 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 2 (Lleida T) 0015 0183 1138

Table 30 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 2

(Lleida T)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

159

045

nq

048

160

nq

nq

1000

1004

Table 31 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 2 (Lleida T) 059 141 327 536 405 186 184 224 lt 005 318 111

Table 32 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 2 (Lleida T) 4443 1067 1429 253 344 204 4116 780 3396 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 2 (Lleida T) 064 65 26 125 59 17 547 65

Table 33 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 2 (Lleida T) 010

17

26 Sludge amended soil from Essen Germany

The German sludge-amended soil from Essen which was provided as the three sludge materials by LUA NRW did not feature significant concentrations of the PCB congeners 28 52 101 118 153 105 138 156 180 170 but had detectable amounts of some PAHs

Table 34 ndash Analytical screening data on the German sludge-amended soil

Parameter Concentration(ngg)

Naphtalene lt10 Acenaphtylene lt10 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene lt10 Fluoranthene 28 Pyrene 20 Benz(a)anthracene 24 Chrysene 47 Benz(b)fluoranthene 76 Benz(k)fluoranthene 20 Benz(a)pyrene 35 Indeno(123-cd)pyrene 35 Dibenzo(ah)anthracene 10 Benzo(ghi)perylene 26

Table 35 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 4 (Essen) 0011 0302 055

Table 36 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 4

(Essen)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

nq

nq

nq

nq

nq

nq

128

191

203

18

Table 37 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 4 (Essen) 052 545 261 805 320 403 273 273 lt 005 295 781

Table 38 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 4 (Essen) 7947 442 085 06 086 007 2163 189 2019 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 4 (Essen) 045 19 42 87 683 60 462 61

Table 39 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 4 (Essen) 004

27 Long-term sludge exposed soil from Hohenheim-Stuttgart Germany

Similarly an additional sludge exposed soil was sampled at the University of Hohenheim Stuttgart were a test soil was long-term exposed to elevated concentrations of sewage sludge

Table 40 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 1 (Stuttgart) 0045 0263 1765

Table 41 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 1

(Stuttgart)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

230

006

004

004

nq

nd

nd

498

500

19

Table 42 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 1 (Stuttgart) 069 127 361 262 504 183 252 262 lt 005 266 142

Table 43 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 1 (Stuttgart) 7194 1006 133 186 366 088 7874 275 3571 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 1 (Stuttgart) 123 50 47 212 85 69 991 129

Table 44 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 1 (Stuttgart) 177

18

Annex 3

Statistical calculations

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 47)Mandels h statistics(Sludge 1 - PBD 47)

Sample Sludge 1 NUM

Element PBD 47

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00213 0001 3 -021 005 - - 10L - - NUM46L 00273 0002 4 016 021 - - 46L - - NUM64L 00059 0000 4 -116 002 NUM - 64L - - NUM12L 00188 0000 4 -036 002 - - 12L - - NUM26L 00499 0024 2 157 223 Fail - - 26L - - NUM

Totgem 0025 0005 mgkg 1-level 172 (185) NUM (10L46L64L12L26L) -1Totstd= 0016 0010 5-level 157 (162) 5

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 5 Labs rejected (10L46L64L12L26L)

000 050 100 150 200 250

k-values

10L

46L

64L

12L

26L

Mandels k statistics(Sludge 1 - PBD 47)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

10L

46L

64L

12L

26L

Labo

rato

ries

NUM

-200 -100 000 100 200

h-values

10L

46L

64L

12L

26L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 47)

Sludge 1-PBD 47

Unit mgkg

Mandels k statistics(Soil 3 - PBD 47)Mandels h statistics(Soil 3 - PBD 47)

Sample Soil 3 Soil 3 - PBD 47 -- Mean PARM = 0001 [mgkg]

Element PBD 47

General calcparmT1= 134814E-02T2= 142830E-05T3= 13T4= 45T5= 22767E-06

n= variabelp= 4

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean26L 00007 0000 2 -143 001 00007 00000 2 1 00046L 00010 0001 4 010 181 00010 00008 4 3 00010L 00011 0000 3 049 023 00011 00001 3 2 00012L 00012 0000 4 084 081 00012 00004 4 3 000

Totgem 0001 0000 mgkg 1-level 149 (177) 4 00010 () 4 3Totstd= 0000 0000 5-level 142 (159)

RESULTS Mean = 000100 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000050 --gt 5031 r = 00014Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000050 --gt 5031 R = 00014Remarks none

000 050 100 150 200

k-values

26L

46L

10L

12L

Mandels k statistics(Soil 3 - PBD 47)

00 00 00 00 00 00 00 00 00 00 00

Deviation from Mean

26L

46L

10L

12L

Labo

rato

ries

Soil 3 - PBD 47 -- Mean PARM = 0001 [mgkg]

-200 -100 000 100

h-values

26L

46L

10L

12L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 47)

Soil 3-PBD 47

Unit mgkg

Mandels k statistics(Compost 1 - PBD 99)Mandels h statistics(Compost 1 - PBD 99)

Sample Compost 1 Compost 1 - PBD 99 -- Mean PARM = 0003 [mgkg]

Element PBD 99

General calcparmT1= 492124E-02T2= 148747E-04T3= 17T4= 61T5= 93196E-06

n= variabelp= 5

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00020 0000 4 -137 053 00020 00004 4 3 000

26L 00025 0000 2 -058 024 00025 00002 2 1 00010L 00029 0000 3 012 032 00029 00003 3 2 00046L 00033 0001 4 069 161 00033 00013 4 3 00012L 00036 0001 4 114 140 00036 00011 4 3 000

Totgem 0003 0001 mgkg 1-level 172 (185) 5 00029 () 5 4Totstd= 0001 0001 5-level 157 (162)

RESULTS Mean = 000286 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000088 --gt 3086 r = 00025Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000101 --gt 3525 R = 00028Remarks none

000 050 100 150 200

k-values

4L

26L

10L

46L

12L

Mandels k statistics(Compost 1 - PBD 99)

00 00 00 00 00 00 00 00 00 00

Deviation from Mean

4L

26L

10L

46L

12L

Labo

rato

ries

Compost 1 - PBD 99 -- Mean PARM = 0003 [mgkg]

-200 -100 000 100 200

h-values

4L

26L

10L

46L

12L

Labo

rato

ries

Mandels h statistics(Compost 1 - PBD 99)

Compost 1-PBD 99

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 99)Mandels h statistics(Sludge 1 - PBD 99)

Sample Sludge 1 Sludge 1 - PBD 99 -- Mean PARM = 0024 [mgkg]

Element PBD 99

General calcparmT1= 448050E-01T2= 112113E-02T3= 19T4= 73T5= 32972E-05

n= variabelp= 5

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean64L 00173 0002 4 -118 041 Fail 00173 00019 4 3 -0014L 00183 0002 4 -104 032 00183 00015 4 3 -001

12L 00227 0001 4 -038 022 00227 00010 4 3 00010L 00290 0001 3 055 021 00290 00010 3 2 00146L 00320 0002 4 100 039 00320 00018 4 3 00126L 00323 0011 2 105 234 - - 26L - - 001

Totgem 0025 0003 mgkg 1-level 187 (177) 5 00239 (26L) 5 4Totstd= 0007 0004 5-level 166 (154) 1

RESULTS Mean = 002385 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000153 --gt 643 r = 00043Between lab variance S2L = 000004Reproducibility var S2R = 000004Reproducibility std SR = 000666 --gt 2791 R = 00186Remarks 1 Lab rejected (26L)

000 050 100 150 200 250

k-values

64L

4L

12L

10L

46L

26L

Mandels k statistics(Sludge 1 - PBD 99)

00 00 00 00 00 00 00 00 00 00

Deviation from Mean

64L

4L

12L

10L

46L

26L

Labo

rato

ries

Sludge 1 - PBD 99 -- Mean PARM = 0024 [mgkg]

-200 -100 000 100 200

h-values

64L

4L

12L

10L

46L

26L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 99)

Sludge 1-PBD 99

Unit mgkg

Mandels k statistics(Soil 3 - PBD 99)Mandels h statistics(Soil 3 - PBD 99)

Sample Soil 3 NUM

Element PBD 99

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00017 0000 4 091 068 - - 10L - - NUM46L 00017 0001 4 100 211 - - 46L - - NUM64L 00005 0000 4 -106 023 NUM - 64L - - NUM12L 00012 0000 4 015 014 - - 12L - - NUM26L 00006 0000 2 -101 012 - - 26L - - NUM

Totgem 0001 0000 mgkg 1-level 172 (173) NUM (10L46L64L12L26L) -1Totstd= 0001 0000 5-level 157 (153) 5

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 5 Labs rejected (10L46L64L12L26L)

000 050 100 150 200 250

k-values

10L

46L

64L

12L

26L

Mandels k statistics(Soil 3 - PBD 99)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

10L

46L

64L

12L

26L

Labo

rato

ries

NUM

-200 -100 000 100 200

h-values

10L

46L

64L

12L

26L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 99)

Soil 3-PBD 99

Unit mgkg

Mandels k statistics(Compost 1 - PBD 100)Mandels h statistics(Compost 1 - PBD 100)

Sample Compost 1 Compost 1 - PBD 100 -- Mean PARM = 0001 [mgkg]

Element PBD 100

General calcparmT1= 124272E-02T2= 113129E-05T3= 14T4= 52T5= 46584E-07

n= variabelp= 4

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean26L 00006 0000 2 -131 037 Fail 00006 00001 2 1 00010L 00009 0000 4 003 083 00009 00002 4 3 00046L 00009 0000 4 016 115 00009 00002 4 3 00012L 00011 0000 4 112 136 Fail 00011 00003 4 3 000

Totgem 0001 0000 mgkg 1-level 149 (167) 4 00009 () 4 3Totstd= 0000 0000 5-level 142 (15)

RESULTS Mean = 000085 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000022 --gt 2531 r = 00006Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000025 --gt 2882 R = 00007Remarks none

000 050 100 150

k-values

26L

10L

46L

12L

Mandels k statistics(Compost 1 - PBD 100)

00 00 00 00 00 00 00 00 00 00 00

Deviation from Mean

26L

10L

46L

12L

Labo

rato

ries

Compost 1 - PBD 100 -- Mean PARM = 0001 [mgkg]

-200 -100 000 100 200

h-values

26L

10L

46L

12L

Labo

rato

ries

Mandels h statistics(Compost 1 - PBD 100)

Compost 1-PBD 100

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 100)Mandels h statistics(Sludge 1 - PBD 100)

Sample Sludge 1 Sludge 1 - PBD 100 -- Mean PARM = 0005 [mgkg]

Element PBD 100

General calcparmT1= 852065E-02T2= 412762E-04T3= 18T4= 68T5= 78914E-07

n= variabelp= 5

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00039 0000 4 -042 007 Fail 00039 00002 4 3 000

12L 00044 0000 4 -041 005 Fail 00044 00001 4 3 00010L 00046 0000 4 -041 013 Fail 00046 00003 4 3 00046L 00056 0000 4 -040 012 Fail 00056 00003 4 3 00026L 00059 0000 2 -040 013 Fail 00059 00003 2 1 00038L 02168 0006 4 204 244 Fail - - 38L - - 021

Totgem 0040 0001 mgkg 1-level 187 (177) 5 00049 (38L) 5 4Totstd= 0087 0002 5-level 166 (154) 1

RESULTS Mean = 000486 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000025 --gt 507 r = 00007Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000084 --gt 1731 R = 00024Remarks 1 Lab rejected (38L)

000 050 100 150 200 250

k-values

4L

12L

10L

46L

26L

38L

Mandels k statistics(Sludge 1 - PBD 100)

-01 00 01 01 02 02 03

Deviation from Mean

4L

12L

10L

46L

26L

38L

Labo

rato

ries

Sludge 1 - PBD 100 -- Mean PARM = 0005 [mgkg]

-100 000 100 200 300

h-values

4L

12L

10L

46L

26L

38L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 100)

Sludge 1-PBD 100

Unit mgkg

Mandels k statistics(Soil 3 - PBD 100)Mandels h statistics(Soil 3 - PBD 100)

Sample Soil 3 NUM

Element PBD 100

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00003 0000 4 -050 000 Fail - - 10L - - NUM46L 00003 0000 4 -050 000 Fail NUM - 46L - - NUM3L 305500 2051 2 150 200 Fail - - 3L - - NUM

26L 00005 0000 2 -050 000 Fail - - 26L - - NUM

Totgem 7638 0513 mgkg 1-level 149 (177) NUM (10L46L3L26L) -1Totstd= 15275 1025 5-level 142 (159) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (10L46L3L26L)

000 050 100 150 200

k-values

10L

46L

3L

26L

Mandels k statistics(Soil 3 - PBD 100)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

10L

46L

3L

26L

Labo

rato

ries

NUM

-100 000 100 200

h-values

10L

46L

3L

26L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 100)

Soil 3-PBD 100

Unit mgkg

Mandels k statistics(Compost 1 - PBD 153)Mandels h statistics(Compost 1 - PBD 153)

Sample Compost 1 NUM

Element PBD 153

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean44L 00053 0001 3 150 157 Fail - - 44L - - NUM46L 00007 0000 4 -044 111 Fail - - 46L - - NUM12L 00005 0000 4 -051 055 Fail - - 12L - - NUM26L 00005 0000 2 -054 001 Fail NUM - 26L - - NUM

Totgem 0002 0000 mgkg 1-level 149 (177) NUM (44L46L12L26L) -1Totstd= 0002 0000 5-level 142 (159) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (44L46L12L26L)

000 050 100 150 200

k-values

44L

46L

12L

26L

Mandels k statistics(Compost 1 - PBD 153)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

44L

46L

12L

26L

Labo

rato

ries

NUM

-100 000 100 200

h-values

44L

46L

12L

26L

Labo

rato

ries

Mandels h statistics(Compost 1 - PBD 153)

Compost 1-PBD 153

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 153)Mandels h statistics(Sludge 1 - PBD 153)

Sample Sludge 1 Sludge 1 - PBD 153 -- Mean PARM = 0004 [mgkg]

Element PBD 153

General calcparmT1= 676738E-02T2= 267609E-04T3= 18T4= 68T5= 19626E-05

n= variabelp= 5

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00024 0000 4 -157 017 00024 00002 4 3 000

12L 00038 0002 4 006 154 00038 00018 4 3 00046L 00039 0000 4 011 026 00039 00003 4 3 00026L 00039 0000 2 018 004 00039 00000 2 1 00064L 00049 0002 4 122 159 00049 00018 4 3 000

Totgem 0004 0001 mgkg 1-level 172 (173) 5 00038 () 5 4Totstd= 0001 0001 5-level 157 (153)

RESULTS Mean = 000378 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000123 --gt 3252 r = 00034Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000142 --gt 3754 R = 00040Remarks none

000 050 100 150 200

k-values

4L

12L

46L

26L

64L

Mandels k statistics(Sludge 1 - PBD 153)

00 00 00 00 00 00 00

Deviation from Mean

4L

12L

46L

26L

64L

Labo

rato

ries

Sludge 1 - PBD 153 -- Mean PARM = 0004 [mgkg]

-200 -100 000 100 200

h-values

4L

12L

46L

26L

64L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 153)

Sludge 1-PBD 153

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 154)Mandels h statistics(Sludge 1 - PBD 154)

Sample Sludge 1 NA

Element PBD 154

General calcparmT1= NAT2= NAT3=T4=T5=

n= variabelp=

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00021 0000 3 -100 021 NA - 4L - - NA

46L 00025 0000 4 115 018 NA - 46L - - NA64L 00021 0001 4 -066 179 - - 64L - - NA12L 00023 0000 4 050 085 - - 12L - - NA

Totgem 0002 0000 mgkg 1-level 149 (167) NA (4L46L64L12L) -1Totstd= 0000 0000 5-level 142 (15) 4

RESULTS Mean = NA mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NAReproducibility var S2R = NAReproducibility std SR = NA --gt NA R = NARemarks 4 Labs rejected (4L46L64L12L)

000 050 100 150 200

k-values

4L

46L

64L

12L

Mandels k statistics(Sludge 1 - PBD 154)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

4L

46L

64L

12L

Labo

rato

ries

NA

-100 000 100 200

h-values

4L

46L

64L

12L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 154)

Sludge 1-PBD 154

Unit mgkg

Mandels k statistics(Soil 3 - PBD 154)Mandels h statistics(Soil 3 - PBD 154)

Sample Soil 3 NUM

Element PBD 154

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

4L 00010 - 1 150 Fail - - 4L - - NUM46L 00001 0000 4 -053 096 Fail - - 46L - - NUM64L 00001 0000 4 -056 105 Fail NUM - 64L - - NUM12L 00002 0000 4 -040 099 Fail - - 12L - - NUM

Totgem 000037 0000 mgkg 1-level 149 (164) NUM (4L46L64L12L) -1Totstd= 000042 0000 5-level 142 (153) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (4L46L64L12L)

000 050 100 150

k-values

4L

46L

64L

12L

Mandels k statistics(Soil 3 - PBD 154)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

4L

46L

64L

12L

Labo

rato

ries

NUM

-100 000 100 200

h-values

4L

46L

64L

12L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 154)

Soil 3-PBD 154

Unit mgkg

Mandels k statistics(Compost 1 - PBD 209)Mandels h statistics(Compost 1 - PBD 209)

Sample Compost 1 NUM

Element PBD 209

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00065 0003 2 -049 032 - - 4L - - NUM

44L 00573 0021 4 150 197 Fail - - 44L - - NUM12L 00078 0001 4 -045 011 - - 12L - - NUM26L 00049 0000 2 -056 000 NUM - 26L - - NUM

Totgem 0019 0006 mgkg 1-level 149 (177) NUM (4L44L12L26L) -1Totstd= 0025 0010 5-level 142 (159) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (4L44L12L26L)

000 050 100 150 200

k-values

4L

44L

12L

26L

Mandels k statistics(Compost 1 - PBD 209)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

4L

44L

12L

26L

Labo

rato

ries

NUM

-100 000 100 200

h-values

4L

44L

12L

26L

Labo

rato

ries

Mandels h statistics(Compost 1 - PBD 209)

Compost 1-PBD 209

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 209)Mandels h statistics(Sludge 1 - PBD 209)

Sample Sludge 1 Sludge 1 - PBD 209 -- Mean PARM = 0249 [mgkg]

Element PBD 209

General calcparmT1= 394542E+00T2= 107296E+00T3= 16T4= 56T5= 19723E-02

n= variabelp= 5

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 01550 0055 4 -112 148 Fail 01550 00551 4 3 -009

46L 02050 0007 2 -053 019 02050 00071 2 1 -00412L 02137 0058 4 -042 155 02137 00576 4 3 -00426L 03149 0021 2 078 057 Fail 03149 00210 2 1 00764L 03577 0007 4 129 020 Fail 03577 00074 4 3 011

Totgem 0249 0030 mgkg 1-level 172 (185) 5 02493 () 5 4Totstd= 0084 0025 5-level 157 (162)

RESULTS Mean = 024926 mgkg

Repeatability variance S2r = 000179Repeatability std Sr = 004234 --gt 1699 r = 01186Between lab variance S2L = 000743Reproducibility var S2R = 000922Reproducibility std SR = 009604 --gt 3853 R = 02689Remarks none

000 050 100 150 200

k-values

4L

46L

12L

26L

64L

Mandels k statistics(Sludge 1 - PBD 209)

-01 -01 00 01 01 02

Deviation from Mean

4L

46L

12L

26L

64L

Labo

rato

ries

Sludge 1 - PBD 209 -- Mean PARM = 0249 [mgkg]

-200 -100 000 100 200

h-values

4L

46L

12L

26L

64L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 209)

Sludge 1-PBD 209

Unit mgkg

Mandels k statistics(Soil 3 - PBD 209)Mandels h statistics(Soil 3 - PBD 209)

Sample Soil 3 Soil 3 - PBD 209 -- Mean PARM = 0258 [mgkg]

Element PBD 209

General calcparmT1= 596398E+00T2= 191917E+00T3= 22T4= 84T5= 13249E-02

n= variabelp= 6

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean26L 01162 0021 2 -108 074 Fail 01162 00207 2 1 -0144L 01303 0031 4 -097 111 Fail 01303 00312 4 3 -013

46L 01975 0036 4 -046 128 Fail 01975 00359 4 3 -00644L 02898 0035 4 024 124 Fail 02898 00346 4 3 00312L 03895 0018 4 100 065 Fail 03895 00181 4 3 01364L 04260 0022 4 127 078 Fail 04260 00219 4 3 017

Totgem 0258 0027 mgkg 1-level 187 (177) 6 02582 () 6 5Totstd= 0132 0008 5-level 166 (154)

RESULTS Mean = 025818 mgkg

Repeatability variance S2r = 000083Repeatability std Sr = 002878 --gt 1115 r = 00806Between lab variance S2L = 001640Reproducibility var S2R = 001723Reproducibility std SR = 013127 --gt 5084 R = 03676Remarks none

000 050 100 150

k-values

26L

4L

46L

44L

12L

64L

Mandels k statistics(Soil 3 - PBD 209)

-02 -01 -01 00 01 01 02 02

Deviation from Mean

26L

4L

46L

44L

12L

64L

Labo

rato

ries

Soil 3 - PBD 209 -- Mean PARM = 0258 [mgkg]

-200 -100 000 100 200

h-values

26L

4L

46L

44L

12L

64L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 209)

Soil 3-PBD 209

Unit mgkg

Mandels k statistics(Compost 1 - Sum PBD)Mandels h statistics(Compost 1 - Sum PBD)

Sample Compost 1 Compost 1 - Sum PBD -- Mean PARM = 0009 [mgkg]

Element Sum PBD

General calcparmT1= 154064E-01T2= 169065E-03T3= 18T4= 68T5= 11354E-04

n= variabelp= 5

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00031 0002 4 -067 016 00031 00016 4 3 -0014L 00055 0005 4 -056 048 00055 00047 4 3 000

46L 00085 0003 4 -042 031 00085 00030 4 3 00026L 00123 0000 2 -024 003 00123 00002 2 1 00012L 00154 0002 4 -011 021 00154 00021 4 3 00144L 00613 0023 4 200 237 Fail - - 44L - - 005

Totgem 0018 0006 mgkg 1-level 187 (177) 5 00089 (44L) 5 4Totstd= 0022 0009 5-level 166 (154) 1

RESULTS Mean = 000893 mgkg

Repeatability variance S2r = 000001Repeatability std Sr = 000296 --gt 3308 r = 00083Between lab variance S2L = 000002Reproducibility var S2R = 000003Reproducibility std SR = 000570 --gt 6374 R = 00159Remarks 1 Lab rejected (44L)

000 050 100 150 200 250

k-values

10L

4L

46L

26L

12L

44L

Mandels k statistics(Compost 1 - Sum PBD)

00 00 00 00 00 00 01 01

Deviation from Mean

10L

4L

46L

26L

12L

44L

Labo

rato

ries

Compost 1 - Sum PBD -- Mean PARM = 0009 [mgkg]

-100 000 100 200

h-values

10L

4L

46L

26L

12L

44L

Labo

rato

ries

Mandels h statistics(Compost 1 - Sum PBD)

Compost 1-Sum PBD

Unit mgkg

Mandels k statistics(Sludge 1 - Sum PBD)Mandels h statistics(Sludge 1 - Sum PBD)

Sample Sludge 1 Sludge 1 - Sum PBD -- Mean PARM = 0256 [mgkg]

Element Sum PBD

General calcparmT1= 531806E+00T2= 162188E+00T3= 22T4= 84T5= 25223E-02

n= variabelp= 6

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00423 0025 4 -156 044 Fail 00423 00252 4 3 -02146L 01808 0118 4 -049 205 - - 46L - - -0074L 01810 0056 4 -049 097 01810 00558 4 3 -007

38L 02168 0006 4 -022 010 02168 00059 4 3 -00412L 02890 0065 4 034 113 02890 00647 4 3 00364L 03958 0008 4 116 014 Fail 03958 00079 4 3 01426L 04094 0034 2 126 059 Fail 04094 00337 2 1 015

Totgem 0245 0044 mgkg 1-level 198 (179) 6 02557 (46L) 6 5Totstd= 0130 0039 5-level 171 (155) 1

RESULTS Mean = 025570 mgkg

Repeatability variance S2r = 000158Repeatability std Sr = 003970 --gt 1553 r = 01112Between lab variance S2L = 001807Reproducibility var S2R = 001964Reproducibility std SR = 014015 --gt 5481 R = 03924Remarks 1 Lab rejected (46L)

000 050 100 150 200 250

k-values

10L

46L

4L

38L

12L

64L

26L

Mandels k statistics(Sludge 1 - Sum PBD)

-03 -02 -02 -01 -01 00 01 01 02 02

Deviation from Mean

10L

46L

4L

38L

12L

64L

26L

Labo

rato

ries

Sludge 1 - Sum PBD -- Mean PARM = 0256 [mgkg]

-200 -100 000 100 200

h-values

10L

46L

4L

38L

12L

64L

26L

Labo

rato

ries

Mandels h statistics(Sludge 1 - Sum PBD)

Sludge 1-Sum PBD

Unit mgkg

Mandels k statistics(Soil 3 - Sum PBD)Mandels h statistics(Soil 3 - Sum PBD)

Sample Soil 3 Soil 3 - Sum PBD -- Mean PARM = 0227 [mgkg]

Element Sum PBD

General calcparmT1= 610980E+00T2= 200876E+00T3= 26T4= 100T5= 13106E-02

n= variabelp= 7

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00028 0001 4 -037 000 Fail 00028 00005 4 3 -02226L 01179 0021 2 -036 003 Fail 01179 00208 2 1 -0114L 01305 0031 4 -036 004 Fail 01305 00308 4 3 -010

46L 02065 0035 4 -036 005 Fail 02065 00350 4 3 -00244L 02923 0037 4 -035 005 Fail 02923 00365 4 3 00712L 04051 0015 4 -034 002 Fail 04051 00149 4 3 01864L 04314 0022 4 -033 003 Fail 04314 00223 4 3 0203L 305500 2051 2 247 283 Fail - - 3L - - 3032

Totgem 4017 0276 mgkg 1-level 206 (181) 7 02266 (3L) 7 6Totstd= 10722 0717 5-level 175 (156) 1

RESULTS Mean = 022663 mgkg

Repeatability variance S2r = 000069Repeatability std Sr = 002626 --gt 1159 r = 00735Between lab variance S2L = 002568Reproducibility var S2R = 002637Reproducibility std SR = 016238 --gt 7165 R = 04547Remarks 1 Lab rejected (3L)

000 050 100 150 200 250 300

k-values

10L

26L

4L

46L

44L

12L

64L

3L

Mandels k statistics(Soil 3 - Sum PBD)

-50 00 50 100 150 200 250 300 350

Deviation from Mean

10L

26L

4L

46L

44L

12L

64L

3L

Labo

rato

ries

Soil 3 - Sum PBD -- Mean PARM = 0227 [mgkg]

-100 000 100 200 300

h-values

10L

26L

4L

46L

44L

12L

64L

3L

Labo

rato

ries

Mandels h statistics(Soil 3 - Sum PBD)

Soil 3-Sum PBD

19

Annex 4

Raw data submitted

Sample Compost1 Sample Compost 1 Sample Compost 1Element PBD 99 Element PBD 100 Element PBD 153

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]4L 00021 10L 00008 44L 000504L 00024 10L 00008 44L 000604L 00014 10L 00007 44L 000504L 00020 10L 00011 46L 00004

10L 00029 46L 00007 46L 0001210L 00027 46L 00012 46L 0000410L 00032 46L 00009 46L 0000946L 00025 46L 00007 12L 0000446L 00052 12L 00008 12L 0000846L 00029 12L 00012 12L 0000446L 00026 12L 00008 12L 0000712L 00026 12L 00014 26L 0000512L 00043 26L 00007 26L 0000512L 00026 26L 0000612L 0004726L 0002626L 00024

Sample Compost 1 Sample Compost 1 Sample Compost 1Element PBD 154 Element PBD 183 Element PBD 196

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]4L 00010 46L 00002 46L 00011

46L 00003 46L 00024 46L 0000846L 00007 46L 00021 12L 0000246L 00003 46L 00003 12L 0000346L 00004 12L 00003 12L 0000112L 00003 12L 00011 12L 0000212L 00005 12L 0000312L 00031 12L 0000312L 00006

Sample Compost 1 Sample Compost 1 Sample Compost 1Element PBD 197 Element PBD 203 Element PBD 209

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00002 46L 00010 4L 0004146L 00023 12L 00002 4L 0008946L 00022 12L 00003 44L 0041012L 00004 12L 00002 44L 0084012L 00006 12L 00002 44L 0064012L 00003 44L 0040012L 00004 12L 00079

12L 0007312L 0006512L 0009326L 0004926L 00049

Sample Compost 1Element PBD 47

LAB PARM [mgkg]26L 0003826L 00039

Element PBD 99 Element PBD 47 Element PBD 209LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]

4L 00170 10L 00210 4L 010004L 00200 10L 00220 4L 018004L 00170 10L 00210 4L 012004L 00190 46L 00300 4L 0220010L 00280 46L 00280 46L 0210010L 00300 46L 00250 46L 0200010L 00290 46L 00260 64L 0351846L 00340 64L 00059 64L 0363846L 00330 64L 00057 64L 0364546L 00300 64L 00062 64L 0350846L 00310 64L 00060 12L 0220964L 00194 12L 00191 12L 0177164L 00154 12L 00187 12L 0292264L 00185 12L 00190 12L 0164664L 00159 12L 00186 26L 0329712L 00242 26L 00666 26L 0300012L 00223 26L 0033212L 0022112L 0022226L 0024626L 00400

Element PBD 203 Element PBD 197 Element PBD 196LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00022 46L 00027 46L 0002446L 00014 46L 00024 46L 0002264L 00036 12L 00161 64L 0005864L 00058 12L 00060 64L 0006512L 00063 12L 00061 12L 0004812L 00034 12L 00036 12L 0002512L 00038 12L 0003212L 00027 12L 00022

Element PBD 183 Element PBD 154 Element PBD 153LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00049 4L 00020 4L 0002246L 00035 4L 00022 4L 0002446L 00036 4L 00020 4L 0002246L 00034 46L 00025 4L 0002664L 00027 46L 00025 46L 0004064L 00023 46L 00025 46L 0004264L 00024 46L 00023 46L 0003564L 00020 64L 00034 46L 0003812L 00230 64L 00023 64L 0007412L 00032 64L 00017 64L 0004712L 00031 64L 00011 64L 0004612L 00030 12L 00030 64L 0003026L 00007 12L 00021 12L 0006526L 00008 12L 00021 12L 00029

12L 00021 12L 0003226L 00015 12L 0002926L 00019 26L 00039

26L 00040

Element PBD 100LAB PARM [mgkg]

4L 000384L 000414L 000374L 00038

38L 0219038L 0220038L 0208038L 0220010L 0004410L 0005010L 0004310L 0004646L 0005746L 0005946L 0005346L 0005312L 0004312L 0004512L 0004312L 0004326L 0006226L 00057

Sample Soil 3 Sample Soil 3 Sample Soil 3Element PBD 99 Element PBD 47 Element PBD 100

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]10L 00016 10L 00011 10L 0000310L 00019 10L 00010 10L 0000410L 00013 10L 00012 10L 0000410L 00019 46L 00007 10L 0000246L 00025 46L 00022 46L 0000246L 00025 46L 00005 46L 0000646L 00008 46L 00007 46L 0000246L 00011 12L 00010 46L 0000264L 00005 12L 00017 3L 29100064L 00005 12L 00010 3L 32000064L 00006 12L 00009 26L 0000564L 00007 26L 00007 26L 0000512L 00012 26L 0000712L 0001312L 0001312L 0001226L 0000526L 00006

Sample Soil 3 Sample Soil 3 Sample Soil 3Element PBD 153 Element PBD 154 Element PBD 196

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]44L 00050 4L 00010 46L 0000744L 00050 46L 00001 46L 0001146L 00002 46L 00002 46L 0000846L 00003 46L 00001 46L 0001146L 00002 46L 00002 64L 0002646L 00002 64L 00001 64L 0002664L 00001 64L 00001 64L 0002964L 00001 64L 00001 64L 0003464L 00001 64L 00002 12L 0004564L 00002 12L 00003 12L 00032

12L 00002 12L 0002212L 00002 12L 0002112L 00002

Sample Soil 3 Sample Soil 3 Sample Soil 3Element PBD 197 Element PBD 203 Element PBD 209

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00006 46L 00011 4L 0091046L 00013 46L 00017 4L 0150046L 00011 46L 00015 4L 0120046L 00013 46L 00018 4L 0160012L 00090 64L 00013 44L 0337012L 00056 64L 00014 44L 0281012L 00033 64L 00016 44L 0287012L 00032 64L 00015 44L 02540

12L 00055 46L 0230012L 00041 46L 0220012L 00027 46L 0150012L 00026 46L 01900

64L 0438164L 0401664L 0414464L 0449812L 0367112L 0397812L 0409112L 03838

Sample Soil 3 26L 0102Element PBD 183 26L 0131

LAB PARM [mgkg]46L 0000746L 0000846L 0005846L 0000764L 0000264L 0000364L 0000364L 0000312L 0001512L 0001112L 0000712L 00007

European Commission EUR 23003 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on polybrominated diphenylethers Author(s) E Sobiecka H van der Sloot D Barcelo B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 68 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07403-5 Abstract Project HORIZONTAL is interdisciplinary aiming at a harmonisation and horizontal standardisation of test procedures in particular for sludge soils and biowastes In the context of this standardization project a series of draft technical specification were designed upon an extensive desk study fine-tuned after expert consultations and finally validated in international intercomparisons exercise This report summarises the work performed within the validation study of the draft standard for the determination of polybrominated diphenylethers (PBDE) in soils sludge and treated bio-waste using gas-chromatography method with mass selective detection (GC-MS) It further explains the underlying statistical concept for the calculation of reproducibility and repeatability from intercomparisons data In addition all single values results of the statistical evaluation as well as background information on the validation materials used are described and explained

The mission of the JRC is to provide customer-driven scientific and technical support for the conception development implementation and monitoring of EU policies As a service of the European Commission the JRC functions as a reference centre of science and technology for the Union Close to the policy-making process it serves the common interest of the Member States while being independent of special interests whether private or national

LB

-NA

-23003-EN

-C

8

enter their data in a structured form For authentication purposes a signed printout had to be submitted by mail The online data submission included a detailed questionnaire for additional information on the measurements

113 Statistical analysis Statistical analysis of data followed the requirements of ISO 5725-21994 and ISO 5725-51998 Appropriate tests for the homogeneity of variance detection of outliers and normal distribution were applied Statistical evaluation was done using an Excel Macro developed tested and successfully applied in other occasion by ECN Evaluation was executed jointly by JRC and ECN

12 Validation exercise for PBDE

121 Compounds to be measured The following compound were selected for the validation exercise Tetra-BDE-47 Penta-BDE-100 Penta-BDE-99 Hexa-BDE-154 Hexa-BDE-153 Hepta-BDE-183 Octa-BDE-196 Octa-BDE-197 Octa-BDE-203 Deca-BDE-209

122 Samples dispatched for the validation of PBDE After a preliminary rough screening the following materials were used for the validation round of PBDE

bull Compost 1 A pollutant loaded compost material from Vienna bull Sewage Sludge 1 A mixed sewage sludge from Essen bull Soil 3 A sludge amended soil from Barcelona

A more detailed description of background concentrations can be found in Annex 2 to this report The samples were dispatched simultaneously to all participants using a private courier service

123 Draft standards to be followed The draft standards to be followed could be downloaded following this link which is situated on the website of the Project HORIZONTAL httpwwwecnnldocssocietyhorizontalBFR_Standard_for_validationpdf

124 Analytical programm Of each of the three materials 2 bottles had to be analysed and each bottle had to analysed independently twice As mentioned above analyses were to be done under repeatability conditions Results were to be reported referring to DRY MATTER content The choice how to apply dm correction was free for each participant

9

125 Timing and Submission of data Dispatch of samples was done on the 18th of October 2006 For users of the Online data submission system (MILC) User Registration was possible from 14th of November 2006 with opening of the MILC Data Submission on 1st of December 2006 The deadline for submission of results has been set for PBDE to the 12th of January 2007 but was extended to the end of the same months After that no further submission was possible Alternatively the participants were allowed to submit data electronically as Excel sheet using simply Email All data were treated in a confidential way Any presentation hereafter will refer only to numerical data and it will not be possible to identify the originating laboratory Lab Codes displayed are NOT related to the order of laboratories hereafter In addition to the information provide an Helpdesk was implemented in order to give quick and individual response to the participants during and immediately after the validation study In case of doubt and suspected transcription errors further enquires were conducted by JRC

10

126 Participants The following table lists the participating organisations and entities in the validation exercise for the horizontal PBDE standard

bull Austria o Umweltbundesamt

bull Czech Republic o Povodi Labe statni podnik - OVHL Laboratory

bull France o CIRSEE o CTC Environnement o INERIS

bull Germany o Federal Environmental Agency Section III 34 Laboratory Methods for

the Surveillance of Waste and Wastewater (UBA) bull Italy

o European Commission DG JRC IES bull Spain

o Consejo Superior de Investigaciones Cientificas (CSIC)

bull Sweden o ALCONTROL AB

11

13 Summary results and derived performance characteristics The result of the various statistical evaluation including outlier tests calculation of repeatability and reproducibility standard deviation for the congeners of interest can be found in Annex 3 of this report In addition all data submitted by the participants as well as those considered for the calculation of the performance characteristics are listed in Annex 3 to this report Based on these calculations the following results were obtained in the validation round upon statistical evaluation according to ISO 5725-2 The average values the repeatability standard deviation (sr) and the reproducibility standard deviation (sR) were obtained (Table1) The repeatability is determined as an interval around a measurement result (ie repeatability limit) This interval corresponds to the maximum difference that can be expected (with a 95 statistical confidence) between one test result and another both test results being obtained under the following conditions The tests are performed in accordance with all the requirements of the present standard by the same laboratory using its own facilities and testing laboratory samples obtained from the same primary field sample and prepared under identical procedures The repeatability limit was calculated using the relationship r test = f radic2 s rtest with the critical range factor f = 2 The reproducibility like repeatability is also determined as an interval around a measurement result (ie reproducibility limit) This interval corresponds to the maximum difference that can be expected (with a 95 statistical confidence) between one test result and another test result obtained by another laboratory both test results being obtained under the following conditions The tests are performed in accordance with all the requirements of the present standard by two different laboratories using their own facilities and testing laboratory samples obtained from the same primary field sample and prepared under identical procedures The reproducibility limit was calculated using the relationship R = f radic2 sR with the critical range factor f = 2

12

Table 1 - Results of the interlaboratory comparison studies of the determination of selected polybrominated diphenyl ethers (PBDE) by gaschromatography with mass spectrometric detection (GC-MS) in soil sludge and treated biowaste All concentrations are expressed in mgkg dm

Matrix Parameter Mean sr sR r R p Outliers Used No of data

No of data reported below

detection

Total no of data

Sludge 1 PBD 47 00181 461 4 15 5 20 Compost 1 00039 94 3 12 0 12 Soil 3 00010 50 50 00014 00014 4 0 13 10 23 Sludge 1 PBD 99 00239 64 28 00043 00186 5 1 19 0 23 Compost 1 00029 31 35 00025 00028 5 0 17 4 21 Soil 3 00013 499 4 16 8 24 Sludge 1 PBD 100 00049 51 17 00007 00024 5 1 18 2 24 Compost 1 00009 25 29 00006 00007 4 0 14 7 21 Soil 3 61103 211 3 10 15 25 Sludge 1 PBD 153 00038 33 38 00034 0004 5 0 18 0 18 Compost 1 00019 116 3 11 3 14 Soil 3 00011 177 2 10 10 20 Sludge 1 PBD 154 00023 234 4 15 2 17 Compost 1 00008 1118 3 9 5 14

13

Matrix Parameter Mean sr sR r R p Outliers Used No of data

No of data reported below

detection

Total no of data

Soil 3 00002 1049 4 13 6 19 Sludge 1 PBD 183 00048 1217 3 12 2 14 Compost 1 00009 1048 2 8 5 13 Soil 3 00011 1395 3 12 6 18 Sludge 1 PBD 196 00037 470 2 8 7 15 Compost 1 00004 950 2 6 4 10 Soil 3 00023 519 3 12 2 14 Sludge 1 PBD 197 00062 834 2 6 8 14 Compost 1 00009 1001 2 7 7 14 Soil 3 00032 904 2 8 6 14 Sludge 1 PBD 203 00037 461 2 8 4 12 Compost 1 00004 978 2 5 3 8 Soil 3 00022 598 3 12 0 12 Sludge 1 PBD 209 02493 170 39 01186 02689 5 0 16 2 18 Compost 1 00273 104 3 10 5 15 Soil 3 02582 1115 51 00806 03676 6 0 22 0 22

14

Matrix Parameter Mean sr sR r R p Outliers Used No of data

No of data reported below

detection

Total no of data

Sludge 1 Sum PBD 0256 155 548 0111 0392 6 1 22 Compost 1 0009 331 637 0008 0016 5 1 18 Soil 3 0227 116 717 0074 0455 7 1 26 Abbreviations sr Repeatability standard deviation SR Reproducibility standard deviation r Repeatability limit (comparing two measurements) R Reproducibility limit (comparing two measurements) p Number of labs determination not possible

15

14 Annexes Annex 1 Model questionnaire to be filled by the participating laboratories Annex 3 Report on the validation materials used Annex 2 Statistical calculations Annex 3 Data submitted

16

Annex 1

Model questionnaire to be filled by the participating laboratories

Model questionnaire to be filled by the participating laboratories Name of laboratory Contact person Contact details email Phone Fax Mail address of lab Dispatch address of lab for shipment of samples (no PO boxes) Title of measurement method (copy attached) Our laboratory is willing to participate in the precision experiment for this draft standard method

Yes No As participant we understand that

bull All essential apparatus chemicals and other requirements specified in the method must be available in our laboratory when the programme begins

bull Specified timing requirements such as starting and finishing date of the programme must be rigidly met

bull The method must be strictly adhered to bull Samples must be handled in accordance with instructions bull A qualified operator must perform the measurements

Having studied the method and having made a fair appraisal of our capabilities and facilities we feel that we will be adequately prepared for cooperative testing of this method Comments helliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphellip Signature Date

17

Annex 2

Report on the validation materials used

VI

Abstract This report gives an overview on the available analytical information on the following raw materials to be used for the production of validation materials of the so-called Project HORIZONTAL

bull Four sludge materials from Duumlsseldorf Germany

bull An agricultural soil material from Reading United Kingdom

bull A compost material from Vienna Austria

bull A compost material from Korschenbroich Germany

bull A sludge-amended agricultural soil from Pavia Province Italy

bull A sludge-amended soil from Barcelona Spain

bull A sludge-amended soil from Essen Germany

bull A long-term sludge exposed soil from Hohenheim Germany

VII

List of Abbreviations Throughout this report the following abbreviations are used

AOX absorbable organic halogens

Corg organic carbon content

Ctotal total carbon content

CAT cation exchangeable

CDD chlorinated dibenzodioxin

CDF chlorinated dibenzofuran

DEHP di(2-ethylhexyl)phthalate

DM dry matter

EPA Environment Protection Agency

EU European Union

FM fresh matter

Hp hepta

Hx hexa

IES Institute for Environment and Sustainability

IRMM Institute for Reference Materials and Measurements

JRC Joint Research Centre

LAS linear alkylsulfonates

LoD limit of detection

LUA Landesumweltamt

Ntotal total nitrogen content

NH4-N Ammonium nitrogen

NO3-N Nitrate nitrogen

NP nonylphenol

NRW North Rhine Westphalia

O octa

P poly

PAH polycyclic aromatic hydrocarbon

PCB polychlorinated biphenyl

Pe penta

T tetra

TEQ toxicity equivalent

UBA Umweltbundesamt

WHO World Health Organization

WWTP waste water treatment plant

6

1 Introduction This report gives an overview on the available analytical information on the following raw materials to be used for the production of validation materials of the so-called Project HORIZONTAL

bull Four sludge materials from Duumlsseldorf Germany

bull An agricultural soil material from Reading United Kingdom

bull A compost material from Vienna Austria

bull A compost material from Korschenbroich Germany

bull A sludge-amended agricultural soil from Pavia Province Italy

bull A sludge-amended soil from Barcelona Spain

bull A sludge-amended soil from Essen Germany

bull A long-term sludge exposed soil from Hohenheim Germany

The following analytical information was gathered partly before and during the sampling of the raw materials to be used for the production of the HORIZONTAL validation materials The material were sampled by IES and shipped to IRMM in the course of the year 2005 The information gathered was then completed by various analytical screenings for PAHs and PCBs done by the Institute for Reference Materials and Measurements Geel Belgium for phthalates done by UBA Berlin Germany for PBDE done by IIQAB-CSIC Barcelona Spain for trace elements and some selected major and minor elements by the Institute for Environment and Sustainability Ispra Italy

The work compiled hereafter is based on the numerous additional efforts of the scientists working at various members of the consortium Project HORIZONTAL-Org and contributing organisations

This work is gratefully acknowledged

2 Overview on property values

21 Sludge materials from Duumlsseldorf Germany

The various sewage sludge materials originate from various installations in the North Rhine Westphalia and were produced and sampled by staff from the Landesumweltamt (LUA) NRW under the responsibility from Dr K Furtmann

In total four sludge materials (Sludge A and D from a major municipal WWTP Sludge B from a municipal WWTP with industrial input and Sludge C from a municipal WWTP with high PCB-Content) were obtained and will be blended to two final materials Before sampling the following analytical data for a typical sample were received

7

Table 1 ndash Analytical data obtained on an average sludge sample in LUA NRW (with courtesy of K Furtmann LUA Duumlsseldorf)

Parameter Concentration PCB 120 ugkg DEHP 110 mgkg PAH 5 mgkg (EPA) PCDDF 15 ng TEkg PBDE 400 ugkg NP 40 mgkg LAS 3 gkg AOX 300 mgkg

Subsequent screening led to the information displayed hereafter It should be stressed that the data were obtained as SCREENING information on the UNTREATED or partially treated raw materials Therefore the final target values which are relevant for the validation intercomparison can be different

Table 2 ndash Analytical data obtained on a first screening on the sludge samples from LUA NRW

Sewage sludge A

Dusseldorf

sewage sludge D

Dusseldorf PCB (ngg) 28 62 35 52 101 65 101 31 38 118 49 40 153 30 33 105 24 11 138 46 38 156 lt1 lt1 180 34 23 170 23 19 PAH (ngg) Naphtalene 34 381 Acenaphtylene 15 43 Acenaphthene 81 108 Fluorene 94 1167 Phenantrene 3440 Anthracene 22 344 Flouranthene 316 4817 Pyrene 235 3011 Benz(a)anthracene 473 791 Chrysene 691 1078 Benz(b)fluoranthene 538 1688 Benz(k)fluoranthene 228 635 Benz(a)pyrene 383 1114 Indeno(123-cd)pyrene 92 229 Dibenzo(ah)anthracene 71 70 Benzo(ghi)perylene 80 185

8

Table 3 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Sludge D (1) 0135 41474 385 Sludge B (2) 0538 0034 30634 547 Sludge A (3) 0184 0037 31399 146 Sludge C (4) 0354 1528 6678 229

Table 4 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Sludge 2

(B)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

554

959

694

591

772

509

nq

nq

970

2216

2379

Table 5 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena IES Ispra Spain) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Sludge 1 (D) 265 290 533 359 1231 338 784 438 lt 005 232 786 Sludge 2 (B) 119 311 626 202 278 299 722 251 lt 005 118 625 Sludge 3 (A) 168 360 621 332 847 416 119 451 lt 005 116 1237 Sludge 4 (C) 563 198 116 273 726 511 473 618 lt 005 444 2015

Table 6 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Sludge 1 (D) 2154 58 844 099 103 101 4367 lt15 50448 Sludge 2 (B) 1067 366 692 046 1491 077 5217 lt15 57633 Sludge 3 (A) 731 663 684 035 1287 068 3733 lt15 60369 Sludge 4 (C) 4379 965 527 163 522 107 5628 lt15 23945

Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM)Sludge 1 (D) 03 2403 101 1002 350 15 1944 132Sludge 2 (B) 031 315 97 879 172 12 514 180Sludge 3 (A) 031 1281 153 1567 265 16 1440 168Sludge 4 (C) 055 231 628 2625 371 81 1101 244

9

22 Agricultural soil material from Reading United Kingdom

The material was proposed by the University of Reading (S Nortcliff) and was sampled from a site called ldquoFrogmore Farmrdquo which was featured in the ldquoMetalsrdquo Report for HORIZONTAL This site is close to Reading with soils developed on flintyloamy periglacial materials over Chalk has a long and well documented history of sludge application The focus of the work of Nortcliff et al undertook at this site and the monitoring and control at the site (by Thames Water and the subsequent subsidiary bodies dealing with sludge application to soil) was on metals (and metal loads) with no analysis or indeed any form of investigation in to organics in the broadest sense

The analytical information produced in the context of the screening of the raw material is displayed below

Table 7 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 3

(Reading) 0032 0119 669

Table 8 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 3 (Reading) 015 706 279 138 152 901 267 300 lt 005 258 931

Table 9 ndash Analytical data obtained on a first screening on the sludge-amended soil from Reading (courtesy of IRMM)

Parameter Concentration

PCB ngg 28 lt1 52 lt1 101 lt1 118 lt1 153 lt1 105 lt1 138 lt1 156 lt1 180 lt1 170 lt1 PAH ngg Naphtalene lt10 Acenaphtylene 21 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene lt10 Flouranthene 818 Pyrene 776 Benz(a)anthracene 565

10

Parameter Concentration

Chrysene 608 Benz(b)fluoranthene 824 Benz(k)fluoranthene 329 Benz(a)pyrene 799 Indeno(123-cd)pyrene

779

Dibenzo(ah)anthracene 118 Benzo(ghi)perylene 394

Table 10 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 3

(Reading)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

103

003

nq

nq

nq

nd

nd

272

273

Table 11 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 3 (Reading) 015 706 279 138 152 901 267 300 lt 005 258 931

Table 12 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 3 (Reading) 7936 477 112 096 194 017 4107 443 2102 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 3 (Reading) 042 13 45 69 69 69 216 92

Table 13 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 3 (Reading) 012

11

23 Compost from Vienna Austria

The fresh compost material was obtained from the Austrian Federal Environment Agency (UBA Vienna) which had used a sub-batch of the raw material for national intercomparson The remainder of the material was stored at 4degC until shipment to IRMM for further processing The following analytical information was provided by UBA Austria and completed with various screenings

Table 14 ndash Analytical data on compost material received from UBA Austria Inorganic and sum parameters

Parameter Unit Sample fraction used Observed mean B CAT mgl FM Fresh sample lt10mm 61 K CAT mgl FM Fresh sample lt10mm 2624 Mg CAT mgl FM Fresh sample lt10mm 242 P CAT mgl FM Fresh sample lt10mm 49 B CAT DM Fresh sample lt10mm 00017 K CAT DM Fresh sample lt10mm 072 Mg CAT DM Fresh sample lt10mm 007 P CAT DM Fresh sample lt10mm 001 NO3-N mgkg FM Fresh sample lt10mm 35 NH4-N mgkg FM Fresh sample lt10mm 230 Ctotal DM lt45degdry milled 29 Corg DM lt45degdry milled 27 Ntotal DM lt45degdry milled 17 P mgkg DM lt45degdry milled 2596 K mgkg DM lt45degdry milled 11019 K DM lt45degdry milled 110 B mgkg DM lt45degdry milled 60 Cd mgkg DM lt45degdry milled 046 Cr mgkg DM lt45degdry milled 25 Cu mgkg DM lt45degdry milled 46 Hg mgkg DM lt45degdry milled 020 Ni mgkg DM lt45degdry milled 18 Pb mgkg DM lt45degdry milled 45 Zn mgkg DM lt45degdry milled 198 Ca mgkg DM lt45degdry milled 68776 Ca DM lt45degdry milled 69 Mo mgkg DM lt45degdry milled 08 S mgkg DM lt45degdry milled 2137 Fe mgkg DM lt45degdry milled 9959 Mn mgkg DM lt45degdry milled 418 Na mgkg DM lt45degdry milled 742 Co mgkg DM lt45degdry milled 41 AOX mgkg DM lt30deg dry milled 62

Table 15 ndash Analytical data on compost material received from UBA Austria Polycyclic aromatic hydrocarbons

PAH Unit Result Naphthaline microgkg DM 93 Acenaphthylene microgkg DM 86 Acenaphthene microgkg DM 5 Fluorene microgkg DM 80 Phenanthrene microgkg DM 89 Anthracene microgkg DM 27 Fluoranthene microgkg DM 487 Pyrene microgkg DM 380

12

PAH Unit Result Benzo(a)anthracene microgkg DM 278 Chrysene microgkg DM 317 Benzo(b)fluoranthene microgkg DM 365 Benzo(k)fluoranthene microgkg DM 193 Benz(a)pyrene microgkg DM 320 Indeno(123-cd)pyrene microgkg DM 233 Dibenz(ah)anthracene microgkg DM 67 Benzo(ghi)perylene microgkg DM 225 Sum EPA microgkg DM 3013 Sum EPA mgkg DM 30

Table 16 ndash Analytical data on compost material received from UBA Austria Sum PCDDs and PCBs

Parameter

Dioxine TEQ (ITEF) ngkg DM 73 TEQ (WHO) ngkg DM 35 PCB Σ Ballschmiter mgkg DM 005

Table 17 ndash Analytical data on compost material obtained by screening in IRMM

Parameter Result in ngg

PCB 28 2 52 2 101 4 118 3 153 10 105 1 138 8 156 1 180 5 170 lt1 PAH Naphtalene lt10 Acenaphtylene lt10 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene 26 Fluoranthene 611 Pyrene 510 Benz(a)anthracene 888 Chrysene 957 Benz(b)fluoranthene 1531 Benz(k)fluoranthene 547 Benz(a)pyrene 1101 Indeno(123-cd)pyrene 416 Dibenzo(ah)anthracene 81 Benzo(ghi)perylene 295

13

Table 18 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Compost 1

(Vienna)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

402

019

259

nq

023

004

nq

nq

144

174

259

Table 19 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Compost 1

(Vienna) 0058 1426 557

Table 20 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Compost 1 (Vienna) 039 736 319 410 365 127 495 004 079 013 208

Table 21 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Compost 1 (Vienna) 2063 431 617 426 199 249 1602 lt15 10521

Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Compost 1 (Vienna) 035 3496 81 375 79 55 653 60

Table 22 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Compost 1 (Vienna) 017

14

24 Agricultural soil sludge amended soil from Pavia Italy

This sludge-amended soil material was obtained during a monitoring campaign which aimed at a generic description of the over-all soil quality in Pavia Province Italy The material which was collected from the upper horizon originates from a small farm called ldquoCascina Novellordquo During the characterisation of the site the following analytical information was obtained on a pooled sample of a sub-area of the farm of 20 X 20 m2

Table 23 ndash Analytical data on Pavia soil

Parameter Result Al 713 Wgt As 224 mgkg Cd 079 mgkg Cr 59 mgkg Cu 308 mgkg Hg 008 mgkg Ni 344 mgkg Pb 246 mgkg Zn 95 mgkg C 091 Wgt 2378-TCDD 0047 pgg 12378-PeCDD 015 pgg 123478-HxCDD 019 pgg 123678-HxCDD 15 pgg 123789-HxCDD 074 pgg 1234678-HpCDD 26 pgg OCDD 382 pgg 2378-TCDF 068 pgg 12378-PeCDF 053 pgg 23478-PeCDF 071 pgg 123478-HxDF 100 pgg 123678-HxDF 066 pgg 234678-HxDF 16 pgg 123789-HxDF 027 pgg 1234678-HpDF 12 pgg 1234789-HpDF 068 pgg OCDF 33 pgg I-TEQ 20 pgg WHO-TEQ 17 pgg

In addition the screening performed at IRMM did not reveal significant quantities of PCBs and PAHs which were all below the LoDs (1 ngg for PCBs and 10 ngg for PAHs respectively)

Table 24 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 5 (Pavia) 0005 0011 154

15

Table 25 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 5

(Pavia)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

039

nq

nq

008

nq

nd

nd

670

671

Table 26 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 5 (Pavia) 033 184 573 225 426 305 206 200 lt 005 381 878

Table 27 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 5 (Pavia) 6939 129 145 224 425 116 6118 255 1789 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 5 (Pavia) 184 62 38 108 55 66 597 110

Table 28 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 5 (Pavia) 006

16

25 Sludge-amended-soil from Barcelona Spain

The sludge-amended soil material from Barcelona sampled upon indication from the Barcelorsquo- Group in Barcelona

Table 29 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 2 (Lleida T) 0015 0183 1138

Table 30 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 2

(Lleida T)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

159

045

nq

048

160

nq

nq

1000

1004

Table 31 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 2 (Lleida T) 059 141 327 536 405 186 184 224 lt 005 318 111

Table 32 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 2 (Lleida T) 4443 1067 1429 253 344 204 4116 780 3396 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 2 (Lleida T) 064 65 26 125 59 17 547 65

Table 33 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 2 (Lleida T) 010

17

26 Sludge amended soil from Essen Germany

The German sludge-amended soil from Essen which was provided as the three sludge materials by LUA NRW did not feature significant concentrations of the PCB congeners 28 52 101 118 153 105 138 156 180 170 but had detectable amounts of some PAHs

Table 34 ndash Analytical screening data on the German sludge-amended soil

Parameter Concentration(ngg)

Naphtalene lt10 Acenaphtylene lt10 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene lt10 Fluoranthene 28 Pyrene 20 Benz(a)anthracene 24 Chrysene 47 Benz(b)fluoranthene 76 Benz(k)fluoranthene 20 Benz(a)pyrene 35 Indeno(123-cd)pyrene 35 Dibenzo(ah)anthracene 10 Benzo(ghi)perylene 26

Table 35 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 4 (Essen) 0011 0302 055

Table 36 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 4

(Essen)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

nq

nq

nq

nq

nq

nq

128

191

203

18

Table 37 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 4 (Essen) 052 545 261 805 320 403 273 273 lt 005 295 781

Table 38 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 4 (Essen) 7947 442 085 06 086 007 2163 189 2019 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 4 (Essen) 045 19 42 87 683 60 462 61

Table 39 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 4 (Essen) 004

27 Long-term sludge exposed soil from Hohenheim-Stuttgart Germany

Similarly an additional sludge exposed soil was sampled at the University of Hohenheim Stuttgart were a test soil was long-term exposed to elevated concentrations of sewage sludge

Table 40 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 1 (Stuttgart) 0045 0263 1765

Table 41 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 1

(Stuttgart)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

230

006

004

004

nq

nd

nd

498

500

19

Table 42 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 1 (Stuttgart) 069 127 361 262 504 183 252 262 lt 005 266 142

Table 43 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 1 (Stuttgart) 7194 1006 133 186 366 088 7874 275 3571 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 1 (Stuttgart) 123 50 47 212 85 69 991 129

Table 44 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 1 (Stuttgart) 177

18

Annex 3

Statistical calculations

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 47)Mandels h statistics(Sludge 1 - PBD 47)

Sample Sludge 1 NUM

Element PBD 47

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00213 0001 3 -021 005 - - 10L - - NUM46L 00273 0002 4 016 021 - - 46L - - NUM64L 00059 0000 4 -116 002 NUM - 64L - - NUM12L 00188 0000 4 -036 002 - - 12L - - NUM26L 00499 0024 2 157 223 Fail - - 26L - - NUM

Totgem 0025 0005 mgkg 1-level 172 (185) NUM (10L46L64L12L26L) -1Totstd= 0016 0010 5-level 157 (162) 5

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 5 Labs rejected (10L46L64L12L26L)

000 050 100 150 200 250

k-values

10L

46L

64L

12L

26L

Mandels k statistics(Sludge 1 - PBD 47)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

10L

46L

64L

12L

26L

Labo

rato

ries

NUM

-200 -100 000 100 200

h-values

10L

46L

64L

12L

26L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 47)

Sludge 1-PBD 47

Unit mgkg

Mandels k statistics(Soil 3 - PBD 47)Mandels h statistics(Soil 3 - PBD 47)

Sample Soil 3 Soil 3 - PBD 47 -- Mean PARM = 0001 [mgkg]

Element PBD 47

General calcparmT1= 134814E-02T2= 142830E-05T3= 13T4= 45T5= 22767E-06

n= variabelp= 4

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean26L 00007 0000 2 -143 001 00007 00000 2 1 00046L 00010 0001 4 010 181 00010 00008 4 3 00010L 00011 0000 3 049 023 00011 00001 3 2 00012L 00012 0000 4 084 081 00012 00004 4 3 000

Totgem 0001 0000 mgkg 1-level 149 (177) 4 00010 () 4 3Totstd= 0000 0000 5-level 142 (159)

RESULTS Mean = 000100 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000050 --gt 5031 r = 00014Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000050 --gt 5031 R = 00014Remarks none

000 050 100 150 200

k-values

26L

46L

10L

12L

Mandels k statistics(Soil 3 - PBD 47)

00 00 00 00 00 00 00 00 00 00 00

Deviation from Mean

26L

46L

10L

12L

Labo

rato

ries

Soil 3 - PBD 47 -- Mean PARM = 0001 [mgkg]

-200 -100 000 100

h-values

26L

46L

10L

12L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 47)

Soil 3-PBD 47

Unit mgkg

Mandels k statistics(Compost 1 - PBD 99)Mandels h statistics(Compost 1 - PBD 99)

Sample Compost 1 Compost 1 - PBD 99 -- Mean PARM = 0003 [mgkg]

Element PBD 99

General calcparmT1= 492124E-02T2= 148747E-04T3= 17T4= 61T5= 93196E-06

n= variabelp= 5

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00020 0000 4 -137 053 00020 00004 4 3 000

26L 00025 0000 2 -058 024 00025 00002 2 1 00010L 00029 0000 3 012 032 00029 00003 3 2 00046L 00033 0001 4 069 161 00033 00013 4 3 00012L 00036 0001 4 114 140 00036 00011 4 3 000

Totgem 0003 0001 mgkg 1-level 172 (185) 5 00029 () 5 4Totstd= 0001 0001 5-level 157 (162)

RESULTS Mean = 000286 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000088 --gt 3086 r = 00025Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000101 --gt 3525 R = 00028Remarks none

000 050 100 150 200

k-values

4L

26L

10L

46L

12L

Mandels k statistics(Compost 1 - PBD 99)

00 00 00 00 00 00 00 00 00 00

Deviation from Mean

4L

26L

10L

46L

12L

Labo

rato

ries

Compost 1 - PBD 99 -- Mean PARM = 0003 [mgkg]

-200 -100 000 100 200

h-values

4L

26L

10L

46L

12L

Labo

rato

ries

Mandels h statistics(Compost 1 - PBD 99)

Compost 1-PBD 99

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 99)Mandels h statistics(Sludge 1 - PBD 99)

Sample Sludge 1 Sludge 1 - PBD 99 -- Mean PARM = 0024 [mgkg]

Element PBD 99

General calcparmT1= 448050E-01T2= 112113E-02T3= 19T4= 73T5= 32972E-05

n= variabelp= 5

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean64L 00173 0002 4 -118 041 Fail 00173 00019 4 3 -0014L 00183 0002 4 -104 032 00183 00015 4 3 -001

12L 00227 0001 4 -038 022 00227 00010 4 3 00010L 00290 0001 3 055 021 00290 00010 3 2 00146L 00320 0002 4 100 039 00320 00018 4 3 00126L 00323 0011 2 105 234 - - 26L - - 001

Totgem 0025 0003 mgkg 1-level 187 (177) 5 00239 (26L) 5 4Totstd= 0007 0004 5-level 166 (154) 1

RESULTS Mean = 002385 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000153 --gt 643 r = 00043Between lab variance S2L = 000004Reproducibility var S2R = 000004Reproducibility std SR = 000666 --gt 2791 R = 00186Remarks 1 Lab rejected (26L)

000 050 100 150 200 250

k-values

64L

4L

12L

10L

46L

26L

Mandels k statistics(Sludge 1 - PBD 99)

00 00 00 00 00 00 00 00 00 00

Deviation from Mean

64L

4L

12L

10L

46L

26L

Labo

rato

ries

Sludge 1 - PBD 99 -- Mean PARM = 0024 [mgkg]

-200 -100 000 100 200

h-values

64L

4L

12L

10L

46L

26L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 99)

Sludge 1-PBD 99

Unit mgkg

Mandels k statistics(Soil 3 - PBD 99)Mandels h statistics(Soil 3 - PBD 99)

Sample Soil 3 NUM

Element PBD 99

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00017 0000 4 091 068 - - 10L - - NUM46L 00017 0001 4 100 211 - - 46L - - NUM64L 00005 0000 4 -106 023 NUM - 64L - - NUM12L 00012 0000 4 015 014 - - 12L - - NUM26L 00006 0000 2 -101 012 - - 26L - - NUM

Totgem 0001 0000 mgkg 1-level 172 (173) NUM (10L46L64L12L26L) -1Totstd= 0001 0000 5-level 157 (153) 5

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 5 Labs rejected (10L46L64L12L26L)

000 050 100 150 200 250

k-values

10L

46L

64L

12L

26L

Mandels k statistics(Soil 3 - PBD 99)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

10L

46L

64L

12L

26L

Labo

rato

ries

NUM

-200 -100 000 100 200

h-values

10L

46L

64L

12L

26L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 99)

Soil 3-PBD 99

Unit mgkg

Mandels k statistics(Compost 1 - PBD 100)Mandels h statistics(Compost 1 - PBD 100)

Sample Compost 1 Compost 1 - PBD 100 -- Mean PARM = 0001 [mgkg]

Element PBD 100

General calcparmT1= 124272E-02T2= 113129E-05T3= 14T4= 52T5= 46584E-07

n= variabelp= 4

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean26L 00006 0000 2 -131 037 Fail 00006 00001 2 1 00010L 00009 0000 4 003 083 00009 00002 4 3 00046L 00009 0000 4 016 115 00009 00002 4 3 00012L 00011 0000 4 112 136 Fail 00011 00003 4 3 000

Totgem 0001 0000 mgkg 1-level 149 (167) 4 00009 () 4 3Totstd= 0000 0000 5-level 142 (15)

RESULTS Mean = 000085 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000022 --gt 2531 r = 00006Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000025 --gt 2882 R = 00007Remarks none

000 050 100 150

k-values

26L

10L

46L

12L

Mandels k statistics(Compost 1 - PBD 100)

00 00 00 00 00 00 00 00 00 00 00

Deviation from Mean

26L

10L

46L

12L

Labo

rato

ries

Compost 1 - PBD 100 -- Mean PARM = 0001 [mgkg]

-200 -100 000 100 200

h-values

26L

10L

46L

12L

Labo

rato

ries

Mandels h statistics(Compost 1 - PBD 100)

Compost 1-PBD 100

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 100)Mandels h statistics(Sludge 1 - PBD 100)

Sample Sludge 1 Sludge 1 - PBD 100 -- Mean PARM = 0005 [mgkg]

Element PBD 100

General calcparmT1= 852065E-02T2= 412762E-04T3= 18T4= 68T5= 78914E-07

n= variabelp= 5

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00039 0000 4 -042 007 Fail 00039 00002 4 3 000

12L 00044 0000 4 -041 005 Fail 00044 00001 4 3 00010L 00046 0000 4 -041 013 Fail 00046 00003 4 3 00046L 00056 0000 4 -040 012 Fail 00056 00003 4 3 00026L 00059 0000 2 -040 013 Fail 00059 00003 2 1 00038L 02168 0006 4 204 244 Fail - - 38L - - 021

Totgem 0040 0001 mgkg 1-level 187 (177) 5 00049 (38L) 5 4Totstd= 0087 0002 5-level 166 (154) 1

RESULTS Mean = 000486 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000025 --gt 507 r = 00007Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000084 --gt 1731 R = 00024Remarks 1 Lab rejected (38L)

000 050 100 150 200 250

k-values

4L

12L

10L

46L

26L

38L

Mandels k statistics(Sludge 1 - PBD 100)

-01 00 01 01 02 02 03

Deviation from Mean

4L

12L

10L

46L

26L

38L

Labo

rato

ries

Sludge 1 - PBD 100 -- Mean PARM = 0005 [mgkg]

-100 000 100 200 300

h-values

4L

12L

10L

46L

26L

38L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 100)

Sludge 1-PBD 100

Unit mgkg

Mandels k statistics(Soil 3 - PBD 100)Mandels h statistics(Soil 3 - PBD 100)

Sample Soil 3 NUM

Element PBD 100

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00003 0000 4 -050 000 Fail - - 10L - - NUM46L 00003 0000 4 -050 000 Fail NUM - 46L - - NUM3L 305500 2051 2 150 200 Fail - - 3L - - NUM

26L 00005 0000 2 -050 000 Fail - - 26L - - NUM

Totgem 7638 0513 mgkg 1-level 149 (177) NUM (10L46L3L26L) -1Totstd= 15275 1025 5-level 142 (159) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (10L46L3L26L)

000 050 100 150 200

k-values

10L

46L

3L

26L

Mandels k statistics(Soil 3 - PBD 100)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

10L

46L

3L

26L

Labo

rato

ries

NUM

-100 000 100 200

h-values

10L

46L

3L

26L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 100)

Soil 3-PBD 100

Unit mgkg

Mandels k statistics(Compost 1 - PBD 153)Mandels h statistics(Compost 1 - PBD 153)

Sample Compost 1 NUM

Element PBD 153

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean44L 00053 0001 3 150 157 Fail - - 44L - - NUM46L 00007 0000 4 -044 111 Fail - - 46L - - NUM12L 00005 0000 4 -051 055 Fail - - 12L - - NUM26L 00005 0000 2 -054 001 Fail NUM - 26L - - NUM

Totgem 0002 0000 mgkg 1-level 149 (177) NUM (44L46L12L26L) -1Totstd= 0002 0000 5-level 142 (159) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (44L46L12L26L)

000 050 100 150 200

k-values

44L

46L

12L

26L

Mandels k statistics(Compost 1 - PBD 153)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

44L

46L

12L

26L

Labo

rato

ries

NUM

-100 000 100 200

h-values

44L

46L

12L

26L

Labo

rato

ries

Mandels h statistics(Compost 1 - PBD 153)

Compost 1-PBD 153

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 153)Mandels h statistics(Sludge 1 - PBD 153)

Sample Sludge 1 Sludge 1 - PBD 153 -- Mean PARM = 0004 [mgkg]

Element PBD 153

General calcparmT1= 676738E-02T2= 267609E-04T3= 18T4= 68T5= 19626E-05

n= variabelp= 5

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00024 0000 4 -157 017 00024 00002 4 3 000

12L 00038 0002 4 006 154 00038 00018 4 3 00046L 00039 0000 4 011 026 00039 00003 4 3 00026L 00039 0000 2 018 004 00039 00000 2 1 00064L 00049 0002 4 122 159 00049 00018 4 3 000

Totgem 0004 0001 mgkg 1-level 172 (173) 5 00038 () 5 4Totstd= 0001 0001 5-level 157 (153)

RESULTS Mean = 000378 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000123 --gt 3252 r = 00034Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000142 --gt 3754 R = 00040Remarks none

000 050 100 150 200

k-values

4L

12L

46L

26L

64L

Mandels k statistics(Sludge 1 - PBD 153)

00 00 00 00 00 00 00

Deviation from Mean

4L

12L

46L

26L

64L

Labo

rato

ries

Sludge 1 - PBD 153 -- Mean PARM = 0004 [mgkg]

-200 -100 000 100 200

h-values

4L

12L

46L

26L

64L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 153)

Sludge 1-PBD 153

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 154)Mandels h statistics(Sludge 1 - PBD 154)

Sample Sludge 1 NA

Element PBD 154

General calcparmT1= NAT2= NAT3=T4=T5=

n= variabelp=

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00021 0000 3 -100 021 NA - 4L - - NA

46L 00025 0000 4 115 018 NA - 46L - - NA64L 00021 0001 4 -066 179 - - 64L - - NA12L 00023 0000 4 050 085 - - 12L - - NA

Totgem 0002 0000 mgkg 1-level 149 (167) NA (4L46L64L12L) -1Totstd= 0000 0000 5-level 142 (15) 4

RESULTS Mean = NA mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NAReproducibility var S2R = NAReproducibility std SR = NA --gt NA R = NARemarks 4 Labs rejected (4L46L64L12L)

000 050 100 150 200

k-values

4L

46L

64L

12L

Mandels k statistics(Sludge 1 - PBD 154)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

4L

46L

64L

12L

Labo

rato

ries

NA

-100 000 100 200

h-values

4L

46L

64L

12L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 154)

Sludge 1-PBD 154

Unit mgkg

Mandels k statistics(Soil 3 - PBD 154)Mandels h statistics(Soil 3 - PBD 154)

Sample Soil 3 NUM

Element PBD 154

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

4L 00010 - 1 150 Fail - - 4L - - NUM46L 00001 0000 4 -053 096 Fail - - 46L - - NUM64L 00001 0000 4 -056 105 Fail NUM - 64L - - NUM12L 00002 0000 4 -040 099 Fail - - 12L - - NUM

Totgem 000037 0000 mgkg 1-level 149 (164) NUM (4L46L64L12L) -1Totstd= 000042 0000 5-level 142 (153) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (4L46L64L12L)

000 050 100 150

k-values

4L

46L

64L

12L

Mandels k statistics(Soil 3 - PBD 154)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

4L

46L

64L

12L

Labo

rato

ries

NUM

-100 000 100 200

h-values

4L

46L

64L

12L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 154)

Soil 3-PBD 154

Unit mgkg

Mandels k statistics(Compost 1 - PBD 209)Mandels h statistics(Compost 1 - PBD 209)

Sample Compost 1 NUM

Element PBD 209

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00065 0003 2 -049 032 - - 4L - - NUM

44L 00573 0021 4 150 197 Fail - - 44L - - NUM12L 00078 0001 4 -045 011 - - 12L - - NUM26L 00049 0000 2 -056 000 NUM - 26L - - NUM

Totgem 0019 0006 mgkg 1-level 149 (177) NUM (4L44L12L26L) -1Totstd= 0025 0010 5-level 142 (159) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (4L44L12L26L)

000 050 100 150 200

k-values

4L

44L

12L

26L

Mandels k statistics(Compost 1 - PBD 209)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

4L

44L

12L

26L

Labo

rato

ries

NUM

-100 000 100 200

h-values

4L

44L

12L

26L

Labo

rato

ries

Mandels h statistics(Compost 1 - PBD 209)

Compost 1-PBD 209

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 209)Mandels h statistics(Sludge 1 - PBD 209)

Sample Sludge 1 Sludge 1 - PBD 209 -- Mean PARM = 0249 [mgkg]

Element PBD 209

General calcparmT1= 394542E+00T2= 107296E+00T3= 16T4= 56T5= 19723E-02

n= variabelp= 5

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 01550 0055 4 -112 148 Fail 01550 00551 4 3 -009

46L 02050 0007 2 -053 019 02050 00071 2 1 -00412L 02137 0058 4 -042 155 02137 00576 4 3 -00426L 03149 0021 2 078 057 Fail 03149 00210 2 1 00764L 03577 0007 4 129 020 Fail 03577 00074 4 3 011

Totgem 0249 0030 mgkg 1-level 172 (185) 5 02493 () 5 4Totstd= 0084 0025 5-level 157 (162)

RESULTS Mean = 024926 mgkg

Repeatability variance S2r = 000179Repeatability std Sr = 004234 --gt 1699 r = 01186Between lab variance S2L = 000743Reproducibility var S2R = 000922Reproducibility std SR = 009604 --gt 3853 R = 02689Remarks none

000 050 100 150 200

k-values

4L

46L

12L

26L

64L

Mandels k statistics(Sludge 1 - PBD 209)

-01 -01 00 01 01 02

Deviation from Mean

4L

46L

12L

26L

64L

Labo

rato

ries

Sludge 1 - PBD 209 -- Mean PARM = 0249 [mgkg]

-200 -100 000 100 200

h-values

4L

46L

12L

26L

64L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 209)

Sludge 1-PBD 209

Unit mgkg

Mandels k statistics(Soil 3 - PBD 209)Mandels h statistics(Soil 3 - PBD 209)

Sample Soil 3 Soil 3 - PBD 209 -- Mean PARM = 0258 [mgkg]

Element PBD 209

General calcparmT1= 596398E+00T2= 191917E+00T3= 22T4= 84T5= 13249E-02

n= variabelp= 6

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean26L 01162 0021 2 -108 074 Fail 01162 00207 2 1 -0144L 01303 0031 4 -097 111 Fail 01303 00312 4 3 -013

46L 01975 0036 4 -046 128 Fail 01975 00359 4 3 -00644L 02898 0035 4 024 124 Fail 02898 00346 4 3 00312L 03895 0018 4 100 065 Fail 03895 00181 4 3 01364L 04260 0022 4 127 078 Fail 04260 00219 4 3 017

Totgem 0258 0027 mgkg 1-level 187 (177) 6 02582 () 6 5Totstd= 0132 0008 5-level 166 (154)

RESULTS Mean = 025818 mgkg

Repeatability variance S2r = 000083Repeatability std Sr = 002878 --gt 1115 r = 00806Between lab variance S2L = 001640Reproducibility var S2R = 001723Reproducibility std SR = 013127 --gt 5084 R = 03676Remarks none

000 050 100 150

k-values

26L

4L

46L

44L

12L

64L

Mandels k statistics(Soil 3 - PBD 209)

-02 -01 -01 00 01 01 02 02

Deviation from Mean

26L

4L

46L

44L

12L

64L

Labo

rato

ries

Soil 3 - PBD 209 -- Mean PARM = 0258 [mgkg]

-200 -100 000 100 200

h-values

26L

4L

46L

44L

12L

64L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 209)

Soil 3-PBD 209

Unit mgkg

Mandels k statistics(Compost 1 - Sum PBD)Mandels h statistics(Compost 1 - Sum PBD)

Sample Compost 1 Compost 1 - Sum PBD -- Mean PARM = 0009 [mgkg]

Element Sum PBD

General calcparmT1= 154064E-01T2= 169065E-03T3= 18T4= 68T5= 11354E-04

n= variabelp= 5

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00031 0002 4 -067 016 00031 00016 4 3 -0014L 00055 0005 4 -056 048 00055 00047 4 3 000

46L 00085 0003 4 -042 031 00085 00030 4 3 00026L 00123 0000 2 -024 003 00123 00002 2 1 00012L 00154 0002 4 -011 021 00154 00021 4 3 00144L 00613 0023 4 200 237 Fail - - 44L - - 005

Totgem 0018 0006 mgkg 1-level 187 (177) 5 00089 (44L) 5 4Totstd= 0022 0009 5-level 166 (154) 1

RESULTS Mean = 000893 mgkg

Repeatability variance S2r = 000001Repeatability std Sr = 000296 --gt 3308 r = 00083Between lab variance S2L = 000002Reproducibility var S2R = 000003Reproducibility std SR = 000570 --gt 6374 R = 00159Remarks 1 Lab rejected (44L)

000 050 100 150 200 250

k-values

10L

4L

46L

26L

12L

44L

Mandels k statistics(Compost 1 - Sum PBD)

00 00 00 00 00 00 01 01

Deviation from Mean

10L

4L

46L

26L

12L

44L

Labo

rato

ries

Compost 1 - Sum PBD -- Mean PARM = 0009 [mgkg]

-100 000 100 200

h-values

10L

4L

46L

26L

12L

44L

Labo

rato

ries

Mandels h statistics(Compost 1 - Sum PBD)

Compost 1-Sum PBD

Unit mgkg

Mandels k statistics(Sludge 1 - Sum PBD)Mandels h statistics(Sludge 1 - Sum PBD)

Sample Sludge 1 Sludge 1 - Sum PBD -- Mean PARM = 0256 [mgkg]

Element Sum PBD

General calcparmT1= 531806E+00T2= 162188E+00T3= 22T4= 84T5= 25223E-02

n= variabelp= 6

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00423 0025 4 -156 044 Fail 00423 00252 4 3 -02146L 01808 0118 4 -049 205 - - 46L - - -0074L 01810 0056 4 -049 097 01810 00558 4 3 -007

38L 02168 0006 4 -022 010 02168 00059 4 3 -00412L 02890 0065 4 034 113 02890 00647 4 3 00364L 03958 0008 4 116 014 Fail 03958 00079 4 3 01426L 04094 0034 2 126 059 Fail 04094 00337 2 1 015

Totgem 0245 0044 mgkg 1-level 198 (179) 6 02557 (46L) 6 5Totstd= 0130 0039 5-level 171 (155) 1

RESULTS Mean = 025570 mgkg

Repeatability variance S2r = 000158Repeatability std Sr = 003970 --gt 1553 r = 01112Between lab variance S2L = 001807Reproducibility var S2R = 001964Reproducibility std SR = 014015 --gt 5481 R = 03924Remarks 1 Lab rejected (46L)

000 050 100 150 200 250

k-values

10L

46L

4L

38L

12L

64L

26L

Mandels k statistics(Sludge 1 - Sum PBD)

-03 -02 -02 -01 -01 00 01 01 02 02

Deviation from Mean

10L

46L

4L

38L

12L

64L

26L

Labo

rato

ries

Sludge 1 - Sum PBD -- Mean PARM = 0256 [mgkg]

-200 -100 000 100 200

h-values

10L

46L

4L

38L

12L

64L

26L

Labo

rato

ries

Mandels h statistics(Sludge 1 - Sum PBD)

Sludge 1-Sum PBD

Unit mgkg

Mandels k statistics(Soil 3 - Sum PBD)Mandels h statistics(Soil 3 - Sum PBD)

Sample Soil 3 Soil 3 - Sum PBD -- Mean PARM = 0227 [mgkg]

Element Sum PBD

General calcparmT1= 610980E+00T2= 200876E+00T3= 26T4= 100T5= 13106E-02

n= variabelp= 7

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00028 0001 4 -037 000 Fail 00028 00005 4 3 -02226L 01179 0021 2 -036 003 Fail 01179 00208 2 1 -0114L 01305 0031 4 -036 004 Fail 01305 00308 4 3 -010

46L 02065 0035 4 -036 005 Fail 02065 00350 4 3 -00244L 02923 0037 4 -035 005 Fail 02923 00365 4 3 00712L 04051 0015 4 -034 002 Fail 04051 00149 4 3 01864L 04314 0022 4 -033 003 Fail 04314 00223 4 3 0203L 305500 2051 2 247 283 Fail - - 3L - - 3032

Totgem 4017 0276 mgkg 1-level 206 (181) 7 02266 (3L) 7 6Totstd= 10722 0717 5-level 175 (156) 1

RESULTS Mean = 022663 mgkg

Repeatability variance S2r = 000069Repeatability std Sr = 002626 --gt 1159 r = 00735Between lab variance S2L = 002568Reproducibility var S2R = 002637Reproducibility std SR = 016238 --gt 7165 R = 04547Remarks 1 Lab rejected (3L)

000 050 100 150 200 250 300

k-values

10L

26L

4L

46L

44L

12L

64L

3L

Mandels k statistics(Soil 3 - Sum PBD)

-50 00 50 100 150 200 250 300 350

Deviation from Mean

10L

26L

4L

46L

44L

12L

64L

3L

Labo

rato

ries

Soil 3 - Sum PBD -- Mean PARM = 0227 [mgkg]

-100 000 100 200 300

h-values

10L

26L

4L

46L

44L

12L

64L

3L

Labo

rato

ries

Mandels h statistics(Soil 3 - Sum PBD)

Soil 3-Sum PBD

19

Annex 4

Raw data submitted

Sample Compost1 Sample Compost 1 Sample Compost 1Element PBD 99 Element PBD 100 Element PBD 153

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]4L 00021 10L 00008 44L 000504L 00024 10L 00008 44L 000604L 00014 10L 00007 44L 000504L 00020 10L 00011 46L 00004

10L 00029 46L 00007 46L 0001210L 00027 46L 00012 46L 0000410L 00032 46L 00009 46L 0000946L 00025 46L 00007 12L 0000446L 00052 12L 00008 12L 0000846L 00029 12L 00012 12L 0000446L 00026 12L 00008 12L 0000712L 00026 12L 00014 26L 0000512L 00043 26L 00007 26L 0000512L 00026 26L 0000612L 0004726L 0002626L 00024

Sample Compost 1 Sample Compost 1 Sample Compost 1Element PBD 154 Element PBD 183 Element PBD 196

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]4L 00010 46L 00002 46L 00011

46L 00003 46L 00024 46L 0000846L 00007 46L 00021 12L 0000246L 00003 46L 00003 12L 0000346L 00004 12L 00003 12L 0000112L 00003 12L 00011 12L 0000212L 00005 12L 0000312L 00031 12L 0000312L 00006

Sample Compost 1 Sample Compost 1 Sample Compost 1Element PBD 197 Element PBD 203 Element PBD 209

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00002 46L 00010 4L 0004146L 00023 12L 00002 4L 0008946L 00022 12L 00003 44L 0041012L 00004 12L 00002 44L 0084012L 00006 12L 00002 44L 0064012L 00003 44L 0040012L 00004 12L 00079

12L 0007312L 0006512L 0009326L 0004926L 00049

Sample Compost 1Element PBD 47

LAB PARM [mgkg]26L 0003826L 00039

Element PBD 99 Element PBD 47 Element PBD 209LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]

4L 00170 10L 00210 4L 010004L 00200 10L 00220 4L 018004L 00170 10L 00210 4L 012004L 00190 46L 00300 4L 0220010L 00280 46L 00280 46L 0210010L 00300 46L 00250 46L 0200010L 00290 46L 00260 64L 0351846L 00340 64L 00059 64L 0363846L 00330 64L 00057 64L 0364546L 00300 64L 00062 64L 0350846L 00310 64L 00060 12L 0220964L 00194 12L 00191 12L 0177164L 00154 12L 00187 12L 0292264L 00185 12L 00190 12L 0164664L 00159 12L 00186 26L 0329712L 00242 26L 00666 26L 0300012L 00223 26L 0033212L 0022112L 0022226L 0024626L 00400

Element PBD 203 Element PBD 197 Element PBD 196LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00022 46L 00027 46L 0002446L 00014 46L 00024 46L 0002264L 00036 12L 00161 64L 0005864L 00058 12L 00060 64L 0006512L 00063 12L 00061 12L 0004812L 00034 12L 00036 12L 0002512L 00038 12L 0003212L 00027 12L 00022

Element PBD 183 Element PBD 154 Element PBD 153LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00049 4L 00020 4L 0002246L 00035 4L 00022 4L 0002446L 00036 4L 00020 4L 0002246L 00034 46L 00025 4L 0002664L 00027 46L 00025 46L 0004064L 00023 46L 00025 46L 0004264L 00024 46L 00023 46L 0003564L 00020 64L 00034 46L 0003812L 00230 64L 00023 64L 0007412L 00032 64L 00017 64L 0004712L 00031 64L 00011 64L 0004612L 00030 12L 00030 64L 0003026L 00007 12L 00021 12L 0006526L 00008 12L 00021 12L 00029

12L 00021 12L 0003226L 00015 12L 0002926L 00019 26L 00039

26L 00040

Element PBD 100LAB PARM [mgkg]

4L 000384L 000414L 000374L 00038

38L 0219038L 0220038L 0208038L 0220010L 0004410L 0005010L 0004310L 0004646L 0005746L 0005946L 0005346L 0005312L 0004312L 0004512L 0004312L 0004326L 0006226L 00057

Sample Soil 3 Sample Soil 3 Sample Soil 3Element PBD 99 Element PBD 47 Element PBD 100

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]10L 00016 10L 00011 10L 0000310L 00019 10L 00010 10L 0000410L 00013 10L 00012 10L 0000410L 00019 46L 00007 10L 0000246L 00025 46L 00022 46L 0000246L 00025 46L 00005 46L 0000646L 00008 46L 00007 46L 0000246L 00011 12L 00010 46L 0000264L 00005 12L 00017 3L 29100064L 00005 12L 00010 3L 32000064L 00006 12L 00009 26L 0000564L 00007 26L 00007 26L 0000512L 00012 26L 0000712L 0001312L 0001312L 0001226L 0000526L 00006

Sample Soil 3 Sample Soil 3 Sample Soil 3Element PBD 153 Element PBD 154 Element PBD 196

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]44L 00050 4L 00010 46L 0000744L 00050 46L 00001 46L 0001146L 00002 46L 00002 46L 0000846L 00003 46L 00001 46L 0001146L 00002 46L 00002 64L 0002646L 00002 64L 00001 64L 0002664L 00001 64L 00001 64L 0002964L 00001 64L 00001 64L 0003464L 00001 64L 00002 12L 0004564L 00002 12L 00003 12L 00032

12L 00002 12L 0002212L 00002 12L 0002112L 00002

Sample Soil 3 Sample Soil 3 Sample Soil 3Element PBD 197 Element PBD 203 Element PBD 209

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00006 46L 00011 4L 0091046L 00013 46L 00017 4L 0150046L 00011 46L 00015 4L 0120046L 00013 46L 00018 4L 0160012L 00090 64L 00013 44L 0337012L 00056 64L 00014 44L 0281012L 00033 64L 00016 44L 0287012L 00032 64L 00015 44L 02540

12L 00055 46L 0230012L 00041 46L 0220012L 00027 46L 0150012L 00026 46L 01900

64L 0438164L 0401664L 0414464L 0449812L 0367112L 0397812L 0409112L 03838

Sample Soil 3 26L 0102Element PBD 183 26L 0131

LAB PARM [mgkg]46L 0000746L 0000846L 0005846L 0000764L 0000264L 0000364L 0000364L 0000312L 0001512L 0001112L 0000712L 00007

European Commission EUR 23003 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on polybrominated diphenylethers Author(s) E Sobiecka H van der Sloot D Barcelo B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 68 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07403-5 Abstract Project HORIZONTAL is interdisciplinary aiming at a harmonisation and horizontal standardisation of test procedures in particular for sludge soils and biowastes In the context of this standardization project a series of draft technical specification were designed upon an extensive desk study fine-tuned after expert consultations and finally validated in international intercomparisons exercise This report summarises the work performed within the validation study of the draft standard for the determination of polybrominated diphenylethers (PBDE) in soils sludge and treated bio-waste using gas-chromatography method with mass selective detection (GC-MS) It further explains the underlying statistical concept for the calculation of reproducibility and repeatability from intercomparisons data In addition all single values results of the statistical evaluation as well as background information on the validation materials used are described and explained

The mission of the JRC is to provide customer-driven scientific and technical support for the conception development implementation and monitoring of EU policies As a service of the European Commission the JRC functions as a reference centre of science and technology for the Union Close to the policy-making process it serves the common interest of the Member States while being independent of special interests whether private or national

LB

-NA

-23003-EN

-C

9

125 Timing and Submission of data Dispatch of samples was done on the 18th of October 2006 For users of the Online data submission system (MILC) User Registration was possible from 14th of November 2006 with opening of the MILC Data Submission on 1st of December 2006 The deadline for submission of results has been set for PBDE to the 12th of January 2007 but was extended to the end of the same months After that no further submission was possible Alternatively the participants were allowed to submit data electronically as Excel sheet using simply Email All data were treated in a confidential way Any presentation hereafter will refer only to numerical data and it will not be possible to identify the originating laboratory Lab Codes displayed are NOT related to the order of laboratories hereafter In addition to the information provide an Helpdesk was implemented in order to give quick and individual response to the participants during and immediately after the validation study In case of doubt and suspected transcription errors further enquires were conducted by JRC

10

126 Participants The following table lists the participating organisations and entities in the validation exercise for the horizontal PBDE standard

bull Austria o Umweltbundesamt

bull Czech Republic o Povodi Labe statni podnik - OVHL Laboratory

bull France o CIRSEE o CTC Environnement o INERIS

bull Germany o Federal Environmental Agency Section III 34 Laboratory Methods for

the Surveillance of Waste and Wastewater (UBA) bull Italy

o European Commission DG JRC IES bull Spain

o Consejo Superior de Investigaciones Cientificas (CSIC)

bull Sweden o ALCONTROL AB

11

13 Summary results and derived performance characteristics The result of the various statistical evaluation including outlier tests calculation of repeatability and reproducibility standard deviation for the congeners of interest can be found in Annex 3 of this report In addition all data submitted by the participants as well as those considered for the calculation of the performance characteristics are listed in Annex 3 to this report Based on these calculations the following results were obtained in the validation round upon statistical evaluation according to ISO 5725-2 The average values the repeatability standard deviation (sr) and the reproducibility standard deviation (sR) were obtained (Table1) The repeatability is determined as an interval around a measurement result (ie repeatability limit) This interval corresponds to the maximum difference that can be expected (with a 95 statistical confidence) between one test result and another both test results being obtained under the following conditions The tests are performed in accordance with all the requirements of the present standard by the same laboratory using its own facilities and testing laboratory samples obtained from the same primary field sample and prepared under identical procedures The repeatability limit was calculated using the relationship r test = f radic2 s rtest with the critical range factor f = 2 The reproducibility like repeatability is also determined as an interval around a measurement result (ie reproducibility limit) This interval corresponds to the maximum difference that can be expected (with a 95 statistical confidence) between one test result and another test result obtained by another laboratory both test results being obtained under the following conditions The tests are performed in accordance with all the requirements of the present standard by two different laboratories using their own facilities and testing laboratory samples obtained from the same primary field sample and prepared under identical procedures The reproducibility limit was calculated using the relationship R = f radic2 sR with the critical range factor f = 2

12

Table 1 - Results of the interlaboratory comparison studies of the determination of selected polybrominated diphenyl ethers (PBDE) by gaschromatography with mass spectrometric detection (GC-MS) in soil sludge and treated biowaste All concentrations are expressed in mgkg dm

Matrix Parameter Mean sr sR r R p Outliers Used No of data

No of data reported below

detection

Total no of data

Sludge 1 PBD 47 00181 461 4 15 5 20 Compost 1 00039 94 3 12 0 12 Soil 3 00010 50 50 00014 00014 4 0 13 10 23 Sludge 1 PBD 99 00239 64 28 00043 00186 5 1 19 0 23 Compost 1 00029 31 35 00025 00028 5 0 17 4 21 Soil 3 00013 499 4 16 8 24 Sludge 1 PBD 100 00049 51 17 00007 00024 5 1 18 2 24 Compost 1 00009 25 29 00006 00007 4 0 14 7 21 Soil 3 61103 211 3 10 15 25 Sludge 1 PBD 153 00038 33 38 00034 0004 5 0 18 0 18 Compost 1 00019 116 3 11 3 14 Soil 3 00011 177 2 10 10 20 Sludge 1 PBD 154 00023 234 4 15 2 17 Compost 1 00008 1118 3 9 5 14

13

Matrix Parameter Mean sr sR r R p Outliers Used No of data

No of data reported below

detection

Total no of data

Soil 3 00002 1049 4 13 6 19 Sludge 1 PBD 183 00048 1217 3 12 2 14 Compost 1 00009 1048 2 8 5 13 Soil 3 00011 1395 3 12 6 18 Sludge 1 PBD 196 00037 470 2 8 7 15 Compost 1 00004 950 2 6 4 10 Soil 3 00023 519 3 12 2 14 Sludge 1 PBD 197 00062 834 2 6 8 14 Compost 1 00009 1001 2 7 7 14 Soil 3 00032 904 2 8 6 14 Sludge 1 PBD 203 00037 461 2 8 4 12 Compost 1 00004 978 2 5 3 8 Soil 3 00022 598 3 12 0 12 Sludge 1 PBD 209 02493 170 39 01186 02689 5 0 16 2 18 Compost 1 00273 104 3 10 5 15 Soil 3 02582 1115 51 00806 03676 6 0 22 0 22

14

Matrix Parameter Mean sr sR r R p Outliers Used No of data

No of data reported below

detection

Total no of data

Sludge 1 Sum PBD 0256 155 548 0111 0392 6 1 22 Compost 1 0009 331 637 0008 0016 5 1 18 Soil 3 0227 116 717 0074 0455 7 1 26 Abbreviations sr Repeatability standard deviation SR Reproducibility standard deviation r Repeatability limit (comparing two measurements) R Reproducibility limit (comparing two measurements) p Number of labs determination not possible

15

14 Annexes Annex 1 Model questionnaire to be filled by the participating laboratories Annex 3 Report on the validation materials used Annex 2 Statistical calculations Annex 3 Data submitted

16

Annex 1

Model questionnaire to be filled by the participating laboratories

Model questionnaire to be filled by the participating laboratories Name of laboratory Contact person Contact details email Phone Fax Mail address of lab Dispatch address of lab for shipment of samples (no PO boxes) Title of measurement method (copy attached) Our laboratory is willing to participate in the precision experiment for this draft standard method

Yes No As participant we understand that

bull All essential apparatus chemicals and other requirements specified in the method must be available in our laboratory when the programme begins

bull Specified timing requirements such as starting and finishing date of the programme must be rigidly met

bull The method must be strictly adhered to bull Samples must be handled in accordance with instructions bull A qualified operator must perform the measurements

Having studied the method and having made a fair appraisal of our capabilities and facilities we feel that we will be adequately prepared for cooperative testing of this method Comments helliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphellip Signature Date

17

Annex 2

Report on the validation materials used

VI

Abstract This report gives an overview on the available analytical information on the following raw materials to be used for the production of validation materials of the so-called Project HORIZONTAL

bull Four sludge materials from Duumlsseldorf Germany

bull An agricultural soil material from Reading United Kingdom

bull A compost material from Vienna Austria

bull A compost material from Korschenbroich Germany

bull A sludge-amended agricultural soil from Pavia Province Italy

bull A sludge-amended soil from Barcelona Spain

bull A sludge-amended soil from Essen Germany

bull A long-term sludge exposed soil from Hohenheim Germany

VII

List of Abbreviations Throughout this report the following abbreviations are used

AOX absorbable organic halogens

Corg organic carbon content

Ctotal total carbon content

CAT cation exchangeable

CDD chlorinated dibenzodioxin

CDF chlorinated dibenzofuran

DEHP di(2-ethylhexyl)phthalate

DM dry matter

EPA Environment Protection Agency

EU European Union

FM fresh matter

Hp hepta

Hx hexa

IES Institute for Environment and Sustainability

IRMM Institute for Reference Materials and Measurements

JRC Joint Research Centre

LAS linear alkylsulfonates

LoD limit of detection

LUA Landesumweltamt

Ntotal total nitrogen content

NH4-N Ammonium nitrogen

NO3-N Nitrate nitrogen

NP nonylphenol

NRW North Rhine Westphalia

O octa

P poly

PAH polycyclic aromatic hydrocarbon

PCB polychlorinated biphenyl

Pe penta

T tetra

TEQ toxicity equivalent

UBA Umweltbundesamt

WHO World Health Organization

WWTP waste water treatment plant

6

1 Introduction This report gives an overview on the available analytical information on the following raw materials to be used for the production of validation materials of the so-called Project HORIZONTAL

bull Four sludge materials from Duumlsseldorf Germany

bull An agricultural soil material from Reading United Kingdom

bull A compost material from Vienna Austria

bull A compost material from Korschenbroich Germany

bull A sludge-amended agricultural soil from Pavia Province Italy

bull A sludge-amended soil from Barcelona Spain

bull A sludge-amended soil from Essen Germany

bull A long-term sludge exposed soil from Hohenheim Germany

The following analytical information was gathered partly before and during the sampling of the raw materials to be used for the production of the HORIZONTAL validation materials The material were sampled by IES and shipped to IRMM in the course of the year 2005 The information gathered was then completed by various analytical screenings for PAHs and PCBs done by the Institute for Reference Materials and Measurements Geel Belgium for phthalates done by UBA Berlin Germany for PBDE done by IIQAB-CSIC Barcelona Spain for trace elements and some selected major and minor elements by the Institute for Environment and Sustainability Ispra Italy

The work compiled hereafter is based on the numerous additional efforts of the scientists working at various members of the consortium Project HORIZONTAL-Org and contributing organisations

This work is gratefully acknowledged

2 Overview on property values

21 Sludge materials from Duumlsseldorf Germany

The various sewage sludge materials originate from various installations in the North Rhine Westphalia and were produced and sampled by staff from the Landesumweltamt (LUA) NRW under the responsibility from Dr K Furtmann

In total four sludge materials (Sludge A and D from a major municipal WWTP Sludge B from a municipal WWTP with industrial input and Sludge C from a municipal WWTP with high PCB-Content) were obtained and will be blended to two final materials Before sampling the following analytical data for a typical sample were received

7

Table 1 ndash Analytical data obtained on an average sludge sample in LUA NRW (with courtesy of K Furtmann LUA Duumlsseldorf)

Parameter Concentration PCB 120 ugkg DEHP 110 mgkg PAH 5 mgkg (EPA) PCDDF 15 ng TEkg PBDE 400 ugkg NP 40 mgkg LAS 3 gkg AOX 300 mgkg

Subsequent screening led to the information displayed hereafter It should be stressed that the data were obtained as SCREENING information on the UNTREATED or partially treated raw materials Therefore the final target values which are relevant for the validation intercomparison can be different

Table 2 ndash Analytical data obtained on a first screening on the sludge samples from LUA NRW

Sewage sludge A

Dusseldorf

sewage sludge D

Dusseldorf PCB (ngg) 28 62 35 52 101 65 101 31 38 118 49 40 153 30 33 105 24 11 138 46 38 156 lt1 lt1 180 34 23 170 23 19 PAH (ngg) Naphtalene 34 381 Acenaphtylene 15 43 Acenaphthene 81 108 Fluorene 94 1167 Phenantrene 3440 Anthracene 22 344 Flouranthene 316 4817 Pyrene 235 3011 Benz(a)anthracene 473 791 Chrysene 691 1078 Benz(b)fluoranthene 538 1688 Benz(k)fluoranthene 228 635 Benz(a)pyrene 383 1114 Indeno(123-cd)pyrene 92 229 Dibenzo(ah)anthracene 71 70 Benzo(ghi)perylene 80 185

8

Table 3 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Sludge D (1) 0135 41474 385 Sludge B (2) 0538 0034 30634 547 Sludge A (3) 0184 0037 31399 146 Sludge C (4) 0354 1528 6678 229

Table 4 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Sludge 2

(B)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

554

959

694

591

772

509

nq

nq

970

2216

2379

Table 5 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena IES Ispra Spain) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Sludge 1 (D) 265 290 533 359 1231 338 784 438 lt 005 232 786 Sludge 2 (B) 119 311 626 202 278 299 722 251 lt 005 118 625 Sludge 3 (A) 168 360 621 332 847 416 119 451 lt 005 116 1237 Sludge 4 (C) 563 198 116 273 726 511 473 618 lt 005 444 2015

Table 6 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Sludge 1 (D) 2154 58 844 099 103 101 4367 lt15 50448 Sludge 2 (B) 1067 366 692 046 1491 077 5217 lt15 57633 Sludge 3 (A) 731 663 684 035 1287 068 3733 lt15 60369 Sludge 4 (C) 4379 965 527 163 522 107 5628 lt15 23945

Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM)Sludge 1 (D) 03 2403 101 1002 350 15 1944 132Sludge 2 (B) 031 315 97 879 172 12 514 180Sludge 3 (A) 031 1281 153 1567 265 16 1440 168Sludge 4 (C) 055 231 628 2625 371 81 1101 244

9

22 Agricultural soil material from Reading United Kingdom

The material was proposed by the University of Reading (S Nortcliff) and was sampled from a site called ldquoFrogmore Farmrdquo which was featured in the ldquoMetalsrdquo Report for HORIZONTAL This site is close to Reading with soils developed on flintyloamy periglacial materials over Chalk has a long and well documented history of sludge application The focus of the work of Nortcliff et al undertook at this site and the monitoring and control at the site (by Thames Water and the subsequent subsidiary bodies dealing with sludge application to soil) was on metals (and metal loads) with no analysis or indeed any form of investigation in to organics in the broadest sense

The analytical information produced in the context of the screening of the raw material is displayed below

Table 7 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 3

(Reading) 0032 0119 669

Table 8 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 3 (Reading) 015 706 279 138 152 901 267 300 lt 005 258 931

Table 9 ndash Analytical data obtained on a first screening on the sludge-amended soil from Reading (courtesy of IRMM)

Parameter Concentration

PCB ngg 28 lt1 52 lt1 101 lt1 118 lt1 153 lt1 105 lt1 138 lt1 156 lt1 180 lt1 170 lt1 PAH ngg Naphtalene lt10 Acenaphtylene 21 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene lt10 Flouranthene 818 Pyrene 776 Benz(a)anthracene 565

10

Parameter Concentration

Chrysene 608 Benz(b)fluoranthene 824 Benz(k)fluoranthene 329 Benz(a)pyrene 799 Indeno(123-cd)pyrene

779

Dibenzo(ah)anthracene 118 Benzo(ghi)perylene 394

Table 10 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 3

(Reading)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

103

003

nq

nq

nq

nd

nd

272

273

Table 11 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 3 (Reading) 015 706 279 138 152 901 267 300 lt 005 258 931

Table 12 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 3 (Reading) 7936 477 112 096 194 017 4107 443 2102 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 3 (Reading) 042 13 45 69 69 69 216 92

Table 13 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 3 (Reading) 012

11

23 Compost from Vienna Austria

The fresh compost material was obtained from the Austrian Federal Environment Agency (UBA Vienna) which had used a sub-batch of the raw material for national intercomparson The remainder of the material was stored at 4degC until shipment to IRMM for further processing The following analytical information was provided by UBA Austria and completed with various screenings

Table 14 ndash Analytical data on compost material received from UBA Austria Inorganic and sum parameters

Parameter Unit Sample fraction used Observed mean B CAT mgl FM Fresh sample lt10mm 61 K CAT mgl FM Fresh sample lt10mm 2624 Mg CAT mgl FM Fresh sample lt10mm 242 P CAT mgl FM Fresh sample lt10mm 49 B CAT DM Fresh sample lt10mm 00017 K CAT DM Fresh sample lt10mm 072 Mg CAT DM Fresh sample lt10mm 007 P CAT DM Fresh sample lt10mm 001 NO3-N mgkg FM Fresh sample lt10mm 35 NH4-N mgkg FM Fresh sample lt10mm 230 Ctotal DM lt45degdry milled 29 Corg DM lt45degdry milled 27 Ntotal DM lt45degdry milled 17 P mgkg DM lt45degdry milled 2596 K mgkg DM lt45degdry milled 11019 K DM lt45degdry milled 110 B mgkg DM lt45degdry milled 60 Cd mgkg DM lt45degdry milled 046 Cr mgkg DM lt45degdry milled 25 Cu mgkg DM lt45degdry milled 46 Hg mgkg DM lt45degdry milled 020 Ni mgkg DM lt45degdry milled 18 Pb mgkg DM lt45degdry milled 45 Zn mgkg DM lt45degdry milled 198 Ca mgkg DM lt45degdry milled 68776 Ca DM lt45degdry milled 69 Mo mgkg DM lt45degdry milled 08 S mgkg DM lt45degdry milled 2137 Fe mgkg DM lt45degdry milled 9959 Mn mgkg DM lt45degdry milled 418 Na mgkg DM lt45degdry milled 742 Co mgkg DM lt45degdry milled 41 AOX mgkg DM lt30deg dry milled 62

Table 15 ndash Analytical data on compost material received from UBA Austria Polycyclic aromatic hydrocarbons

PAH Unit Result Naphthaline microgkg DM 93 Acenaphthylene microgkg DM 86 Acenaphthene microgkg DM 5 Fluorene microgkg DM 80 Phenanthrene microgkg DM 89 Anthracene microgkg DM 27 Fluoranthene microgkg DM 487 Pyrene microgkg DM 380

12

PAH Unit Result Benzo(a)anthracene microgkg DM 278 Chrysene microgkg DM 317 Benzo(b)fluoranthene microgkg DM 365 Benzo(k)fluoranthene microgkg DM 193 Benz(a)pyrene microgkg DM 320 Indeno(123-cd)pyrene microgkg DM 233 Dibenz(ah)anthracene microgkg DM 67 Benzo(ghi)perylene microgkg DM 225 Sum EPA microgkg DM 3013 Sum EPA mgkg DM 30

Table 16 ndash Analytical data on compost material received from UBA Austria Sum PCDDs and PCBs

Parameter

Dioxine TEQ (ITEF) ngkg DM 73 TEQ (WHO) ngkg DM 35 PCB Σ Ballschmiter mgkg DM 005

Table 17 ndash Analytical data on compost material obtained by screening in IRMM

Parameter Result in ngg

PCB 28 2 52 2 101 4 118 3 153 10 105 1 138 8 156 1 180 5 170 lt1 PAH Naphtalene lt10 Acenaphtylene lt10 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene 26 Fluoranthene 611 Pyrene 510 Benz(a)anthracene 888 Chrysene 957 Benz(b)fluoranthene 1531 Benz(k)fluoranthene 547 Benz(a)pyrene 1101 Indeno(123-cd)pyrene 416 Dibenzo(ah)anthracene 81 Benzo(ghi)perylene 295

13

Table 18 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Compost 1

(Vienna)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

402

019

259

nq

023

004

nq

nq

144

174

259

Table 19 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Compost 1

(Vienna) 0058 1426 557

Table 20 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Compost 1 (Vienna) 039 736 319 410 365 127 495 004 079 013 208

Table 21 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Compost 1 (Vienna) 2063 431 617 426 199 249 1602 lt15 10521

Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Compost 1 (Vienna) 035 3496 81 375 79 55 653 60

Table 22 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Compost 1 (Vienna) 017

14

24 Agricultural soil sludge amended soil from Pavia Italy

This sludge-amended soil material was obtained during a monitoring campaign which aimed at a generic description of the over-all soil quality in Pavia Province Italy The material which was collected from the upper horizon originates from a small farm called ldquoCascina Novellordquo During the characterisation of the site the following analytical information was obtained on a pooled sample of a sub-area of the farm of 20 X 20 m2

Table 23 ndash Analytical data on Pavia soil

Parameter Result Al 713 Wgt As 224 mgkg Cd 079 mgkg Cr 59 mgkg Cu 308 mgkg Hg 008 mgkg Ni 344 mgkg Pb 246 mgkg Zn 95 mgkg C 091 Wgt 2378-TCDD 0047 pgg 12378-PeCDD 015 pgg 123478-HxCDD 019 pgg 123678-HxCDD 15 pgg 123789-HxCDD 074 pgg 1234678-HpCDD 26 pgg OCDD 382 pgg 2378-TCDF 068 pgg 12378-PeCDF 053 pgg 23478-PeCDF 071 pgg 123478-HxDF 100 pgg 123678-HxDF 066 pgg 234678-HxDF 16 pgg 123789-HxDF 027 pgg 1234678-HpDF 12 pgg 1234789-HpDF 068 pgg OCDF 33 pgg I-TEQ 20 pgg WHO-TEQ 17 pgg

In addition the screening performed at IRMM did not reveal significant quantities of PCBs and PAHs which were all below the LoDs (1 ngg for PCBs and 10 ngg for PAHs respectively)

Table 24 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 5 (Pavia) 0005 0011 154

15

Table 25 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 5

(Pavia)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

039

nq

nq

008

nq

nd

nd

670

671

Table 26 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 5 (Pavia) 033 184 573 225 426 305 206 200 lt 005 381 878

Table 27 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 5 (Pavia) 6939 129 145 224 425 116 6118 255 1789 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 5 (Pavia) 184 62 38 108 55 66 597 110

Table 28 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 5 (Pavia) 006

16

25 Sludge-amended-soil from Barcelona Spain

The sludge-amended soil material from Barcelona sampled upon indication from the Barcelorsquo- Group in Barcelona

Table 29 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 2 (Lleida T) 0015 0183 1138

Table 30 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 2

(Lleida T)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

159

045

nq

048

160

nq

nq

1000

1004

Table 31 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 2 (Lleida T) 059 141 327 536 405 186 184 224 lt 005 318 111

Table 32 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 2 (Lleida T) 4443 1067 1429 253 344 204 4116 780 3396 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 2 (Lleida T) 064 65 26 125 59 17 547 65

Table 33 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 2 (Lleida T) 010

17

26 Sludge amended soil from Essen Germany

The German sludge-amended soil from Essen which was provided as the three sludge materials by LUA NRW did not feature significant concentrations of the PCB congeners 28 52 101 118 153 105 138 156 180 170 but had detectable amounts of some PAHs

Table 34 ndash Analytical screening data on the German sludge-amended soil

Parameter Concentration(ngg)

Naphtalene lt10 Acenaphtylene lt10 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene lt10 Fluoranthene 28 Pyrene 20 Benz(a)anthracene 24 Chrysene 47 Benz(b)fluoranthene 76 Benz(k)fluoranthene 20 Benz(a)pyrene 35 Indeno(123-cd)pyrene 35 Dibenzo(ah)anthracene 10 Benzo(ghi)perylene 26

Table 35 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 4 (Essen) 0011 0302 055

Table 36 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 4

(Essen)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

nq

nq

nq

nq

nq

nq

128

191

203

18

Table 37 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 4 (Essen) 052 545 261 805 320 403 273 273 lt 005 295 781

Table 38 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 4 (Essen) 7947 442 085 06 086 007 2163 189 2019 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 4 (Essen) 045 19 42 87 683 60 462 61

Table 39 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 4 (Essen) 004

27 Long-term sludge exposed soil from Hohenheim-Stuttgart Germany

Similarly an additional sludge exposed soil was sampled at the University of Hohenheim Stuttgart were a test soil was long-term exposed to elevated concentrations of sewage sludge

Table 40 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 1 (Stuttgart) 0045 0263 1765

Table 41 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 1

(Stuttgart)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

230

006

004

004

nq

nd

nd

498

500

19

Table 42 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 1 (Stuttgart) 069 127 361 262 504 183 252 262 lt 005 266 142

Table 43 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 1 (Stuttgart) 7194 1006 133 186 366 088 7874 275 3571 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 1 (Stuttgart) 123 50 47 212 85 69 991 129

Table 44 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 1 (Stuttgart) 177

18

Annex 3

Statistical calculations

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 47)Mandels h statistics(Sludge 1 - PBD 47)

Sample Sludge 1 NUM

Element PBD 47

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00213 0001 3 -021 005 - - 10L - - NUM46L 00273 0002 4 016 021 - - 46L - - NUM64L 00059 0000 4 -116 002 NUM - 64L - - NUM12L 00188 0000 4 -036 002 - - 12L - - NUM26L 00499 0024 2 157 223 Fail - - 26L - - NUM

Totgem 0025 0005 mgkg 1-level 172 (185) NUM (10L46L64L12L26L) -1Totstd= 0016 0010 5-level 157 (162) 5

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 5 Labs rejected (10L46L64L12L26L)

000 050 100 150 200 250

k-values

10L

46L

64L

12L

26L

Mandels k statistics(Sludge 1 - PBD 47)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

10L

46L

64L

12L

26L

Labo

rato

ries

NUM

-200 -100 000 100 200

h-values

10L

46L

64L

12L

26L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 47)

Sludge 1-PBD 47

Unit mgkg

Mandels k statistics(Soil 3 - PBD 47)Mandels h statistics(Soil 3 - PBD 47)

Sample Soil 3 Soil 3 - PBD 47 -- Mean PARM = 0001 [mgkg]

Element PBD 47

General calcparmT1= 134814E-02T2= 142830E-05T3= 13T4= 45T5= 22767E-06

n= variabelp= 4

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean26L 00007 0000 2 -143 001 00007 00000 2 1 00046L 00010 0001 4 010 181 00010 00008 4 3 00010L 00011 0000 3 049 023 00011 00001 3 2 00012L 00012 0000 4 084 081 00012 00004 4 3 000

Totgem 0001 0000 mgkg 1-level 149 (177) 4 00010 () 4 3Totstd= 0000 0000 5-level 142 (159)

RESULTS Mean = 000100 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000050 --gt 5031 r = 00014Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000050 --gt 5031 R = 00014Remarks none

000 050 100 150 200

k-values

26L

46L

10L

12L

Mandels k statistics(Soil 3 - PBD 47)

00 00 00 00 00 00 00 00 00 00 00

Deviation from Mean

26L

46L

10L

12L

Labo

rato

ries

Soil 3 - PBD 47 -- Mean PARM = 0001 [mgkg]

-200 -100 000 100

h-values

26L

46L

10L

12L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 47)

Soil 3-PBD 47

Unit mgkg

Mandels k statistics(Compost 1 - PBD 99)Mandels h statistics(Compost 1 - PBD 99)

Sample Compost 1 Compost 1 - PBD 99 -- Mean PARM = 0003 [mgkg]

Element PBD 99

General calcparmT1= 492124E-02T2= 148747E-04T3= 17T4= 61T5= 93196E-06

n= variabelp= 5

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00020 0000 4 -137 053 00020 00004 4 3 000

26L 00025 0000 2 -058 024 00025 00002 2 1 00010L 00029 0000 3 012 032 00029 00003 3 2 00046L 00033 0001 4 069 161 00033 00013 4 3 00012L 00036 0001 4 114 140 00036 00011 4 3 000

Totgem 0003 0001 mgkg 1-level 172 (185) 5 00029 () 5 4Totstd= 0001 0001 5-level 157 (162)

RESULTS Mean = 000286 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000088 --gt 3086 r = 00025Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000101 --gt 3525 R = 00028Remarks none

000 050 100 150 200

k-values

4L

26L

10L

46L

12L

Mandels k statistics(Compost 1 - PBD 99)

00 00 00 00 00 00 00 00 00 00

Deviation from Mean

4L

26L

10L

46L

12L

Labo

rato

ries

Compost 1 - PBD 99 -- Mean PARM = 0003 [mgkg]

-200 -100 000 100 200

h-values

4L

26L

10L

46L

12L

Labo

rato

ries

Mandels h statistics(Compost 1 - PBD 99)

Compost 1-PBD 99

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 99)Mandels h statistics(Sludge 1 - PBD 99)

Sample Sludge 1 Sludge 1 - PBD 99 -- Mean PARM = 0024 [mgkg]

Element PBD 99

General calcparmT1= 448050E-01T2= 112113E-02T3= 19T4= 73T5= 32972E-05

n= variabelp= 5

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean64L 00173 0002 4 -118 041 Fail 00173 00019 4 3 -0014L 00183 0002 4 -104 032 00183 00015 4 3 -001

12L 00227 0001 4 -038 022 00227 00010 4 3 00010L 00290 0001 3 055 021 00290 00010 3 2 00146L 00320 0002 4 100 039 00320 00018 4 3 00126L 00323 0011 2 105 234 - - 26L - - 001

Totgem 0025 0003 mgkg 1-level 187 (177) 5 00239 (26L) 5 4Totstd= 0007 0004 5-level 166 (154) 1

RESULTS Mean = 002385 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000153 --gt 643 r = 00043Between lab variance S2L = 000004Reproducibility var S2R = 000004Reproducibility std SR = 000666 --gt 2791 R = 00186Remarks 1 Lab rejected (26L)

000 050 100 150 200 250

k-values

64L

4L

12L

10L

46L

26L

Mandels k statistics(Sludge 1 - PBD 99)

00 00 00 00 00 00 00 00 00 00

Deviation from Mean

64L

4L

12L

10L

46L

26L

Labo

rato

ries

Sludge 1 - PBD 99 -- Mean PARM = 0024 [mgkg]

-200 -100 000 100 200

h-values

64L

4L

12L

10L

46L

26L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 99)

Sludge 1-PBD 99

Unit mgkg

Mandels k statistics(Soil 3 - PBD 99)Mandels h statistics(Soil 3 - PBD 99)

Sample Soil 3 NUM

Element PBD 99

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00017 0000 4 091 068 - - 10L - - NUM46L 00017 0001 4 100 211 - - 46L - - NUM64L 00005 0000 4 -106 023 NUM - 64L - - NUM12L 00012 0000 4 015 014 - - 12L - - NUM26L 00006 0000 2 -101 012 - - 26L - - NUM

Totgem 0001 0000 mgkg 1-level 172 (173) NUM (10L46L64L12L26L) -1Totstd= 0001 0000 5-level 157 (153) 5

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 5 Labs rejected (10L46L64L12L26L)

000 050 100 150 200 250

k-values

10L

46L

64L

12L

26L

Mandels k statistics(Soil 3 - PBD 99)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

10L

46L

64L

12L

26L

Labo

rato

ries

NUM

-200 -100 000 100 200

h-values

10L

46L

64L

12L

26L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 99)

Soil 3-PBD 99

Unit mgkg

Mandels k statistics(Compost 1 - PBD 100)Mandels h statistics(Compost 1 - PBD 100)

Sample Compost 1 Compost 1 - PBD 100 -- Mean PARM = 0001 [mgkg]

Element PBD 100

General calcparmT1= 124272E-02T2= 113129E-05T3= 14T4= 52T5= 46584E-07

n= variabelp= 4

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean26L 00006 0000 2 -131 037 Fail 00006 00001 2 1 00010L 00009 0000 4 003 083 00009 00002 4 3 00046L 00009 0000 4 016 115 00009 00002 4 3 00012L 00011 0000 4 112 136 Fail 00011 00003 4 3 000

Totgem 0001 0000 mgkg 1-level 149 (167) 4 00009 () 4 3Totstd= 0000 0000 5-level 142 (15)

RESULTS Mean = 000085 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000022 --gt 2531 r = 00006Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000025 --gt 2882 R = 00007Remarks none

000 050 100 150

k-values

26L

10L

46L

12L

Mandels k statistics(Compost 1 - PBD 100)

00 00 00 00 00 00 00 00 00 00 00

Deviation from Mean

26L

10L

46L

12L

Labo

rato

ries

Compost 1 - PBD 100 -- Mean PARM = 0001 [mgkg]

-200 -100 000 100 200

h-values

26L

10L

46L

12L

Labo

rato

ries

Mandels h statistics(Compost 1 - PBD 100)

Compost 1-PBD 100

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 100)Mandels h statistics(Sludge 1 - PBD 100)

Sample Sludge 1 Sludge 1 - PBD 100 -- Mean PARM = 0005 [mgkg]

Element PBD 100

General calcparmT1= 852065E-02T2= 412762E-04T3= 18T4= 68T5= 78914E-07

n= variabelp= 5

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00039 0000 4 -042 007 Fail 00039 00002 4 3 000

12L 00044 0000 4 -041 005 Fail 00044 00001 4 3 00010L 00046 0000 4 -041 013 Fail 00046 00003 4 3 00046L 00056 0000 4 -040 012 Fail 00056 00003 4 3 00026L 00059 0000 2 -040 013 Fail 00059 00003 2 1 00038L 02168 0006 4 204 244 Fail - - 38L - - 021

Totgem 0040 0001 mgkg 1-level 187 (177) 5 00049 (38L) 5 4Totstd= 0087 0002 5-level 166 (154) 1

RESULTS Mean = 000486 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000025 --gt 507 r = 00007Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000084 --gt 1731 R = 00024Remarks 1 Lab rejected (38L)

000 050 100 150 200 250

k-values

4L

12L

10L

46L

26L

38L

Mandels k statistics(Sludge 1 - PBD 100)

-01 00 01 01 02 02 03

Deviation from Mean

4L

12L

10L

46L

26L

38L

Labo

rato

ries

Sludge 1 - PBD 100 -- Mean PARM = 0005 [mgkg]

-100 000 100 200 300

h-values

4L

12L

10L

46L

26L

38L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 100)

Sludge 1-PBD 100

Unit mgkg

Mandels k statistics(Soil 3 - PBD 100)Mandels h statistics(Soil 3 - PBD 100)

Sample Soil 3 NUM

Element PBD 100

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00003 0000 4 -050 000 Fail - - 10L - - NUM46L 00003 0000 4 -050 000 Fail NUM - 46L - - NUM3L 305500 2051 2 150 200 Fail - - 3L - - NUM

26L 00005 0000 2 -050 000 Fail - - 26L - - NUM

Totgem 7638 0513 mgkg 1-level 149 (177) NUM (10L46L3L26L) -1Totstd= 15275 1025 5-level 142 (159) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (10L46L3L26L)

000 050 100 150 200

k-values

10L

46L

3L

26L

Mandels k statistics(Soil 3 - PBD 100)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

10L

46L

3L

26L

Labo

rato

ries

NUM

-100 000 100 200

h-values

10L

46L

3L

26L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 100)

Soil 3-PBD 100

Unit mgkg

Mandels k statistics(Compost 1 - PBD 153)Mandels h statistics(Compost 1 - PBD 153)

Sample Compost 1 NUM

Element PBD 153

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean44L 00053 0001 3 150 157 Fail - - 44L - - NUM46L 00007 0000 4 -044 111 Fail - - 46L - - NUM12L 00005 0000 4 -051 055 Fail - - 12L - - NUM26L 00005 0000 2 -054 001 Fail NUM - 26L - - NUM

Totgem 0002 0000 mgkg 1-level 149 (177) NUM (44L46L12L26L) -1Totstd= 0002 0000 5-level 142 (159) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (44L46L12L26L)

000 050 100 150 200

k-values

44L

46L

12L

26L

Mandels k statistics(Compost 1 - PBD 153)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

44L

46L

12L

26L

Labo

rato

ries

NUM

-100 000 100 200

h-values

44L

46L

12L

26L

Labo

rato

ries

Mandels h statistics(Compost 1 - PBD 153)

Compost 1-PBD 153

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 153)Mandels h statistics(Sludge 1 - PBD 153)

Sample Sludge 1 Sludge 1 - PBD 153 -- Mean PARM = 0004 [mgkg]

Element PBD 153

General calcparmT1= 676738E-02T2= 267609E-04T3= 18T4= 68T5= 19626E-05

n= variabelp= 5

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00024 0000 4 -157 017 00024 00002 4 3 000

12L 00038 0002 4 006 154 00038 00018 4 3 00046L 00039 0000 4 011 026 00039 00003 4 3 00026L 00039 0000 2 018 004 00039 00000 2 1 00064L 00049 0002 4 122 159 00049 00018 4 3 000

Totgem 0004 0001 mgkg 1-level 172 (173) 5 00038 () 5 4Totstd= 0001 0001 5-level 157 (153)

RESULTS Mean = 000378 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000123 --gt 3252 r = 00034Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000142 --gt 3754 R = 00040Remarks none

000 050 100 150 200

k-values

4L

12L

46L

26L

64L

Mandels k statistics(Sludge 1 - PBD 153)

00 00 00 00 00 00 00

Deviation from Mean

4L

12L

46L

26L

64L

Labo

rato

ries

Sludge 1 - PBD 153 -- Mean PARM = 0004 [mgkg]

-200 -100 000 100 200

h-values

4L

12L

46L

26L

64L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 153)

Sludge 1-PBD 153

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 154)Mandels h statistics(Sludge 1 - PBD 154)

Sample Sludge 1 NA

Element PBD 154

General calcparmT1= NAT2= NAT3=T4=T5=

n= variabelp=

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00021 0000 3 -100 021 NA - 4L - - NA

46L 00025 0000 4 115 018 NA - 46L - - NA64L 00021 0001 4 -066 179 - - 64L - - NA12L 00023 0000 4 050 085 - - 12L - - NA

Totgem 0002 0000 mgkg 1-level 149 (167) NA (4L46L64L12L) -1Totstd= 0000 0000 5-level 142 (15) 4

RESULTS Mean = NA mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NAReproducibility var S2R = NAReproducibility std SR = NA --gt NA R = NARemarks 4 Labs rejected (4L46L64L12L)

000 050 100 150 200

k-values

4L

46L

64L

12L

Mandels k statistics(Sludge 1 - PBD 154)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

4L

46L

64L

12L

Labo

rato

ries

NA

-100 000 100 200

h-values

4L

46L

64L

12L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 154)

Sludge 1-PBD 154

Unit mgkg

Mandels k statistics(Soil 3 - PBD 154)Mandels h statistics(Soil 3 - PBD 154)

Sample Soil 3 NUM

Element PBD 154

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

4L 00010 - 1 150 Fail - - 4L - - NUM46L 00001 0000 4 -053 096 Fail - - 46L - - NUM64L 00001 0000 4 -056 105 Fail NUM - 64L - - NUM12L 00002 0000 4 -040 099 Fail - - 12L - - NUM

Totgem 000037 0000 mgkg 1-level 149 (164) NUM (4L46L64L12L) -1Totstd= 000042 0000 5-level 142 (153) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (4L46L64L12L)

000 050 100 150

k-values

4L

46L

64L

12L

Mandels k statistics(Soil 3 - PBD 154)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

4L

46L

64L

12L

Labo

rato

ries

NUM

-100 000 100 200

h-values

4L

46L

64L

12L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 154)

Soil 3-PBD 154

Unit mgkg

Mandels k statistics(Compost 1 - PBD 209)Mandels h statistics(Compost 1 - PBD 209)

Sample Compost 1 NUM

Element PBD 209

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00065 0003 2 -049 032 - - 4L - - NUM

44L 00573 0021 4 150 197 Fail - - 44L - - NUM12L 00078 0001 4 -045 011 - - 12L - - NUM26L 00049 0000 2 -056 000 NUM - 26L - - NUM

Totgem 0019 0006 mgkg 1-level 149 (177) NUM (4L44L12L26L) -1Totstd= 0025 0010 5-level 142 (159) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (4L44L12L26L)

000 050 100 150 200

k-values

4L

44L

12L

26L

Mandels k statistics(Compost 1 - PBD 209)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

4L

44L

12L

26L

Labo

rato

ries

NUM

-100 000 100 200

h-values

4L

44L

12L

26L

Labo

rato

ries

Mandels h statistics(Compost 1 - PBD 209)

Compost 1-PBD 209

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 209)Mandels h statistics(Sludge 1 - PBD 209)

Sample Sludge 1 Sludge 1 - PBD 209 -- Mean PARM = 0249 [mgkg]

Element PBD 209

General calcparmT1= 394542E+00T2= 107296E+00T3= 16T4= 56T5= 19723E-02

n= variabelp= 5

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 01550 0055 4 -112 148 Fail 01550 00551 4 3 -009

46L 02050 0007 2 -053 019 02050 00071 2 1 -00412L 02137 0058 4 -042 155 02137 00576 4 3 -00426L 03149 0021 2 078 057 Fail 03149 00210 2 1 00764L 03577 0007 4 129 020 Fail 03577 00074 4 3 011

Totgem 0249 0030 mgkg 1-level 172 (185) 5 02493 () 5 4Totstd= 0084 0025 5-level 157 (162)

RESULTS Mean = 024926 mgkg

Repeatability variance S2r = 000179Repeatability std Sr = 004234 --gt 1699 r = 01186Between lab variance S2L = 000743Reproducibility var S2R = 000922Reproducibility std SR = 009604 --gt 3853 R = 02689Remarks none

000 050 100 150 200

k-values

4L

46L

12L

26L

64L

Mandels k statistics(Sludge 1 - PBD 209)

-01 -01 00 01 01 02

Deviation from Mean

4L

46L

12L

26L

64L

Labo

rato

ries

Sludge 1 - PBD 209 -- Mean PARM = 0249 [mgkg]

-200 -100 000 100 200

h-values

4L

46L

12L

26L

64L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 209)

Sludge 1-PBD 209

Unit mgkg

Mandels k statistics(Soil 3 - PBD 209)Mandels h statistics(Soil 3 - PBD 209)

Sample Soil 3 Soil 3 - PBD 209 -- Mean PARM = 0258 [mgkg]

Element PBD 209

General calcparmT1= 596398E+00T2= 191917E+00T3= 22T4= 84T5= 13249E-02

n= variabelp= 6

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean26L 01162 0021 2 -108 074 Fail 01162 00207 2 1 -0144L 01303 0031 4 -097 111 Fail 01303 00312 4 3 -013

46L 01975 0036 4 -046 128 Fail 01975 00359 4 3 -00644L 02898 0035 4 024 124 Fail 02898 00346 4 3 00312L 03895 0018 4 100 065 Fail 03895 00181 4 3 01364L 04260 0022 4 127 078 Fail 04260 00219 4 3 017

Totgem 0258 0027 mgkg 1-level 187 (177) 6 02582 () 6 5Totstd= 0132 0008 5-level 166 (154)

RESULTS Mean = 025818 mgkg

Repeatability variance S2r = 000083Repeatability std Sr = 002878 --gt 1115 r = 00806Between lab variance S2L = 001640Reproducibility var S2R = 001723Reproducibility std SR = 013127 --gt 5084 R = 03676Remarks none

000 050 100 150

k-values

26L

4L

46L

44L

12L

64L

Mandels k statistics(Soil 3 - PBD 209)

-02 -01 -01 00 01 01 02 02

Deviation from Mean

26L

4L

46L

44L

12L

64L

Labo

rato

ries

Soil 3 - PBD 209 -- Mean PARM = 0258 [mgkg]

-200 -100 000 100 200

h-values

26L

4L

46L

44L

12L

64L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 209)

Soil 3-PBD 209

Unit mgkg

Mandels k statistics(Compost 1 - Sum PBD)Mandels h statistics(Compost 1 - Sum PBD)

Sample Compost 1 Compost 1 - Sum PBD -- Mean PARM = 0009 [mgkg]

Element Sum PBD

General calcparmT1= 154064E-01T2= 169065E-03T3= 18T4= 68T5= 11354E-04

n= variabelp= 5

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00031 0002 4 -067 016 00031 00016 4 3 -0014L 00055 0005 4 -056 048 00055 00047 4 3 000

46L 00085 0003 4 -042 031 00085 00030 4 3 00026L 00123 0000 2 -024 003 00123 00002 2 1 00012L 00154 0002 4 -011 021 00154 00021 4 3 00144L 00613 0023 4 200 237 Fail - - 44L - - 005

Totgem 0018 0006 mgkg 1-level 187 (177) 5 00089 (44L) 5 4Totstd= 0022 0009 5-level 166 (154) 1

RESULTS Mean = 000893 mgkg

Repeatability variance S2r = 000001Repeatability std Sr = 000296 --gt 3308 r = 00083Between lab variance S2L = 000002Reproducibility var S2R = 000003Reproducibility std SR = 000570 --gt 6374 R = 00159Remarks 1 Lab rejected (44L)

000 050 100 150 200 250

k-values

10L

4L

46L

26L

12L

44L

Mandels k statistics(Compost 1 - Sum PBD)

00 00 00 00 00 00 01 01

Deviation from Mean

10L

4L

46L

26L

12L

44L

Labo

rato

ries

Compost 1 - Sum PBD -- Mean PARM = 0009 [mgkg]

-100 000 100 200

h-values

10L

4L

46L

26L

12L

44L

Labo

rato

ries

Mandels h statistics(Compost 1 - Sum PBD)

Compost 1-Sum PBD

Unit mgkg

Mandels k statistics(Sludge 1 - Sum PBD)Mandels h statistics(Sludge 1 - Sum PBD)

Sample Sludge 1 Sludge 1 - Sum PBD -- Mean PARM = 0256 [mgkg]

Element Sum PBD

General calcparmT1= 531806E+00T2= 162188E+00T3= 22T4= 84T5= 25223E-02

n= variabelp= 6

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00423 0025 4 -156 044 Fail 00423 00252 4 3 -02146L 01808 0118 4 -049 205 - - 46L - - -0074L 01810 0056 4 -049 097 01810 00558 4 3 -007

38L 02168 0006 4 -022 010 02168 00059 4 3 -00412L 02890 0065 4 034 113 02890 00647 4 3 00364L 03958 0008 4 116 014 Fail 03958 00079 4 3 01426L 04094 0034 2 126 059 Fail 04094 00337 2 1 015

Totgem 0245 0044 mgkg 1-level 198 (179) 6 02557 (46L) 6 5Totstd= 0130 0039 5-level 171 (155) 1

RESULTS Mean = 025570 mgkg

Repeatability variance S2r = 000158Repeatability std Sr = 003970 --gt 1553 r = 01112Between lab variance S2L = 001807Reproducibility var S2R = 001964Reproducibility std SR = 014015 --gt 5481 R = 03924Remarks 1 Lab rejected (46L)

000 050 100 150 200 250

k-values

10L

46L

4L

38L

12L

64L

26L

Mandels k statistics(Sludge 1 - Sum PBD)

-03 -02 -02 -01 -01 00 01 01 02 02

Deviation from Mean

10L

46L

4L

38L

12L

64L

26L

Labo

rato

ries

Sludge 1 - Sum PBD -- Mean PARM = 0256 [mgkg]

-200 -100 000 100 200

h-values

10L

46L

4L

38L

12L

64L

26L

Labo

rato

ries

Mandels h statistics(Sludge 1 - Sum PBD)

Sludge 1-Sum PBD

Unit mgkg

Mandels k statistics(Soil 3 - Sum PBD)Mandels h statistics(Soil 3 - Sum PBD)

Sample Soil 3 Soil 3 - Sum PBD -- Mean PARM = 0227 [mgkg]

Element Sum PBD

General calcparmT1= 610980E+00T2= 200876E+00T3= 26T4= 100T5= 13106E-02

n= variabelp= 7

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00028 0001 4 -037 000 Fail 00028 00005 4 3 -02226L 01179 0021 2 -036 003 Fail 01179 00208 2 1 -0114L 01305 0031 4 -036 004 Fail 01305 00308 4 3 -010

46L 02065 0035 4 -036 005 Fail 02065 00350 4 3 -00244L 02923 0037 4 -035 005 Fail 02923 00365 4 3 00712L 04051 0015 4 -034 002 Fail 04051 00149 4 3 01864L 04314 0022 4 -033 003 Fail 04314 00223 4 3 0203L 305500 2051 2 247 283 Fail - - 3L - - 3032

Totgem 4017 0276 mgkg 1-level 206 (181) 7 02266 (3L) 7 6Totstd= 10722 0717 5-level 175 (156) 1

RESULTS Mean = 022663 mgkg

Repeatability variance S2r = 000069Repeatability std Sr = 002626 --gt 1159 r = 00735Between lab variance S2L = 002568Reproducibility var S2R = 002637Reproducibility std SR = 016238 --gt 7165 R = 04547Remarks 1 Lab rejected (3L)

000 050 100 150 200 250 300

k-values

10L

26L

4L

46L

44L

12L

64L

3L

Mandels k statistics(Soil 3 - Sum PBD)

-50 00 50 100 150 200 250 300 350

Deviation from Mean

10L

26L

4L

46L

44L

12L

64L

3L

Labo

rato

ries

Soil 3 - Sum PBD -- Mean PARM = 0227 [mgkg]

-100 000 100 200 300

h-values

10L

26L

4L

46L

44L

12L

64L

3L

Labo

rato

ries

Mandels h statistics(Soil 3 - Sum PBD)

Soil 3-Sum PBD

19

Annex 4

Raw data submitted

Sample Compost1 Sample Compost 1 Sample Compost 1Element PBD 99 Element PBD 100 Element PBD 153

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]4L 00021 10L 00008 44L 000504L 00024 10L 00008 44L 000604L 00014 10L 00007 44L 000504L 00020 10L 00011 46L 00004

10L 00029 46L 00007 46L 0001210L 00027 46L 00012 46L 0000410L 00032 46L 00009 46L 0000946L 00025 46L 00007 12L 0000446L 00052 12L 00008 12L 0000846L 00029 12L 00012 12L 0000446L 00026 12L 00008 12L 0000712L 00026 12L 00014 26L 0000512L 00043 26L 00007 26L 0000512L 00026 26L 0000612L 0004726L 0002626L 00024

Sample Compost 1 Sample Compost 1 Sample Compost 1Element PBD 154 Element PBD 183 Element PBD 196

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]4L 00010 46L 00002 46L 00011

46L 00003 46L 00024 46L 0000846L 00007 46L 00021 12L 0000246L 00003 46L 00003 12L 0000346L 00004 12L 00003 12L 0000112L 00003 12L 00011 12L 0000212L 00005 12L 0000312L 00031 12L 0000312L 00006

Sample Compost 1 Sample Compost 1 Sample Compost 1Element PBD 197 Element PBD 203 Element PBD 209

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00002 46L 00010 4L 0004146L 00023 12L 00002 4L 0008946L 00022 12L 00003 44L 0041012L 00004 12L 00002 44L 0084012L 00006 12L 00002 44L 0064012L 00003 44L 0040012L 00004 12L 00079

12L 0007312L 0006512L 0009326L 0004926L 00049

Sample Compost 1Element PBD 47

LAB PARM [mgkg]26L 0003826L 00039

Element PBD 99 Element PBD 47 Element PBD 209LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]

4L 00170 10L 00210 4L 010004L 00200 10L 00220 4L 018004L 00170 10L 00210 4L 012004L 00190 46L 00300 4L 0220010L 00280 46L 00280 46L 0210010L 00300 46L 00250 46L 0200010L 00290 46L 00260 64L 0351846L 00340 64L 00059 64L 0363846L 00330 64L 00057 64L 0364546L 00300 64L 00062 64L 0350846L 00310 64L 00060 12L 0220964L 00194 12L 00191 12L 0177164L 00154 12L 00187 12L 0292264L 00185 12L 00190 12L 0164664L 00159 12L 00186 26L 0329712L 00242 26L 00666 26L 0300012L 00223 26L 0033212L 0022112L 0022226L 0024626L 00400

Element PBD 203 Element PBD 197 Element PBD 196LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00022 46L 00027 46L 0002446L 00014 46L 00024 46L 0002264L 00036 12L 00161 64L 0005864L 00058 12L 00060 64L 0006512L 00063 12L 00061 12L 0004812L 00034 12L 00036 12L 0002512L 00038 12L 0003212L 00027 12L 00022

Element PBD 183 Element PBD 154 Element PBD 153LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00049 4L 00020 4L 0002246L 00035 4L 00022 4L 0002446L 00036 4L 00020 4L 0002246L 00034 46L 00025 4L 0002664L 00027 46L 00025 46L 0004064L 00023 46L 00025 46L 0004264L 00024 46L 00023 46L 0003564L 00020 64L 00034 46L 0003812L 00230 64L 00023 64L 0007412L 00032 64L 00017 64L 0004712L 00031 64L 00011 64L 0004612L 00030 12L 00030 64L 0003026L 00007 12L 00021 12L 0006526L 00008 12L 00021 12L 00029

12L 00021 12L 0003226L 00015 12L 0002926L 00019 26L 00039

26L 00040

Element PBD 100LAB PARM [mgkg]

4L 000384L 000414L 000374L 00038

38L 0219038L 0220038L 0208038L 0220010L 0004410L 0005010L 0004310L 0004646L 0005746L 0005946L 0005346L 0005312L 0004312L 0004512L 0004312L 0004326L 0006226L 00057

Sample Soil 3 Sample Soil 3 Sample Soil 3Element PBD 99 Element PBD 47 Element PBD 100

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]10L 00016 10L 00011 10L 0000310L 00019 10L 00010 10L 0000410L 00013 10L 00012 10L 0000410L 00019 46L 00007 10L 0000246L 00025 46L 00022 46L 0000246L 00025 46L 00005 46L 0000646L 00008 46L 00007 46L 0000246L 00011 12L 00010 46L 0000264L 00005 12L 00017 3L 29100064L 00005 12L 00010 3L 32000064L 00006 12L 00009 26L 0000564L 00007 26L 00007 26L 0000512L 00012 26L 0000712L 0001312L 0001312L 0001226L 0000526L 00006

Sample Soil 3 Sample Soil 3 Sample Soil 3Element PBD 153 Element PBD 154 Element PBD 196

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]44L 00050 4L 00010 46L 0000744L 00050 46L 00001 46L 0001146L 00002 46L 00002 46L 0000846L 00003 46L 00001 46L 0001146L 00002 46L 00002 64L 0002646L 00002 64L 00001 64L 0002664L 00001 64L 00001 64L 0002964L 00001 64L 00001 64L 0003464L 00001 64L 00002 12L 0004564L 00002 12L 00003 12L 00032

12L 00002 12L 0002212L 00002 12L 0002112L 00002

Sample Soil 3 Sample Soil 3 Sample Soil 3Element PBD 197 Element PBD 203 Element PBD 209

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00006 46L 00011 4L 0091046L 00013 46L 00017 4L 0150046L 00011 46L 00015 4L 0120046L 00013 46L 00018 4L 0160012L 00090 64L 00013 44L 0337012L 00056 64L 00014 44L 0281012L 00033 64L 00016 44L 0287012L 00032 64L 00015 44L 02540

12L 00055 46L 0230012L 00041 46L 0220012L 00027 46L 0150012L 00026 46L 01900

64L 0438164L 0401664L 0414464L 0449812L 0367112L 0397812L 0409112L 03838

Sample Soil 3 26L 0102Element PBD 183 26L 0131

LAB PARM [mgkg]46L 0000746L 0000846L 0005846L 0000764L 0000264L 0000364L 0000364L 0000312L 0001512L 0001112L 0000712L 00007

European Commission EUR 23003 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on polybrominated diphenylethers Author(s) E Sobiecka H van der Sloot D Barcelo B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 68 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07403-5 Abstract Project HORIZONTAL is interdisciplinary aiming at a harmonisation and horizontal standardisation of test procedures in particular for sludge soils and biowastes In the context of this standardization project a series of draft technical specification were designed upon an extensive desk study fine-tuned after expert consultations and finally validated in international intercomparisons exercise This report summarises the work performed within the validation study of the draft standard for the determination of polybrominated diphenylethers (PBDE) in soils sludge and treated bio-waste using gas-chromatography method with mass selective detection (GC-MS) It further explains the underlying statistical concept for the calculation of reproducibility and repeatability from intercomparisons data In addition all single values results of the statistical evaluation as well as background information on the validation materials used are described and explained

The mission of the JRC is to provide customer-driven scientific and technical support for the conception development implementation and monitoring of EU policies As a service of the European Commission the JRC functions as a reference centre of science and technology for the Union Close to the policy-making process it serves the common interest of the Member States while being independent of special interests whether private or national

LB

-NA

-23003-EN

-C

10

126 Participants The following table lists the participating organisations and entities in the validation exercise for the horizontal PBDE standard

bull Austria o Umweltbundesamt

bull Czech Republic o Povodi Labe statni podnik - OVHL Laboratory

bull France o CIRSEE o CTC Environnement o INERIS

bull Germany o Federal Environmental Agency Section III 34 Laboratory Methods for

the Surveillance of Waste and Wastewater (UBA) bull Italy

o European Commission DG JRC IES bull Spain

o Consejo Superior de Investigaciones Cientificas (CSIC)

bull Sweden o ALCONTROL AB

11

13 Summary results and derived performance characteristics The result of the various statistical evaluation including outlier tests calculation of repeatability and reproducibility standard deviation for the congeners of interest can be found in Annex 3 of this report In addition all data submitted by the participants as well as those considered for the calculation of the performance characteristics are listed in Annex 3 to this report Based on these calculations the following results were obtained in the validation round upon statistical evaluation according to ISO 5725-2 The average values the repeatability standard deviation (sr) and the reproducibility standard deviation (sR) were obtained (Table1) The repeatability is determined as an interval around a measurement result (ie repeatability limit) This interval corresponds to the maximum difference that can be expected (with a 95 statistical confidence) between one test result and another both test results being obtained under the following conditions The tests are performed in accordance with all the requirements of the present standard by the same laboratory using its own facilities and testing laboratory samples obtained from the same primary field sample and prepared under identical procedures The repeatability limit was calculated using the relationship r test = f radic2 s rtest with the critical range factor f = 2 The reproducibility like repeatability is also determined as an interval around a measurement result (ie reproducibility limit) This interval corresponds to the maximum difference that can be expected (with a 95 statistical confidence) between one test result and another test result obtained by another laboratory both test results being obtained under the following conditions The tests are performed in accordance with all the requirements of the present standard by two different laboratories using their own facilities and testing laboratory samples obtained from the same primary field sample and prepared under identical procedures The reproducibility limit was calculated using the relationship R = f radic2 sR with the critical range factor f = 2

12

Table 1 - Results of the interlaboratory comparison studies of the determination of selected polybrominated diphenyl ethers (PBDE) by gaschromatography with mass spectrometric detection (GC-MS) in soil sludge and treated biowaste All concentrations are expressed in mgkg dm

Matrix Parameter Mean sr sR r R p Outliers Used No of data

No of data reported below

detection

Total no of data

Sludge 1 PBD 47 00181 461 4 15 5 20 Compost 1 00039 94 3 12 0 12 Soil 3 00010 50 50 00014 00014 4 0 13 10 23 Sludge 1 PBD 99 00239 64 28 00043 00186 5 1 19 0 23 Compost 1 00029 31 35 00025 00028 5 0 17 4 21 Soil 3 00013 499 4 16 8 24 Sludge 1 PBD 100 00049 51 17 00007 00024 5 1 18 2 24 Compost 1 00009 25 29 00006 00007 4 0 14 7 21 Soil 3 61103 211 3 10 15 25 Sludge 1 PBD 153 00038 33 38 00034 0004 5 0 18 0 18 Compost 1 00019 116 3 11 3 14 Soil 3 00011 177 2 10 10 20 Sludge 1 PBD 154 00023 234 4 15 2 17 Compost 1 00008 1118 3 9 5 14

13

Matrix Parameter Mean sr sR r R p Outliers Used No of data

No of data reported below

detection

Total no of data

Soil 3 00002 1049 4 13 6 19 Sludge 1 PBD 183 00048 1217 3 12 2 14 Compost 1 00009 1048 2 8 5 13 Soil 3 00011 1395 3 12 6 18 Sludge 1 PBD 196 00037 470 2 8 7 15 Compost 1 00004 950 2 6 4 10 Soil 3 00023 519 3 12 2 14 Sludge 1 PBD 197 00062 834 2 6 8 14 Compost 1 00009 1001 2 7 7 14 Soil 3 00032 904 2 8 6 14 Sludge 1 PBD 203 00037 461 2 8 4 12 Compost 1 00004 978 2 5 3 8 Soil 3 00022 598 3 12 0 12 Sludge 1 PBD 209 02493 170 39 01186 02689 5 0 16 2 18 Compost 1 00273 104 3 10 5 15 Soil 3 02582 1115 51 00806 03676 6 0 22 0 22

14

Matrix Parameter Mean sr sR r R p Outliers Used No of data

No of data reported below

detection

Total no of data

Sludge 1 Sum PBD 0256 155 548 0111 0392 6 1 22 Compost 1 0009 331 637 0008 0016 5 1 18 Soil 3 0227 116 717 0074 0455 7 1 26 Abbreviations sr Repeatability standard deviation SR Reproducibility standard deviation r Repeatability limit (comparing two measurements) R Reproducibility limit (comparing two measurements) p Number of labs determination not possible

15

14 Annexes Annex 1 Model questionnaire to be filled by the participating laboratories Annex 3 Report on the validation materials used Annex 2 Statistical calculations Annex 3 Data submitted

16

Annex 1

Model questionnaire to be filled by the participating laboratories

Model questionnaire to be filled by the participating laboratories Name of laboratory Contact person Contact details email Phone Fax Mail address of lab Dispatch address of lab for shipment of samples (no PO boxes) Title of measurement method (copy attached) Our laboratory is willing to participate in the precision experiment for this draft standard method

Yes No As participant we understand that

bull All essential apparatus chemicals and other requirements specified in the method must be available in our laboratory when the programme begins

bull Specified timing requirements such as starting and finishing date of the programme must be rigidly met

bull The method must be strictly adhered to bull Samples must be handled in accordance with instructions bull A qualified operator must perform the measurements

Having studied the method and having made a fair appraisal of our capabilities and facilities we feel that we will be adequately prepared for cooperative testing of this method Comments helliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphellip Signature Date

17

Annex 2

Report on the validation materials used

VI

Abstract This report gives an overview on the available analytical information on the following raw materials to be used for the production of validation materials of the so-called Project HORIZONTAL

bull Four sludge materials from Duumlsseldorf Germany

bull An agricultural soil material from Reading United Kingdom

bull A compost material from Vienna Austria

bull A compost material from Korschenbroich Germany

bull A sludge-amended agricultural soil from Pavia Province Italy

bull A sludge-amended soil from Barcelona Spain

bull A sludge-amended soil from Essen Germany

bull A long-term sludge exposed soil from Hohenheim Germany

VII

List of Abbreviations Throughout this report the following abbreviations are used

AOX absorbable organic halogens

Corg organic carbon content

Ctotal total carbon content

CAT cation exchangeable

CDD chlorinated dibenzodioxin

CDF chlorinated dibenzofuran

DEHP di(2-ethylhexyl)phthalate

DM dry matter

EPA Environment Protection Agency

EU European Union

FM fresh matter

Hp hepta

Hx hexa

IES Institute for Environment and Sustainability

IRMM Institute for Reference Materials and Measurements

JRC Joint Research Centre

LAS linear alkylsulfonates

LoD limit of detection

LUA Landesumweltamt

Ntotal total nitrogen content

NH4-N Ammonium nitrogen

NO3-N Nitrate nitrogen

NP nonylphenol

NRW North Rhine Westphalia

O octa

P poly

PAH polycyclic aromatic hydrocarbon

PCB polychlorinated biphenyl

Pe penta

T tetra

TEQ toxicity equivalent

UBA Umweltbundesamt

WHO World Health Organization

WWTP waste water treatment plant

6

1 Introduction This report gives an overview on the available analytical information on the following raw materials to be used for the production of validation materials of the so-called Project HORIZONTAL

bull Four sludge materials from Duumlsseldorf Germany

bull An agricultural soil material from Reading United Kingdom

bull A compost material from Vienna Austria

bull A compost material from Korschenbroich Germany

bull A sludge-amended agricultural soil from Pavia Province Italy

bull A sludge-amended soil from Barcelona Spain

bull A sludge-amended soil from Essen Germany

bull A long-term sludge exposed soil from Hohenheim Germany

The following analytical information was gathered partly before and during the sampling of the raw materials to be used for the production of the HORIZONTAL validation materials The material were sampled by IES and shipped to IRMM in the course of the year 2005 The information gathered was then completed by various analytical screenings for PAHs and PCBs done by the Institute for Reference Materials and Measurements Geel Belgium for phthalates done by UBA Berlin Germany for PBDE done by IIQAB-CSIC Barcelona Spain for trace elements and some selected major and minor elements by the Institute for Environment and Sustainability Ispra Italy

The work compiled hereafter is based on the numerous additional efforts of the scientists working at various members of the consortium Project HORIZONTAL-Org and contributing organisations

This work is gratefully acknowledged

2 Overview on property values

21 Sludge materials from Duumlsseldorf Germany

The various sewage sludge materials originate from various installations in the North Rhine Westphalia and were produced and sampled by staff from the Landesumweltamt (LUA) NRW under the responsibility from Dr K Furtmann

In total four sludge materials (Sludge A and D from a major municipal WWTP Sludge B from a municipal WWTP with industrial input and Sludge C from a municipal WWTP with high PCB-Content) were obtained and will be blended to two final materials Before sampling the following analytical data for a typical sample were received

7

Table 1 ndash Analytical data obtained on an average sludge sample in LUA NRW (with courtesy of K Furtmann LUA Duumlsseldorf)

Parameter Concentration PCB 120 ugkg DEHP 110 mgkg PAH 5 mgkg (EPA) PCDDF 15 ng TEkg PBDE 400 ugkg NP 40 mgkg LAS 3 gkg AOX 300 mgkg

Subsequent screening led to the information displayed hereafter It should be stressed that the data were obtained as SCREENING information on the UNTREATED or partially treated raw materials Therefore the final target values which are relevant for the validation intercomparison can be different

Table 2 ndash Analytical data obtained on a first screening on the sludge samples from LUA NRW

Sewage sludge A

Dusseldorf

sewage sludge D

Dusseldorf PCB (ngg) 28 62 35 52 101 65 101 31 38 118 49 40 153 30 33 105 24 11 138 46 38 156 lt1 lt1 180 34 23 170 23 19 PAH (ngg) Naphtalene 34 381 Acenaphtylene 15 43 Acenaphthene 81 108 Fluorene 94 1167 Phenantrene 3440 Anthracene 22 344 Flouranthene 316 4817 Pyrene 235 3011 Benz(a)anthracene 473 791 Chrysene 691 1078 Benz(b)fluoranthene 538 1688 Benz(k)fluoranthene 228 635 Benz(a)pyrene 383 1114 Indeno(123-cd)pyrene 92 229 Dibenzo(ah)anthracene 71 70 Benzo(ghi)perylene 80 185

8

Table 3 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Sludge D (1) 0135 41474 385 Sludge B (2) 0538 0034 30634 547 Sludge A (3) 0184 0037 31399 146 Sludge C (4) 0354 1528 6678 229

Table 4 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Sludge 2

(B)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

554

959

694

591

772

509

nq

nq

970

2216

2379

Table 5 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena IES Ispra Spain) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Sludge 1 (D) 265 290 533 359 1231 338 784 438 lt 005 232 786 Sludge 2 (B) 119 311 626 202 278 299 722 251 lt 005 118 625 Sludge 3 (A) 168 360 621 332 847 416 119 451 lt 005 116 1237 Sludge 4 (C) 563 198 116 273 726 511 473 618 lt 005 444 2015

Table 6 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Sludge 1 (D) 2154 58 844 099 103 101 4367 lt15 50448 Sludge 2 (B) 1067 366 692 046 1491 077 5217 lt15 57633 Sludge 3 (A) 731 663 684 035 1287 068 3733 lt15 60369 Sludge 4 (C) 4379 965 527 163 522 107 5628 lt15 23945

Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM)Sludge 1 (D) 03 2403 101 1002 350 15 1944 132Sludge 2 (B) 031 315 97 879 172 12 514 180Sludge 3 (A) 031 1281 153 1567 265 16 1440 168Sludge 4 (C) 055 231 628 2625 371 81 1101 244

9

22 Agricultural soil material from Reading United Kingdom

The material was proposed by the University of Reading (S Nortcliff) and was sampled from a site called ldquoFrogmore Farmrdquo which was featured in the ldquoMetalsrdquo Report for HORIZONTAL This site is close to Reading with soils developed on flintyloamy periglacial materials over Chalk has a long and well documented history of sludge application The focus of the work of Nortcliff et al undertook at this site and the monitoring and control at the site (by Thames Water and the subsequent subsidiary bodies dealing with sludge application to soil) was on metals (and metal loads) with no analysis or indeed any form of investigation in to organics in the broadest sense

The analytical information produced in the context of the screening of the raw material is displayed below

Table 7 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 3

(Reading) 0032 0119 669

Table 8 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 3 (Reading) 015 706 279 138 152 901 267 300 lt 005 258 931

Table 9 ndash Analytical data obtained on a first screening on the sludge-amended soil from Reading (courtesy of IRMM)

Parameter Concentration

PCB ngg 28 lt1 52 lt1 101 lt1 118 lt1 153 lt1 105 lt1 138 lt1 156 lt1 180 lt1 170 lt1 PAH ngg Naphtalene lt10 Acenaphtylene 21 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene lt10 Flouranthene 818 Pyrene 776 Benz(a)anthracene 565

10

Parameter Concentration

Chrysene 608 Benz(b)fluoranthene 824 Benz(k)fluoranthene 329 Benz(a)pyrene 799 Indeno(123-cd)pyrene

779

Dibenzo(ah)anthracene 118 Benzo(ghi)perylene 394

Table 10 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 3

(Reading)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

103

003

nq

nq

nq

nd

nd

272

273

Table 11 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 3 (Reading) 015 706 279 138 152 901 267 300 lt 005 258 931

Table 12 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 3 (Reading) 7936 477 112 096 194 017 4107 443 2102 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 3 (Reading) 042 13 45 69 69 69 216 92

Table 13 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 3 (Reading) 012

11

23 Compost from Vienna Austria

The fresh compost material was obtained from the Austrian Federal Environment Agency (UBA Vienna) which had used a sub-batch of the raw material for national intercomparson The remainder of the material was stored at 4degC until shipment to IRMM for further processing The following analytical information was provided by UBA Austria and completed with various screenings

Table 14 ndash Analytical data on compost material received from UBA Austria Inorganic and sum parameters

Parameter Unit Sample fraction used Observed mean B CAT mgl FM Fresh sample lt10mm 61 K CAT mgl FM Fresh sample lt10mm 2624 Mg CAT mgl FM Fresh sample lt10mm 242 P CAT mgl FM Fresh sample lt10mm 49 B CAT DM Fresh sample lt10mm 00017 K CAT DM Fresh sample lt10mm 072 Mg CAT DM Fresh sample lt10mm 007 P CAT DM Fresh sample lt10mm 001 NO3-N mgkg FM Fresh sample lt10mm 35 NH4-N mgkg FM Fresh sample lt10mm 230 Ctotal DM lt45degdry milled 29 Corg DM lt45degdry milled 27 Ntotal DM lt45degdry milled 17 P mgkg DM lt45degdry milled 2596 K mgkg DM lt45degdry milled 11019 K DM lt45degdry milled 110 B mgkg DM lt45degdry milled 60 Cd mgkg DM lt45degdry milled 046 Cr mgkg DM lt45degdry milled 25 Cu mgkg DM lt45degdry milled 46 Hg mgkg DM lt45degdry milled 020 Ni mgkg DM lt45degdry milled 18 Pb mgkg DM lt45degdry milled 45 Zn mgkg DM lt45degdry milled 198 Ca mgkg DM lt45degdry milled 68776 Ca DM lt45degdry milled 69 Mo mgkg DM lt45degdry milled 08 S mgkg DM lt45degdry milled 2137 Fe mgkg DM lt45degdry milled 9959 Mn mgkg DM lt45degdry milled 418 Na mgkg DM lt45degdry milled 742 Co mgkg DM lt45degdry milled 41 AOX mgkg DM lt30deg dry milled 62

Table 15 ndash Analytical data on compost material received from UBA Austria Polycyclic aromatic hydrocarbons

PAH Unit Result Naphthaline microgkg DM 93 Acenaphthylene microgkg DM 86 Acenaphthene microgkg DM 5 Fluorene microgkg DM 80 Phenanthrene microgkg DM 89 Anthracene microgkg DM 27 Fluoranthene microgkg DM 487 Pyrene microgkg DM 380

12

PAH Unit Result Benzo(a)anthracene microgkg DM 278 Chrysene microgkg DM 317 Benzo(b)fluoranthene microgkg DM 365 Benzo(k)fluoranthene microgkg DM 193 Benz(a)pyrene microgkg DM 320 Indeno(123-cd)pyrene microgkg DM 233 Dibenz(ah)anthracene microgkg DM 67 Benzo(ghi)perylene microgkg DM 225 Sum EPA microgkg DM 3013 Sum EPA mgkg DM 30

Table 16 ndash Analytical data on compost material received from UBA Austria Sum PCDDs and PCBs

Parameter

Dioxine TEQ (ITEF) ngkg DM 73 TEQ (WHO) ngkg DM 35 PCB Σ Ballschmiter mgkg DM 005

Table 17 ndash Analytical data on compost material obtained by screening in IRMM

Parameter Result in ngg

PCB 28 2 52 2 101 4 118 3 153 10 105 1 138 8 156 1 180 5 170 lt1 PAH Naphtalene lt10 Acenaphtylene lt10 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene 26 Fluoranthene 611 Pyrene 510 Benz(a)anthracene 888 Chrysene 957 Benz(b)fluoranthene 1531 Benz(k)fluoranthene 547 Benz(a)pyrene 1101 Indeno(123-cd)pyrene 416 Dibenzo(ah)anthracene 81 Benzo(ghi)perylene 295

13

Table 18 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Compost 1

(Vienna)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

402

019

259

nq

023

004

nq

nq

144

174

259

Table 19 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Compost 1

(Vienna) 0058 1426 557

Table 20 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Compost 1 (Vienna) 039 736 319 410 365 127 495 004 079 013 208

Table 21 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Compost 1 (Vienna) 2063 431 617 426 199 249 1602 lt15 10521

Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Compost 1 (Vienna) 035 3496 81 375 79 55 653 60

Table 22 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Compost 1 (Vienna) 017

14

24 Agricultural soil sludge amended soil from Pavia Italy

This sludge-amended soil material was obtained during a monitoring campaign which aimed at a generic description of the over-all soil quality in Pavia Province Italy The material which was collected from the upper horizon originates from a small farm called ldquoCascina Novellordquo During the characterisation of the site the following analytical information was obtained on a pooled sample of a sub-area of the farm of 20 X 20 m2

Table 23 ndash Analytical data on Pavia soil

Parameter Result Al 713 Wgt As 224 mgkg Cd 079 mgkg Cr 59 mgkg Cu 308 mgkg Hg 008 mgkg Ni 344 mgkg Pb 246 mgkg Zn 95 mgkg C 091 Wgt 2378-TCDD 0047 pgg 12378-PeCDD 015 pgg 123478-HxCDD 019 pgg 123678-HxCDD 15 pgg 123789-HxCDD 074 pgg 1234678-HpCDD 26 pgg OCDD 382 pgg 2378-TCDF 068 pgg 12378-PeCDF 053 pgg 23478-PeCDF 071 pgg 123478-HxDF 100 pgg 123678-HxDF 066 pgg 234678-HxDF 16 pgg 123789-HxDF 027 pgg 1234678-HpDF 12 pgg 1234789-HpDF 068 pgg OCDF 33 pgg I-TEQ 20 pgg WHO-TEQ 17 pgg

In addition the screening performed at IRMM did not reveal significant quantities of PCBs and PAHs which were all below the LoDs (1 ngg for PCBs and 10 ngg for PAHs respectively)

Table 24 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 5 (Pavia) 0005 0011 154

15

Table 25 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 5

(Pavia)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

039

nq

nq

008

nq

nd

nd

670

671

Table 26 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 5 (Pavia) 033 184 573 225 426 305 206 200 lt 005 381 878

Table 27 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 5 (Pavia) 6939 129 145 224 425 116 6118 255 1789 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 5 (Pavia) 184 62 38 108 55 66 597 110

Table 28 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 5 (Pavia) 006

16

25 Sludge-amended-soil from Barcelona Spain

The sludge-amended soil material from Barcelona sampled upon indication from the Barcelorsquo- Group in Barcelona

Table 29 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 2 (Lleida T) 0015 0183 1138

Table 30 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 2

(Lleida T)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

159

045

nq

048

160

nq

nq

1000

1004

Table 31 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 2 (Lleida T) 059 141 327 536 405 186 184 224 lt 005 318 111

Table 32 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 2 (Lleida T) 4443 1067 1429 253 344 204 4116 780 3396 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 2 (Lleida T) 064 65 26 125 59 17 547 65

Table 33 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 2 (Lleida T) 010

17

26 Sludge amended soil from Essen Germany

The German sludge-amended soil from Essen which was provided as the three sludge materials by LUA NRW did not feature significant concentrations of the PCB congeners 28 52 101 118 153 105 138 156 180 170 but had detectable amounts of some PAHs

Table 34 ndash Analytical screening data on the German sludge-amended soil

Parameter Concentration(ngg)

Naphtalene lt10 Acenaphtylene lt10 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene lt10 Fluoranthene 28 Pyrene 20 Benz(a)anthracene 24 Chrysene 47 Benz(b)fluoranthene 76 Benz(k)fluoranthene 20 Benz(a)pyrene 35 Indeno(123-cd)pyrene 35 Dibenzo(ah)anthracene 10 Benzo(ghi)perylene 26

Table 35 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 4 (Essen) 0011 0302 055

Table 36 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 4

(Essen)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

nq

nq

nq

nq

nq

nq

128

191

203

18

Table 37 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 4 (Essen) 052 545 261 805 320 403 273 273 lt 005 295 781

Table 38 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 4 (Essen) 7947 442 085 06 086 007 2163 189 2019 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 4 (Essen) 045 19 42 87 683 60 462 61

Table 39 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 4 (Essen) 004

27 Long-term sludge exposed soil from Hohenheim-Stuttgart Germany

Similarly an additional sludge exposed soil was sampled at the University of Hohenheim Stuttgart were a test soil was long-term exposed to elevated concentrations of sewage sludge

Table 40 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 1 (Stuttgart) 0045 0263 1765

Table 41 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 1

(Stuttgart)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

230

006

004

004

nq

nd

nd

498

500

19

Table 42 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 1 (Stuttgart) 069 127 361 262 504 183 252 262 lt 005 266 142

Table 43 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 1 (Stuttgart) 7194 1006 133 186 366 088 7874 275 3571 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 1 (Stuttgart) 123 50 47 212 85 69 991 129

Table 44 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 1 (Stuttgart) 177

18

Annex 3

Statistical calculations

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 47)Mandels h statistics(Sludge 1 - PBD 47)

Sample Sludge 1 NUM

Element PBD 47

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00213 0001 3 -021 005 - - 10L - - NUM46L 00273 0002 4 016 021 - - 46L - - NUM64L 00059 0000 4 -116 002 NUM - 64L - - NUM12L 00188 0000 4 -036 002 - - 12L - - NUM26L 00499 0024 2 157 223 Fail - - 26L - - NUM

Totgem 0025 0005 mgkg 1-level 172 (185) NUM (10L46L64L12L26L) -1Totstd= 0016 0010 5-level 157 (162) 5

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 5 Labs rejected (10L46L64L12L26L)

000 050 100 150 200 250

k-values

10L

46L

64L

12L

26L

Mandels k statistics(Sludge 1 - PBD 47)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

10L

46L

64L

12L

26L

Labo

rato

ries

NUM

-200 -100 000 100 200

h-values

10L

46L

64L

12L

26L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 47)

Sludge 1-PBD 47

Unit mgkg

Mandels k statistics(Soil 3 - PBD 47)Mandels h statistics(Soil 3 - PBD 47)

Sample Soil 3 Soil 3 - PBD 47 -- Mean PARM = 0001 [mgkg]

Element PBD 47

General calcparmT1= 134814E-02T2= 142830E-05T3= 13T4= 45T5= 22767E-06

n= variabelp= 4

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean26L 00007 0000 2 -143 001 00007 00000 2 1 00046L 00010 0001 4 010 181 00010 00008 4 3 00010L 00011 0000 3 049 023 00011 00001 3 2 00012L 00012 0000 4 084 081 00012 00004 4 3 000

Totgem 0001 0000 mgkg 1-level 149 (177) 4 00010 () 4 3Totstd= 0000 0000 5-level 142 (159)

RESULTS Mean = 000100 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000050 --gt 5031 r = 00014Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000050 --gt 5031 R = 00014Remarks none

000 050 100 150 200

k-values

26L

46L

10L

12L

Mandels k statistics(Soil 3 - PBD 47)

00 00 00 00 00 00 00 00 00 00 00

Deviation from Mean

26L

46L

10L

12L

Labo

rato

ries

Soil 3 - PBD 47 -- Mean PARM = 0001 [mgkg]

-200 -100 000 100

h-values

26L

46L

10L

12L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 47)

Soil 3-PBD 47

Unit mgkg

Mandels k statistics(Compost 1 - PBD 99)Mandels h statistics(Compost 1 - PBD 99)

Sample Compost 1 Compost 1 - PBD 99 -- Mean PARM = 0003 [mgkg]

Element PBD 99

General calcparmT1= 492124E-02T2= 148747E-04T3= 17T4= 61T5= 93196E-06

n= variabelp= 5

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00020 0000 4 -137 053 00020 00004 4 3 000

26L 00025 0000 2 -058 024 00025 00002 2 1 00010L 00029 0000 3 012 032 00029 00003 3 2 00046L 00033 0001 4 069 161 00033 00013 4 3 00012L 00036 0001 4 114 140 00036 00011 4 3 000

Totgem 0003 0001 mgkg 1-level 172 (185) 5 00029 () 5 4Totstd= 0001 0001 5-level 157 (162)

RESULTS Mean = 000286 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000088 --gt 3086 r = 00025Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000101 --gt 3525 R = 00028Remarks none

000 050 100 150 200

k-values

4L

26L

10L

46L

12L

Mandels k statistics(Compost 1 - PBD 99)

00 00 00 00 00 00 00 00 00 00

Deviation from Mean

4L

26L

10L

46L

12L

Labo

rato

ries

Compost 1 - PBD 99 -- Mean PARM = 0003 [mgkg]

-200 -100 000 100 200

h-values

4L

26L

10L

46L

12L

Labo

rato

ries

Mandels h statistics(Compost 1 - PBD 99)

Compost 1-PBD 99

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 99)Mandels h statistics(Sludge 1 - PBD 99)

Sample Sludge 1 Sludge 1 - PBD 99 -- Mean PARM = 0024 [mgkg]

Element PBD 99

General calcparmT1= 448050E-01T2= 112113E-02T3= 19T4= 73T5= 32972E-05

n= variabelp= 5

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean64L 00173 0002 4 -118 041 Fail 00173 00019 4 3 -0014L 00183 0002 4 -104 032 00183 00015 4 3 -001

12L 00227 0001 4 -038 022 00227 00010 4 3 00010L 00290 0001 3 055 021 00290 00010 3 2 00146L 00320 0002 4 100 039 00320 00018 4 3 00126L 00323 0011 2 105 234 - - 26L - - 001

Totgem 0025 0003 mgkg 1-level 187 (177) 5 00239 (26L) 5 4Totstd= 0007 0004 5-level 166 (154) 1

RESULTS Mean = 002385 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000153 --gt 643 r = 00043Between lab variance S2L = 000004Reproducibility var S2R = 000004Reproducibility std SR = 000666 --gt 2791 R = 00186Remarks 1 Lab rejected (26L)

000 050 100 150 200 250

k-values

64L

4L

12L

10L

46L

26L

Mandels k statistics(Sludge 1 - PBD 99)

00 00 00 00 00 00 00 00 00 00

Deviation from Mean

64L

4L

12L

10L

46L

26L

Labo

rato

ries

Sludge 1 - PBD 99 -- Mean PARM = 0024 [mgkg]

-200 -100 000 100 200

h-values

64L

4L

12L

10L

46L

26L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 99)

Sludge 1-PBD 99

Unit mgkg

Mandels k statistics(Soil 3 - PBD 99)Mandels h statistics(Soil 3 - PBD 99)

Sample Soil 3 NUM

Element PBD 99

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00017 0000 4 091 068 - - 10L - - NUM46L 00017 0001 4 100 211 - - 46L - - NUM64L 00005 0000 4 -106 023 NUM - 64L - - NUM12L 00012 0000 4 015 014 - - 12L - - NUM26L 00006 0000 2 -101 012 - - 26L - - NUM

Totgem 0001 0000 mgkg 1-level 172 (173) NUM (10L46L64L12L26L) -1Totstd= 0001 0000 5-level 157 (153) 5

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 5 Labs rejected (10L46L64L12L26L)

000 050 100 150 200 250

k-values

10L

46L

64L

12L

26L

Mandels k statistics(Soil 3 - PBD 99)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

10L

46L

64L

12L

26L

Labo

rato

ries

NUM

-200 -100 000 100 200

h-values

10L

46L

64L

12L

26L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 99)

Soil 3-PBD 99

Unit mgkg

Mandels k statistics(Compost 1 - PBD 100)Mandels h statistics(Compost 1 - PBD 100)

Sample Compost 1 Compost 1 - PBD 100 -- Mean PARM = 0001 [mgkg]

Element PBD 100

General calcparmT1= 124272E-02T2= 113129E-05T3= 14T4= 52T5= 46584E-07

n= variabelp= 4

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean26L 00006 0000 2 -131 037 Fail 00006 00001 2 1 00010L 00009 0000 4 003 083 00009 00002 4 3 00046L 00009 0000 4 016 115 00009 00002 4 3 00012L 00011 0000 4 112 136 Fail 00011 00003 4 3 000

Totgem 0001 0000 mgkg 1-level 149 (167) 4 00009 () 4 3Totstd= 0000 0000 5-level 142 (15)

RESULTS Mean = 000085 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000022 --gt 2531 r = 00006Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000025 --gt 2882 R = 00007Remarks none

000 050 100 150

k-values

26L

10L

46L

12L

Mandels k statistics(Compost 1 - PBD 100)

00 00 00 00 00 00 00 00 00 00 00

Deviation from Mean

26L

10L

46L

12L

Labo

rato

ries

Compost 1 - PBD 100 -- Mean PARM = 0001 [mgkg]

-200 -100 000 100 200

h-values

26L

10L

46L

12L

Labo

rato

ries

Mandels h statistics(Compost 1 - PBD 100)

Compost 1-PBD 100

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 100)Mandels h statistics(Sludge 1 - PBD 100)

Sample Sludge 1 Sludge 1 - PBD 100 -- Mean PARM = 0005 [mgkg]

Element PBD 100

General calcparmT1= 852065E-02T2= 412762E-04T3= 18T4= 68T5= 78914E-07

n= variabelp= 5

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00039 0000 4 -042 007 Fail 00039 00002 4 3 000

12L 00044 0000 4 -041 005 Fail 00044 00001 4 3 00010L 00046 0000 4 -041 013 Fail 00046 00003 4 3 00046L 00056 0000 4 -040 012 Fail 00056 00003 4 3 00026L 00059 0000 2 -040 013 Fail 00059 00003 2 1 00038L 02168 0006 4 204 244 Fail - - 38L - - 021

Totgem 0040 0001 mgkg 1-level 187 (177) 5 00049 (38L) 5 4Totstd= 0087 0002 5-level 166 (154) 1

RESULTS Mean = 000486 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000025 --gt 507 r = 00007Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000084 --gt 1731 R = 00024Remarks 1 Lab rejected (38L)

000 050 100 150 200 250

k-values

4L

12L

10L

46L

26L

38L

Mandels k statistics(Sludge 1 - PBD 100)

-01 00 01 01 02 02 03

Deviation from Mean

4L

12L

10L

46L

26L

38L

Labo

rato

ries

Sludge 1 - PBD 100 -- Mean PARM = 0005 [mgkg]

-100 000 100 200 300

h-values

4L

12L

10L

46L

26L

38L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 100)

Sludge 1-PBD 100

Unit mgkg

Mandels k statistics(Soil 3 - PBD 100)Mandels h statistics(Soil 3 - PBD 100)

Sample Soil 3 NUM

Element PBD 100

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00003 0000 4 -050 000 Fail - - 10L - - NUM46L 00003 0000 4 -050 000 Fail NUM - 46L - - NUM3L 305500 2051 2 150 200 Fail - - 3L - - NUM

26L 00005 0000 2 -050 000 Fail - - 26L - - NUM

Totgem 7638 0513 mgkg 1-level 149 (177) NUM (10L46L3L26L) -1Totstd= 15275 1025 5-level 142 (159) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (10L46L3L26L)

000 050 100 150 200

k-values

10L

46L

3L

26L

Mandels k statistics(Soil 3 - PBD 100)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

10L

46L

3L

26L

Labo

rato

ries

NUM

-100 000 100 200

h-values

10L

46L

3L

26L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 100)

Soil 3-PBD 100

Unit mgkg

Mandels k statistics(Compost 1 - PBD 153)Mandels h statistics(Compost 1 - PBD 153)

Sample Compost 1 NUM

Element PBD 153

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean44L 00053 0001 3 150 157 Fail - - 44L - - NUM46L 00007 0000 4 -044 111 Fail - - 46L - - NUM12L 00005 0000 4 -051 055 Fail - - 12L - - NUM26L 00005 0000 2 -054 001 Fail NUM - 26L - - NUM

Totgem 0002 0000 mgkg 1-level 149 (177) NUM (44L46L12L26L) -1Totstd= 0002 0000 5-level 142 (159) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (44L46L12L26L)

000 050 100 150 200

k-values

44L

46L

12L

26L

Mandels k statistics(Compost 1 - PBD 153)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

44L

46L

12L

26L

Labo

rato

ries

NUM

-100 000 100 200

h-values

44L

46L

12L

26L

Labo

rato

ries

Mandels h statistics(Compost 1 - PBD 153)

Compost 1-PBD 153

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 153)Mandels h statistics(Sludge 1 - PBD 153)

Sample Sludge 1 Sludge 1 - PBD 153 -- Mean PARM = 0004 [mgkg]

Element PBD 153

General calcparmT1= 676738E-02T2= 267609E-04T3= 18T4= 68T5= 19626E-05

n= variabelp= 5

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00024 0000 4 -157 017 00024 00002 4 3 000

12L 00038 0002 4 006 154 00038 00018 4 3 00046L 00039 0000 4 011 026 00039 00003 4 3 00026L 00039 0000 2 018 004 00039 00000 2 1 00064L 00049 0002 4 122 159 00049 00018 4 3 000

Totgem 0004 0001 mgkg 1-level 172 (173) 5 00038 () 5 4Totstd= 0001 0001 5-level 157 (153)

RESULTS Mean = 000378 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000123 --gt 3252 r = 00034Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000142 --gt 3754 R = 00040Remarks none

000 050 100 150 200

k-values

4L

12L

46L

26L

64L

Mandels k statistics(Sludge 1 - PBD 153)

00 00 00 00 00 00 00

Deviation from Mean

4L

12L

46L

26L

64L

Labo

rato

ries

Sludge 1 - PBD 153 -- Mean PARM = 0004 [mgkg]

-200 -100 000 100 200

h-values

4L

12L

46L

26L

64L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 153)

Sludge 1-PBD 153

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 154)Mandels h statistics(Sludge 1 - PBD 154)

Sample Sludge 1 NA

Element PBD 154

General calcparmT1= NAT2= NAT3=T4=T5=

n= variabelp=

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00021 0000 3 -100 021 NA - 4L - - NA

46L 00025 0000 4 115 018 NA - 46L - - NA64L 00021 0001 4 -066 179 - - 64L - - NA12L 00023 0000 4 050 085 - - 12L - - NA

Totgem 0002 0000 mgkg 1-level 149 (167) NA (4L46L64L12L) -1Totstd= 0000 0000 5-level 142 (15) 4

RESULTS Mean = NA mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NAReproducibility var S2R = NAReproducibility std SR = NA --gt NA R = NARemarks 4 Labs rejected (4L46L64L12L)

000 050 100 150 200

k-values

4L

46L

64L

12L

Mandels k statistics(Sludge 1 - PBD 154)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

4L

46L

64L

12L

Labo

rato

ries

NA

-100 000 100 200

h-values

4L

46L

64L

12L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 154)

Sludge 1-PBD 154

Unit mgkg

Mandels k statistics(Soil 3 - PBD 154)Mandels h statistics(Soil 3 - PBD 154)

Sample Soil 3 NUM

Element PBD 154

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

4L 00010 - 1 150 Fail - - 4L - - NUM46L 00001 0000 4 -053 096 Fail - - 46L - - NUM64L 00001 0000 4 -056 105 Fail NUM - 64L - - NUM12L 00002 0000 4 -040 099 Fail - - 12L - - NUM

Totgem 000037 0000 mgkg 1-level 149 (164) NUM (4L46L64L12L) -1Totstd= 000042 0000 5-level 142 (153) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (4L46L64L12L)

000 050 100 150

k-values

4L

46L

64L

12L

Mandels k statistics(Soil 3 - PBD 154)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

4L

46L

64L

12L

Labo

rato

ries

NUM

-100 000 100 200

h-values

4L

46L

64L

12L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 154)

Soil 3-PBD 154

Unit mgkg

Mandels k statistics(Compost 1 - PBD 209)Mandels h statistics(Compost 1 - PBD 209)

Sample Compost 1 NUM

Element PBD 209

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00065 0003 2 -049 032 - - 4L - - NUM

44L 00573 0021 4 150 197 Fail - - 44L - - NUM12L 00078 0001 4 -045 011 - - 12L - - NUM26L 00049 0000 2 -056 000 NUM - 26L - - NUM

Totgem 0019 0006 mgkg 1-level 149 (177) NUM (4L44L12L26L) -1Totstd= 0025 0010 5-level 142 (159) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (4L44L12L26L)

000 050 100 150 200

k-values

4L

44L

12L

26L

Mandels k statistics(Compost 1 - PBD 209)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

4L

44L

12L

26L

Labo

rato

ries

NUM

-100 000 100 200

h-values

4L

44L

12L

26L

Labo

rato

ries

Mandels h statistics(Compost 1 - PBD 209)

Compost 1-PBD 209

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 209)Mandels h statistics(Sludge 1 - PBD 209)

Sample Sludge 1 Sludge 1 - PBD 209 -- Mean PARM = 0249 [mgkg]

Element PBD 209

General calcparmT1= 394542E+00T2= 107296E+00T3= 16T4= 56T5= 19723E-02

n= variabelp= 5

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 01550 0055 4 -112 148 Fail 01550 00551 4 3 -009

46L 02050 0007 2 -053 019 02050 00071 2 1 -00412L 02137 0058 4 -042 155 02137 00576 4 3 -00426L 03149 0021 2 078 057 Fail 03149 00210 2 1 00764L 03577 0007 4 129 020 Fail 03577 00074 4 3 011

Totgem 0249 0030 mgkg 1-level 172 (185) 5 02493 () 5 4Totstd= 0084 0025 5-level 157 (162)

RESULTS Mean = 024926 mgkg

Repeatability variance S2r = 000179Repeatability std Sr = 004234 --gt 1699 r = 01186Between lab variance S2L = 000743Reproducibility var S2R = 000922Reproducibility std SR = 009604 --gt 3853 R = 02689Remarks none

000 050 100 150 200

k-values

4L

46L

12L

26L

64L

Mandels k statistics(Sludge 1 - PBD 209)

-01 -01 00 01 01 02

Deviation from Mean

4L

46L

12L

26L

64L

Labo

rato

ries

Sludge 1 - PBD 209 -- Mean PARM = 0249 [mgkg]

-200 -100 000 100 200

h-values

4L

46L

12L

26L

64L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 209)

Sludge 1-PBD 209

Unit mgkg

Mandels k statistics(Soil 3 - PBD 209)Mandels h statistics(Soil 3 - PBD 209)

Sample Soil 3 Soil 3 - PBD 209 -- Mean PARM = 0258 [mgkg]

Element PBD 209

General calcparmT1= 596398E+00T2= 191917E+00T3= 22T4= 84T5= 13249E-02

n= variabelp= 6

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean26L 01162 0021 2 -108 074 Fail 01162 00207 2 1 -0144L 01303 0031 4 -097 111 Fail 01303 00312 4 3 -013

46L 01975 0036 4 -046 128 Fail 01975 00359 4 3 -00644L 02898 0035 4 024 124 Fail 02898 00346 4 3 00312L 03895 0018 4 100 065 Fail 03895 00181 4 3 01364L 04260 0022 4 127 078 Fail 04260 00219 4 3 017

Totgem 0258 0027 mgkg 1-level 187 (177) 6 02582 () 6 5Totstd= 0132 0008 5-level 166 (154)

RESULTS Mean = 025818 mgkg

Repeatability variance S2r = 000083Repeatability std Sr = 002878 --gt 1115 r = 00806Between lab variance S2L = 001640Reproducibility var S2R = 001723Reproducibility std SR = 013127 --gt 5084 R = 03676Remarks none

000 050 100 150

k-values

26L

4L

46L

44L

12L

64L

Mandels k statistics(Soil 3 - PBD 209)

-02 -01 -01 00 01 01 02 02

Deviation from Mean

26L

4L

46L

44L

12L

64L

Labo

rato

ries

Soil 3 - PBD 209 -- Mean PARM = 0258 [mgkg]

-200 -100 000 100 200

h-values

26L

4L

46L

44L

12L

64L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 209)

Soil 3-PBD 209

Unit mgkg

Mandels k statistics(Compost 1 - Sum PBD)Mandels h statistics(Compost 1 - Sum PBD)

Sample Compost 1 Compost 1 - Sum PBD -- Mean PARM = 0009 [mgkg]

Element Sum PBD

General calcparmT1= 154064E-01T2= 169065E-03T3= 18T4= 68T5= 11354E-04

n= variabelp= 5

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00031 0002 4 -067 016 00031 00016 4 3 -0014L 00055 0005 4 -056 048 00055 00047 4 3 000

46L 00085 0003 4 -042 031 00085 00030 4 3 00026L 00123 0000 2 -024 003 00123 00002 2 1 00012L 00154 0002 4 -011 021 00154 00021 4 3 00144L 00613 0023 4 200 237 Fail - - 44L - - 005

Totgem 0018 0006 mgkg 1-level 187 (177) 5 00089 (44L) 5 4Totstd= 0022 0009 5-level 166 (154) 1

RESULTS Mean = 000893 mgkg

Repeatability variance S2r = 000001Repeatability std Sr = 000296 --gt 3308 r = 00083Between lab variance S2L = 000002Reproducibility var S2R = 000003Reproducibility std SR = 000570 --gt 6374 R = 00159Remarks 1 Lab rejected (44L)

000 050 100 150 200 250

k-values

10L

4L

46L

26L

12L

44L

Mandels k statistics(Compost 1 - Sum PBD)

00 00 00 00 00 00 01 01

Deviation from Mean

10L

4L

46L

26L

12L

44L

Labo

rato

ries

Compost 1 - Sum PBD -- Mean PARM = 0009 [mgkg]

-100 000 100 200

h-values

10L

4L

46L

26L

12L

44L

Labo

rato

ries

Mandels h statistics(Compost 1 - Sum PBD)

Compost 1-Sum PBD

Unit mgkg

Mandels k statistics(Sludge 1 - Sum PBD)Mandels h statistics(Sludge 1 - Sum PBD)

Sample Sludge 1 Sludge 1 - Sum PBD -- Mean PARM = 0256 [mgkg]

Element Sum PBD

General calcparmT1= 531806E+00T2= 162188E+00T3= 22T4= 84T5= 25223E-02

n= variabelp= 6

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00423 0025 4 -156 044 Fail 00423 00252 4 3 -02146L 01808 0118 4 -049 205 - - 46L - - -0074L 01810 0056 4 -049 097 01810 00558 4 3 -007

38L 02168 0006 4 -022 010 02168 00059 4 3 -00412L 02890 0065 4 034 113 02890 00647 4 3 00364L 03958 0008 4 116 014 Fail 03958 00079 4 3 01426L 04094 0034 2 126 059 Fail 04094 00337 2 1 015

Totgem 0245 0044 mgkg 1-level 198 (179) 6 02557 (46L) 6 5Totstd= 0130 0039 5-level 171 (155) 1

RESULTS Mean = 025570 mgkg

Repeatability variance S2r = 000158Repeatability std Sr = 003970 --gt 1553 r = 01112Between lab variance S2L = 001807Reproducibility var S2R = 001964Reproducibility std SR = 014015 --gt 5481 R = 03924Remarks 1 Lab rejected (46L)

000 050 100 150 200 250

k-values

10L

46L

4L

38L

12L

64L

26L

Mandels k statistics(Sludge 1 - Sum PBD)

-03 -02 -02 -01 -01 00 01 01 02 02

Deviation from Mean

10L

46L

4L

38L

12L

64L

26L

Labo

rato

ries

Sludge 1 - Sum PBD -- Mean PARM = 0256 [mgkg]

-200 -100 000 100 200

h-values

10L

46L

4L

38L

12L

64L

26L

Labo

rato

ries

Mandels h statistics(Sludge 1 - Sum PBD)

Sludge 1-Sum PBD

Unit mgkg

Mandels k statistics(Soil 3 - Sum PBD)Mandels h statistics(Soil 3 - Sum PBD)

Sample Soil 3 Soil 3 - Sum PBD -- Mean PARM = 0227 [mgkg]

Element Sum PBD

General calcparmT1= 610980E+00T2= 200876E+00T3= 26T4= 100T5= 13106E-02

n= variabelp= 7

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00028 0001 4 -037 000 Fail 00028 00005 4 3 -02226L 01179 0021 2 -036 003 Fail 01179 00208 2 1 -0114L 01305 0031 4 -036 004 Fail 01305 00308 4 3 -010

46L 02065 0035 4 -036 005 Fail 02065 00350 4 3 -00244L 02923 0037 4 -035 005 Fail 02923 00365 4 3 00712L 04051 0015 4 -034 002 Fail 04051 00149 4 3 01864L 04314 0022 4 -033 003 Fail 04314 00223 4 3 0203L 305500 2051 2 247 283 Fail - - 3L - - 3032

Totgem 4017 0276 mgkg 1-level 206 (181) 7 02266 (3L) 7 6Totstd= 10722 0717 5-level 175 (156) 1

RESULTS Mean = 022663 mgkg

Repeatability variance S2r = 000069Repeatability std Sr = 002626 --gt 1159 r = 00735Between lab variance S2L = 002568Reproducibility var S2R = 002637Reproducibility std SR = 016238 --gt 7165 R = 04547Remarks 1 Lab rejected (3L)

000 050 100 150 200 250 300

k-values

10L

26L

4L

46L

44L

12L

64L

3L

Mandels k statistics(Soil 3 - Sum PBD)

-50 00 50 100 150 200 250 300 350

Deviation from Mean

10L

26L

4L

46L

44L

12L

64L

3L

Labo

rato

ries

Soil 3 - Sum PBD -- Mean PARM = 0227 [mgkg]

-100 000 100 200 300

h-values

10L

26L

4L

46L

44L

12L

64L

3L

Labo

rato

ries

Mandels h statistics(Soil 3 - Sum PBD)

Soil 3-Sum PBD

19

Annex 4

Raw data submitted

Sample Compost1 Sample Compost 1 Sample Compost 1Element PBD 99 Element PBD 100 Element PBD 153

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]4L 00021 10L 00008 44L 000504L 00024 10L 00008 44L 000604L 00014 10L 00007 44L 000504L 00020 10L 00011 46L 00004

10L 00029 46L 00007 46L 0001210L 00027 46L 00012 46L 0000410L 00032 46L 00009 46L 0000946L 00025 46L 00007 12L 0000446L 00052 12L 00008 12L 0000846L 00029 12L 00012 12L 0000446L 00026 12L 00008 12L 0000712L 00026 12L 00014 26L 0000512L 00043 26L 00007 26L 0000512L 00026 26L 0000612L 0004726L 0002626L 00024

Sample Compost 1 Sample Compost 1 Sample Compost 1Element PBD 154 Element PBD 183 Element PBD 196

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]4L 00010 46L 00002 46L 00011

46L 00003 46L 00024 46L 0000846L 00007 46L 00021 12L 0000246L 00003 46L 00003 12L 0000346L 00004 12L 00003 12L 0000112L 00003 12L 00011 12L 0000212L 00005 12L 0000312L 00031 12L 0000312L 00006

Sample Compost 1 Sample Compost 1 Sample Compost 1Element PBD 197 Element PBD 203 Element PBD 209

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00002 46L 00010 4L 0004146L 00023 12L 00002 4L 0008946L 00022 12L 00003 44L 0041012L 00004 12L 00002 44L 0084012L 00006 12L 00002 44L 0064012L 00003 44L 0040012L 00004 12L 00079

12L 0007312L 0006512L 0009326L 0004926L 00049

Sample Compost 1Element PBD 47

LAB PARM [mgkg]26L 0003826L 00039

Element PBD 99 Element PBD 47 Element PBD 209LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]

4L 00170 10L 00210 4L 010004L 00200 10L 00220 4L 018004L 00170 10L 00210 4L 012004L 00190 46L 00300 4L 0220010L 00280 46L 00280 46L 0210010L 00300 46L 00250 46L 0200010L 00290 46L 00260 64L 0351846L 00340 64L 00059 64L 0363846L 00330 64L 00057 64L 0364546L 00300 64L 00062 64L 0350846L 00310 64L 00060 12L 0220964L 00194 12L 00191 12L 0177164L 00154 12L 00187 12L 0292264L 00185 12L 00190 12L 0164664L 00159 12L 00186 26L 0329712L 00242 26L 00666 26L 0300012L 00223 26L 0033212L 0022112L 0022226L 0024626L 00400

Element PBD 203 Element PBD 197 Element PBD 196LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00022 46L 00027 46L 0002446L 00014 46L 00024 46L 0002264L 00036 12L 00161 64L 0005864L 00058 12L 00060 64L 0006512L 00063 12L 00061 12L 0004812L 00034 12L 00036 12L 0002512L 00038 12L 0003212L 00027 12L 00022

Element PBD 183 Element PBD 154 Element PBD 153LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00049 4L 00020 4L 0002246L 00035 4L 00022 4L 0002446L 00036 4L 00020 4L 0002246L 00034 46L 00025 4L 0002664L 00027 46L 00025 46L 0004064L 00023 46L 00025 46L 0004264L 00024 46L 00023 46L 0003564L 00020 64L 00034 46L 0003812L 00230 64L 00023 64L 0007412L 00032 64L 00017 64L 0004712L 00031 64L 00011 64L 0004612L 00030 12L 00030 64L 0003026L 00007 12L 00021 12L 0006526L 00008 12L 00021 12L 00029

12L 00021 12L 0003226L 00015 12L 0002926L 00019 26L 00039

26L 00040

Element PBD 100LAB PARM [mgkg]

4L 000384L 000414L 000374L 00038

38L 0219038L 0220038L 0208038L 0220010L 0004410L 0005010L 0004310L 0004646L 0005746L 0005946L 0005346L 0005312L 0004312L 0004512L 0004312L 0004326L 0006226L 00057

Sample Soil 3 Sample Soil 3 Sample Soil 3Element PBD 99 Element PBD 47 Element PBD 100

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]10L 00016 10L 00011 10L 0000310L 00019 10L 00010 10L 0000410L 00013 10L 00012 10L 0000410L 00019 46L 00007 10L 0000246L 00025 46L 00022 46L 0000246L 00025 46L 00005 46L 0000646L 00008 46L 00007 46L 0000246L 00011 12L 00010 46L 0000264L 00005 12L 00017 3L 29100064L 00005 12L 00010 3L 32000064L 00006 12L 00009 26L 0000564L 00007 26L 00007 26L 0000512L 00012 26L 0000712L 0001312L 0001312L 0001226L 0000526L 00006

Sample Soil 3 Sample Soil 3 Sample Soil 3Element PBD 153 Element PBD 154 Element PBD 196

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]44L 00050 4L 00010 46L 0000744L 00050 46L 00001 46L 0001146L 00002 46L 00002 46L 0000846L 00003 46L 00001 46L 0001146L 00002 46L 00002 64L 0002646L 00002 64L 00001 64L 0002664L 00001 64L 00001 64L 0002964L 00001 64L 00001 64L 0003464L 00001 64L 00002 12L 0004564L 00002 12L 00003 12L 00032

12L 00002 12L 0002212L 00002 12L 0002112L 00002

Sample Soil 3 Sample Soil 3 Sample Soil 3Element PBD 197 Element PBD 203 Element PBD 209

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00006 46L 00011 4L 0091046L 00013 46L 00017 4L 0150046L 00011 46L 00015 4L 0120046L 00013 46L 00018 4L 0160012L 00090 64L 00013 44L 0337012L 00056 64L 00014 44L 0281012L 00033 64L 00016 44L 0287012L 00032 64L 00015 44L 02540

12L 00055 46L 0230012L 00041 46L 0220012L 00027 46L 0150012L 00026 46L 01900

64L 0438164L 0401664L 0414464L 0449812L 0367112L 0397812L 0409112L 03838

Sample Soil 3 26L 0102Element PBD 183 26L 0131

LAB PARM [mgkg]46L 0000746L 0000846L 0005846L 0000764L 0000264L 0000364L 0000364L 0000312L 0001512L 0001112L 0000712L 00007

European Commission EUR 23003 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on polybrominated diphenylethers Author(s) E Sobiecka H van der Sloot D Barcelo B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 68 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07403-5 Abstract Project HORIZONTAL is interdisciplinary aiming at a harmonisation and horizontal standardisation of test procedures in particular for sludge soils and biowastes In the context of this standardization project a series of draft technical specification were designed upon an extensive desk study fine-tuned after expert consultations and finally validated in international intercomparisons exercise This report summarises the work performed within the validation study of the draft standard for the determination of polybrominated diphenylethers (PBDE) in soils sludge and treated bio-waste using gas-chromatography method with mass selective detection (GC-MS) It further explains the underlying statistical concept for the calculation of reproducibility and repeatability from intercomparisons data In addition all single values results of the statistical evaluation as well as background information on the validation materials used are described and explained

The mission of the JRC is to provide customer-driven scientific and technical support for the conception development implementation and monitoring of EU policies As a service of the European Commission the JRC functions as a reference centre of science and technology for the Union Close to the policy-making process it serves the common interest of the Member States while being independent of special interests whether private or national

LB

-NA

-23003-EN

-C

11

13 Summary results and derived performance characteristics The result of the various statistical evaluation including outlier tests calculation of repeatability and reproducibility standard deviation for the congeners of interest can be found in Annex 3 of this report In addition all data submitted by the participants as well as those considered for the calculation of the performance characteristics are listed in Annex 3 to this report Based on these calculations the following results were obtained in the validation round upon statistical evaluation according to ISO 5725-2 The average values the repeatability standard deviation (sr) and the reproducibility standard deviation (sR) were obtained (Table1) The repeatability is determined as an interval around a measurement result (ie repeatability limit) This interval corresponds to the maximum difference that can be expected (with a 95 statistical confidence) between one test result and another both test results being obtained under the following conditions The tests are performed in accordance with all the requirements of the present standard by the same laboratory using its own facilities and testing laboratory samples obtained from the same primary field sample and prepared under identical procedures The repeatability limit was calculated using the relationship r test = f radic2 s rtest with the critical range factor f = 2 The reproducibility like repeatability is also determined as an interval around a measurement result (ie reproducibility limit) This interval corresponds to the maximum difference that can be expected (with a 95 statistical confidence) between one test result and another test result obtained by another laboratory both test results being obtained under the following conditions The tests are performed in accordance with all the requirements of the present standard by two different laboratories using their own facilities and testing laboratory samples obtained from the same primary field sample and prepared under identical procedures The reproducibility limit was calculated using the relationship R = f radic2 sR with the critical range factor f = 2

12

Table 1 - Results of the interlaboratory comparison studies of the determination of selected polybrominated diphenyl ethers (PBDE) by gaschromatography with mass spectrometric detection (GC-MS) in soil sludge and treated biowaste All concentrations are expressed in mgkg dm

Matrix Parameter Mean sr sR r R p Outliers Used No of data

No of data reported below

detection

Total no of data

Sludge 1 PBD 47 00181 461 4 15 5 20 Compost 1 00039 94 3 12 0 12 Soil 3 00010 50 50 00014 00014 4 0 13 10 23 Sludge 1 PBD 99 00239 64 28 00043 00186 5 1 19 0 23 Compost 1 00029 31 35 00025 00028 5 0 17 4 21 Soil 3 00013 499 4 16 8 24 Sludge 1 PBD 100 00049 51 17 00007 00024 5 1 18 2 24 Compost 1 00009 25 29 00006 00007 4 0 14 7 21 Soil 3 61103 211 3 10 15 25 Sludge 1 PBD 153 00038 33 38 00034 0004 5 0 18 0 18 Compost 1 00019 116 3 11 3 14 Soil 3 00011 177 2 10 10 20 Sludge 1 PBD 154 00023 234 4 15 2 17 Compost 1 00008 1118 3 9 5 14

13

Matrix Parameter Mean sr sR r R p Outliers Used No of data

No of data reported below

detection

Total no of data

Soil 3 00002 1049 4 13 6 19 Sludge 1 PBD 183 00048 1217 3 12 2 14 Compost 1 00009 1048 2 8 5 13 Soil 3 00011 1395 3 12 6 18 Sludge 1 PBD 196 00037 470 2 8 7 15 Compost 1 00004 950 2 6 4 10 Soil 3 00023 519 3 12 2 14 Sludge 1 PBD 197 00062 834 2 6 8 14 Compost 1 00009 1001 2 7 7 14 Soil 3 00032 904 2 8 6 14 Sludge 1 PBD 203 00037 461 2 8 4 12 Compost 1 00004 978 2 5 3 8 Soil 3 00022 598 3 12 0 12 Sludge 1 PBD 209 02493 170 39 01186 02689 5 0 16 2 18 Compost 1 00273 104 3 10 5 15 Soil 3 02582 1115 51 00806 03676 6 0 22 0 22

14

Matrix Parameter Mean sr sR r R p Outliers Used No of data

No of data reported below

detection

Total no of data

Sludge 1 Sum PBD 0256 155 548 0111 0392 6 1 22 Compost 1 0009 331 637 0008 0016 5 1 18 Soil 3 0227 116 717 0074 0455 7 1 26 Abbreviations sr Repeatability standard deviation SR Reproducibility standard deviation r Repeatability limit (comparing two measurements) R Reproducibility limit (comparing two measurements) p Number of labs determination not possible

15

14 Annexes Annex 1 Model questionnaire to be filled by the participating laboratories Annex 3 Report on the validation materials used Annex 2 Statistical calculations Annex 3 Data submitted

16

Annex 1

Model questionnaire to be filled by the participating laboratories

Model questionnaire to be filled by the participating laboratories Name of laboratory Contact person Contact details email Phone Fax Mail address of lab Dispatch address of lab for shipment of samples (no PO boxes) Title of measurement method (copy attached) Our laboratory is willing to participate in the precision experiment for this draft standard method

Yes No As participant we understand that

bull All essential apparatus chemicals and other requirements specified in the method must be available in our laboratory when the programme begins

bull Specified timing requirements such as starting and finishing date of the programme must be rigidly met

bull The method must be strictly adhered to bull Samples must be handled in accordance with instructions bull A qualified operator must perform the measurements

Having studied the method and having made a fair appraisal of our capabilities and facilities we feel that we will be adequately prepared for cooperative testing of this method Comments helliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphellip Signature Date

17

Annex 2

Report on the validation materials used

VI

Abstract This report gives an overview on the available analytical information on the following raw materials to be used for the production of validation materials of the so-called Project HORIZONTAL

bull Four sludge materials from Duumlsseldorf Germany

bull An agricultural soil material from Reading United Kingdom

bull A compost material from Vienna Austria

bull A compost material from Korschenbroich Germany

bull A sludge-amended agricultural soil from Pavia Province Italy

bull A sludge-amended soil from Barcelona Spain

bull A sludge-amended soil from Essen Germany

bull A long-term sludge exposed soil from Hohenheim Germany

VII

List of Abbreviations Throughout this report the following abbreviations are used

AOX absorbable organic halogens

Corg organic carbon content

Ctotal total carbon content

CAT cation exchangeable

CDD chlorinated dibenzodioxin

CDF chlorinated dibenzofuran

DEHP di(2-ethylhexyl)phthalate

DM dry matter

EPA Environment Protection Agency

EU European Union

FM fresh matter

Hp hepta

Hx hexa

IES Institute for Environment and Sustainability

IRMM Institute for Reference Materials and Measurements

JRC Joint Research Centre

LAS linear alkylsulfonates

LoD limit of detection

LUA Landesumweltamt

Ntotal total nitrogen content

NH4-N Ammonium nitrogen

NO3-N Nitrate nitrogen

NP nonylphenol

NRW North Rhine Westphalia

O octa

P poly

PAH polycyclic aromatic hydrocarbon

PCB polychlorinated biphenyl

Pe penta

T tetra

TEQ toxicity equivalent

UBA Umweltbundesamt

WHO World Health Organization

WWTP waste water treatment plant

6

1 Introduction This report gives an overview on the available analytical information on the following raw materials to be used for the production of validation materials of the so-called Project HORIZONTAL

bull Four sludge materials from Duumlsseldorf Germany

bull An agricultural soil material from Reading United Kingdom

bull A compost material from Vienna Austria

bull A compost material from Korschenbroich Germany

bull A sludge-amended agricultural soil from Pavia Province Italy

bull A sludge-amended soil from Barcelona Spain

bull A sludge-amended soil from Essen Germany

bull A long-term sludge exposed soil from Hohenheim Germany

The following analytical information was gathered partly before and during the sampling of the raw materials to be used for the production of the HORIZONTAL validation materials The material were sampled by IES and shipped to IRMM in the course of the year 2005 The information gathered was then completed by various analytical screenings for PAHs and PCBs done by the Institute for Reference Materials and Measurements Geel Belgium for phthalates done by UBA Berlin Germany for PBDE done by IIQAB-CSIC Barcelona Spain for trace elements and some selected major and minor elements by the Institute for Environment and Sustainability Ispra Italy

The work compiled hereafter is based on the numerous additional efforts of the scientists working at various members of the consortium Project HORIZONTAL-Org and contributing organisations

This work is gratefully acknowledged

2 Overview on property values

21 Sludge materials from Duumlsseldorf Germany

The various sewage sludge materials originate from various installations in the North Rhine Westphalia and were produced and sampled by staff from the Landesumweltamt (LUA) NRW under the responsibility from Dr K Furtmann

In total four sludge materials (Sludge A and D from a major municipal WWTP Sludge B from a municipal WWTP with industrial input and Sludge C from a municipal WWTP with high PCB-Content) were obtained and will be blended to two final materials Before sampling the following analytical data for a typical sample were received

7

Table 1 ndash Analytical data obtained on an average sludge sample in LUA NRW (with courtesy of K Furtmann LUA Duumlsseldorf)

Parameter Concentration PCB 120 ugkg DEHP 110 mgkg PAH 5 mgkg (EPA) PCDDF 15 ng TEkg PBDE 400 ugkg NP 40 mgkg LAS 3 gkg AOX 300 mgkg

Subsequent screening led to the information displayed hereafter It should be stressed that the data were obtained as SCREENING information on the UNTREATED or partially treated raw materials Therefore the final target values which are relevant for the validation intercomparison can be different

Table 2 ndash Analytical data obtained on a first screening on the sludge samples from LUA NRW

Sewage sludge A

Dusseldorf

sewage sludge D

Dusseldorf PCB (ngg) 28 62 35 52 101 65 101 31 38 118 49 40 153 30 33 105 24 11 138 46 38 156 lt1 lt1 180 34 23 170 23 19 PAH (ngg) Naphtalene 34 381 Acenaphtylene 15 43 Acenaphthene 81 108 Fluorene 94 1167 Phenantrene 3440 Anthracene 22 344 Flouranthene 316 4817 Pyrene 235 3011 Benz(a)anthracene 473 791 Chrysene 691 1078 Benz(b)fluoranthene 538 1688 Benz(k)fluoranthene 228 635 Benz(a)pyrene 383 1114 Indeno(123-cd)pyrene 92 229 Dibenzo(ah)anthracene 71 70 Benzo(ghi)perylene 80 185

8

Table 3 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Sludge D (1) 0135 41474 385 Sludge B (2) 0538 0034 30634 547 Sludge A (3) 0184 0037 31399 146 Sludge C (4) 0354 1528 6678 229

Table 4 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Sludge 2

(B)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

554

959

694

591

772

509

nq

nq

970

2216

2379

Table 5 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena IES Ispra Spain) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Sludge 1 (D) 265 290 533 359 1231 338 784 438 lt 005 232 786 Sludge 2 (B) 119 311 626 202 278 299 722 251 lt 005 118 625 Sludge 3 (A) 168 360 621 332 847 416 119 451 lt 005 116 1237 Sludge 4 (C) 563 198 116 273 726 511 473 618 lt 005 444 2015

Table 6 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Sludge 1 (D) 2154 58 844 099 103 101 4367 lt15 50448 Sludge 2 (B) 1067 366 692 046 1491 077 5217 lt15 57633 Sludge 3 (A) 731 663 684 035 1287 068 3733 lt15 60369 Sludge 4 (C) 4379 965 527 163 522 107 5628 lt15 23945

Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM)Sludge 1 (D) 03 2403 101 1002 350 15 1944 132Sludge 2 (B) 031 315 97 879 172 12 514 180Sludge 3 (A) 031 1281 153 1567 265 16 1440 168Sludge 4 (C) 055 231 628 2625 371 81 1101 244

9

22 Agricultural soil material from Reading United Kingdom

The material was proposed by the University of Reading (S Nortcliff) and was sampled from a site called ldquoFrogmore Farmrdquo which was featured in the ldquoMetalsrdquo Report for HORIZONTAL This site is close to Reading with soils developed on flintyloamy periglacial materials over Chalk has a long and well documented history of sludge application The focus of the work of Nortcliff et al undertook at this site and the monitoring and control at the site (by Thames Water and the subsequent subsidiary bodies dealing with sludge application to soil) was on metals (and metal loads) with no analysis or indeed any form of investigation in to organics in the broadest sense

The analytical information produced in the context of the screening of the raw material is displayed below

Table 7 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 3

(Reading) 0032 0119 669

Table 8 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 3 (Reading) 015 706 279 138 152 901 267 300 lt 005 258 931

Table 9 ndash Analytical data obtained on a first screening on the sludge-amended soil from Reading (courtesy of IRMM)

Parameter Concentration

PCB ngg 28 lt1 52 lt1 101 lt1 118 lt1 153 lt1 105 lt1 138 lt1 156 lt1 180 lt1 170 lt1 PAH ngg Naphtalene lt10 Acenaphtylene 21 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene lt10 Flouranthene 818 Pyrene 776 Benz(a)anthracene 565

10

Parameter Concentration

Chrysene 608 Benz(b)fluoranthene 824 Benz(k)fluoranthene 329 Benz(a)pyrene 799 Indeno(123-cd)pyrene

779

Dibenzo(ah)anthracene 118 Benzo(ghi)perylene 394

Table 10 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 3

(Reading)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

103

003

nq

nq

nq

nd

nd

272

273

Table 11 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 3 (Reading) 015 706 279 138 152 901 267 300 lt 005 258 931

Table 12 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 3 (Reading) 7936 477 112 096 194 017 4107 443 2102 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 3 (Reading) 042 13 45 69 69 69 216 92

Table 13 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 3 (Reading) 012

11

23 Compost from Vienna Austria

The fresh compost material was obtained from the Austrian Federal Environment Agency (UBA Vienna) which had used a sub-batch of the raw material for national intercomparson The remainder of the material was stored at 4degC until shipment to IRMM for further processing The following analytical information was provided by UBA Austria and completed with various screenings

Table 14 ndash Analytical data on compost material received from UBA Austria Inorganic and sum parameters

Parameter Unit Sample fraction used Observed mean B CAT mgl FM Fresh sample lt10mm 61 K CAT mgl FM Fresh sample lt10mm 2624 Mg CAT mgl FM Fresh sample lt10mm 242 P CAT mgl FM Fresh sample lt10mm 49 B CAT DM Fresh sample lt10mm 00017 K CAT DM Fresh sample lt10mm 072 Mg CAT DM Fresh sample lt10mm 007 P CAT DM Fresh sample lt10mm 001 NO3-N mgkg FM Fresh sample lt10mm 35 NH4-N mgkg FM Fresh sample lt10mm 230 Ctotal DM lt45degdry milled 29 Corg DM lt45degdry milled 27 Ntotal DM lt45degdry milled 17 P mgkg DM lt45degdry milled 2596 K mgkg DM lt45degdry milled 11019 K DM lt45degdry milled 110 B mgkg DM lt45degdry milled 60 Cd mgkg DM lt45degdry milled 046 Cr mgkg DM lt45degdry milled 25 Cu mgkg DM lt45degdry milled 46 Hg mgkg DM lt45degdry milled 020 Ni mgkg DM lt45degdry milled 18 Pb mgkg DM lt45degdry milled 45 Zn mgkg DM lt45degdry milled 198 Ca mgkg DM lt45degdry milled 68776 Ca DM lt45degdry milled 69 Mo mgkg DM lt45degdry milled 08 S mgkg DM lt45degdry milled 2137 Fe mgkg DM lt45degdry milled 9959 Mn mgkg DM lt45degdry milled 418 Na mgkg DM lt45degdry milled 742 Co mgkg DM lt45degdry milled 41 AOX mgkg DM lt30deg dry milled 62

Table 15 ndash Analytical data on compost material received from UBA Austria Polycyclic aromatic hydrocarbons

PAH Unit Result Naphthaline microgkg DM 93 Acenaphthylene microgkg DM 86 Acenaphthene microgkg DM 5 Fluorene microgkg DM 80 Phenanthrene microgkg DM 89 Anthracene microgkg DM 27 Fluoranthene microgkg DM 487 Pyrene microgkg DM 380

12

PAH Unit Result Benzo(a)anthracene microgkg DM 278 Chrysene microgkg DM 317 Benzo(b)fluoranthene microgkg DM 365 Benzo(k)fluoranthene microgkg DM 193 Benz(a)pyrene microgkg DM 320 Indeno(123-cd)pyrene microgkg DM 233 Dibenz(ah)anthracene microgkg DM 67 Benzo(ghi)perylene microgkg DM 225 Sum EPA microgkg DM 3013 Sum EPA mgkg DM 30

Table 16 ndash Analytical data on compost material received from UBA Austria Sum PCDDs and PCBs

Parameter

Dioxine TEQ (ITEF) ngkg DM 73 TEQ (WHO) ngkg DM 35 PCB Σ Ballschmiter mgkg DM 005

Table 17 ndash Analytical data on compost material obtained by screening in IRMM

Parameter Result in ngg

PCB 28 2 52 2 101 4 118 3 153 10 105 1 138 8 156 1 180 5 170 lt1 PAH Naphtalene lt10 Acenaphtylene lt10 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene 26 Fluoranthene 611 Pyrene 510 Benz(a)anthracene 888 Chrysene 957 Benz(b)fluoranthene 1531 Benz(k)fluoranthene 547 Benz(a)pyrene 1101 Indeno(123-cd)pyrene 416 Dibenzo(ah)anthracene 81 Benzo(ghi)perylene 295

13

Table 18 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Compost 1

(Vienna)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

402

019

259

nq

023

004

nq

nq

144

174

259

Table 19 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Compost 1

(Vienna) 0058 1426 557

Table 20 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Compost 1 (Vienna) 039 736 319 410 365 127 495 004 079 013 208

Table 21 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Compost 1 (Vienna) 2063 431 617 426 199 249 1602 lt15 10521

Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Compost 1 (Vienna) 035 3496 81 375 79 55 653 60

Table 22 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Compost 1 (Vienna) 017

14

24 Agricultural soil sludge amended soil from Pavia Italy

This sludge-amended soil material was obtained during a monitoring campaign which aimed at a generic description of the over-all soil quality in Pavia Province Italy The material which was collected from the upper horizon originates from a small farm called ldquoCascina Novellordquo During the characterisation of the site the following analytical information was obtained on a pooled sample of a sub-area of the farm of 20 X 20 m2

Table 23 ndash Analytical data on Pavia soil

Parameter Result Al 713 Wgt As 224 mgkg Cd 079 mgkg Cr 59 mgkg Cu 308 mgkg Hg 008 mgkg Ni 344 mgkg Pb 246 mgkg Zn 95 mgkg C 091 Wgt 2378-TCDD 0047 pgg 12378-PeCDD 015 pgg 123478-HxCDD 019 pgg 123678-HxCDD 15 pgg 123789-HxCDD 074 pgg 1234678-HpCDD 26 pgg OCDD 382 pgg 2378-TCDF 068 pgg 12378-PeCDF 053 pgg 23478-PeCDF 071 pgg 123478-HxDF 100 pgg 123678-HxDF 066 pgg 234678-HxDF 16 pgg 123789-HxDF 027 pgg 1234678-HpDF 12 pgg 1234789-HpDF 068 pgg OCDF 33 pgg I-TEQ 20 pgg WHO-TEQ 17 pgg

In addition the screening performed at IRMM did not reveal significant quantities of PCBs and PAHs which were all below the LoDs (1 ngg for PCBs and 10 ngg for PAHs respectively)

Table 24 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 5 (Pavia) 0005 0011 154

15

Table 25 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 5

(Pavia)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

039

nq

nq

008

nq

nd

nd

670

671

Table 26 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 5 (Pavia) 033 184 573 225 426 305 206 200 lt 005 381 878

Table 27 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 5 (Pavia) 6939 129 145 224 425 116 6118 255 1789 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 5 (Pavia) 184 62 38 108 55 66 597 110

Table 28 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 5 (Pavia) 006

16

25 Sludge-amended-soil from Barcelona Spain

The sludge-amended soil material from Barcelona sampled upon indication from the Barcelorsquo- Group in Barcelona

Table 29 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 2 (Lleida T) 0015 0183 1138

Table 30 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 2

(Lleida T)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

159

045

nq

048

160

nq

nq

1000

1004

Table 31 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 2 (Lleida T) 059 141 327 536 405 186 184 224 lt 005 318 111

Table 32 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 2 (Lleida T) 4443 1067 1429 253 344 204 4116 780 3396 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 2 (Lleida T) 064 65 26 125 59 17 547 65

Table 33 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 2 (Lleida T) 010

17

26 Sludge amended soil from Essen Germany

The German sludge-amended soil from Essen which was provided as the three sludge materials by LUA NRW did not feature significant concentrations of the PCB congeners 28 52 101 118 153 105 138 156 180 170 but had detectable amounts of some PAHs

Table 34 ndash Analytical screening data on the German sludge-amended soil

Parameter Concentration(ngg)

Naphtalene lt10 Acenaphtylene lt10 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene lt10 Fluoranthene 28 Pyrene 20 Benz(a)anthracene 24 Chrysene 47 Benz(b)fluoranthene 76 Benz(k)fluoranthene 20 Benz(a)pyrene 35 Indeno(123-cd)pyrene 35 Dibenzo(ah)anthracene 10 Benzo(ghi)perylene 26

Table 35 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 4 (Essen) 0011 0302 055

Table 36 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 4

(Essen)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

nq

nq

nq

nq

nq

nq

128

191

203

18

Table 37 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 4 (Essen) 052 545 261 805 320 403 273 273 lt 005 295 781

Table 38 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 4 (Essen) 7947 442 085 06 086 007 2163 189 2019 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 4 (Essen) 045 19 42 87 683 60 462 61

Table 39 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 4 (Essen) 004

27 Long-term sludge exposed soil from Hohenheim-Stuttgart Germany

Similarly an additional sludge exposed soil was sampled at the University of Hohenheim Stuttgart were a test soil was long-term exposed to elevated concentrations of sewage sludge

Table 40 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 1 (Stuttgart) 0045 0263 1765

Table 41 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 1

(Stuttgart)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

230

006

004

004

nq

nd

nd

498

500

19

Table 42 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 1 (Stuttgart) 069 127 361 262 504 183 252 262 lt 005 266 142

Table 43 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 1 (Stuttgart) 7194 1006 133 186 366 088 7874 275 3571 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 1 (Stuttgart) 123 50 47 212 85 69 991 129

Table 44 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 1 (Stuttgart) 177

18

Annex 3

Statistical calculations

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 47)Mandels h statistics(Sludge 1 - PBD 47)

Sample Sludge 1 NUM

Element PBD 47

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00213 0001 3 -021 005 - - 10L - - NUM46L 00273 0002 4 016 021 - - 46L - - NUM64L 00059 0000 4 -116 002 NUM - 64L - - NUM12L 00188 0000 4 -036 002 - - 12L - - NUM26L 00499 0024 2 157 223 Fail - - 26L - - NUM

Totgem 0025 0005 mgkg 1-level 172 (185) NUM (10L46L64L12L26L) -1Totstd= 0016 0010 5-level 157 (162) 5

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 5 Labs rejected (10L46L64L12L26L)

000 050 100 150 200 250

k-values

10L

46L

64L

12L

26L

Mandels k statistics(Sludge 1 - PBD 47)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

10L

46L

64L

12L

26L

Labo

rato

ries

NUM

-200 -100 000 100 200

h-values

10L

46L

64L

12L

26L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 47)

Sludge 1-PBD 47

Unit mgkg

Mandels k statistics(Soil 3 - PBD 47)Mandels h statistics(Soil 3 - PBD 47)

Sample Soil 3 Soil 3 - PBD 47 -- Mean PARM = 0001 [mgkg]

Element PBD 47

General calcparmT1= 134814E-02T2= 142830E-05T3= 13T4= 45T5= 22767E-06

n= variabelp= 4

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean26L 00007 0000 2 -143 001 00007 00000 2 1 00046L 00010 0001 4 010 181 00010 00008 4 3 00010L 00011 0000 3 049 023 00011 00001 3 2 00012L 00012 0000 4 084 081 00012 00004 4 3 000

Totgem 0001 0000 mgkg 1-level 149 (177) 4 00010 () 4 3Totstd= 0000 0000 5-level 142 (159)

RESULTS Mean = 000100 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000050 --gt 5031 r = 00014Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000050 --gt 5031 R = 00014Remarks none

000 050 100 150 200

k-values

26L

46L

10L

12L

Mandels k statistics(Soil 3 - PBD 47)

00 00 00 00 00 00 00 00 00 00 00

Deviation from Mean

26L

46L

10L

12L

Labo

rato

ries

Soil 3 - PBD 47 -- Mean PARM = 0001 [mgkg]

-200 -100 000 100

h-values

26L

46L

10L

12L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 47)

Soil 3-PBD 47

Unit mgkg

Mandels k statistics(Compost 1 - PBD 99)Mandels h statistics(Compost 1 - PBD 99)

Sample Compost 1 Compost 1 - PBD 99 -- Mean PARM = 0003 [mgkg]

Element PBD 99

General calcparmT1= 492124E-02T2= 148747E-04T3= 17T4= 61T5= 93196E-06

n= variabelp= 5

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00020 0000 4 -137 053 00020 00004 4 3 000

26L 00025 0000 2 -058 024 00025 00002 2 1 00010L 00029 0000 3 012 032 00029 00003 3 2 00046L 00033 0001 4 069 161 00033 00013 4 3 00012L 00036 0001 4 114 140 00036 00011 4 3 000

Totgem 0003 0001 mgkg 1-level 172 (185) 5 00029 () 5 4Totstd= 0001 0001 5-level 157 (162)

RESULTS Mean = 000286 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000088 --gt 3086 r = 00025Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000101 --gt 3525 R = 00028Remarks none

000 050 100 150 200

k-values

4L

26L

10L

46L

12L

Mandels k statistics(Compost 1 - PBD 99)

00 00 00 00 00 00 00 00 00 00

Deviation from Mean

4L

26L

10L

46L

12L

Labo

rato

ries

Compost 1 - PBD 99 -- Mean PARM = 0003 [mgkg]

-200 -100 000 100 200

h-values

4L

26L

10L

46L

12L

Labo

rato

ries

Mandels h statistics(Compost 1 - PBD 99)

Compost 1-PBD 99

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 99)Mandels h statistics(Sludge 1 - PBD 99)

Sample Sludge 1 Sludge 1 - PBD 99 -- Mean PARM = 0024 [mgkg]

Element PBD 99

General calcparmT1= 448050E-01T2= 112113E-02T3= 19T4= 73T5= 32972E-05

n= variabelp= 5

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean64L 00173 0002 4 -118 041 Fail 00173 00019 4 3 -0014L 00183 0002 4 -104 032 00183 00015 4 3 -001

12L 00227 0001 4 -038 022 00227 00010 4 3 00010L 00290 0001 3 055 021 00290 00010 3 2 00146L 00320 0002 4 100 039 00320 00018 4 3 00126L 00323 0011 2 105 234 - - 26L - - 001

Totgem 0025 0003 mgkg 1-level 187 (177) 5 00239 (26L) 5 4Totstd= 0007 0004 5-level 166 (154) 1

RESULTS Mean = 002385 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000153 --gt 643 r = 00043Between lab variance S2L = 000004Reproducibility var S2R = 000004Reproducibility std SR = 000666 --gt 2791 R = 00186Remarks 1 Lab rejected (26L)

000 050 100 150 200 250

k-values

64L

4L

12L

10L

46L

26L

Mandels k statistics(Sludge 1 - PBD 99)

00 00 00 00 00 00 00 00 00 00

Deviation from Mean

64L

4L

12L

10L

46L

26L

Labo

rato

ries

Sludge 1 - PBD 99 -- Mean PARM = 0024 [mgkg]

-200 -100 000 100 200

h-values

64L

4L

12L

10L

46L

26L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 99)

Sludge 1-PBD 99

Unit mgkg

Mandels k statistics(Soil 3 - PBD 99)Mandels h statistics(Soil 3 - PBD 99)

Sample Soil 3 NUM

Element PBD 99

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00017 0000 4 091 068 - - 10L - - NUM46L 00017 0001 4 100 211 - - 46L - - NUM64L 00005 0000 4 -106 023 NUM - 64L - - NUM12L 00012 0000 4 015 014 - - 12L - - NUM26L 00006 0000 2 -101 012 - - 26L - - NUM

Totgem 0001 0000 mgkg 1-level 172 (173) NUM (10L46L64L12L26L) -1Totstd= 0001 0000 5-level 157 (153) 5

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 5 Labs rejected (10L46L64L12L26L)

000 050 100 150 200 250

k-values

10L

46L

64L

12L

26L

Mandels k statistics(Soil 3 - PBD 99)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

10L

46L

64L

12L

26L

Labo

rato

ries

NUM

-200 -100 000 100 200

h-values

10L

46L

64L

12L

26L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 99)

Soil 3-PBD 99

Unit mgkg

Mandels k statistics(Compost 1 - PBD 100)Mandels h statistics(Compost 1 - PBD 100)

Sample Compost 1 Compost 1 - PBD 100 -- Mean PARM = 0001 [mgkg]

Element PBD 100

General calcparmT1= 124272E-02T2= 113129E-05T3= 14T4= 52T5= 46584E-07

n= variabelp= 4

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean26L 00006 0000 2 -131 037 Fail 00006 00001 2 1 00010L 00009 0000 4 003 083 00009 00002 4 3 00046L 00009 0000 4 016 115 00009 00002 4 3 00012L 00011 0000 4 112 136 Fail 00011 00003 4 3 000

Totgem 0001 0000 mgkg 1-level 149 (167) 4 00009 () 4 3Totstd= 0000 0000 5-level 142 (15)

RESULTS Mean = 000085 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000022 --gt 2531 r = 00006Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000025 --gt 2882 R = 00007Remarks none

000 050 100 150

k-values

26L

10L

46L

12L

Mandels k statistics(Compost 1 - PBD 100)

00 00 00 00 00 00 00 00 00 00 00

Deviation from Mean

26L

10L

46L

12L

Labo

rato

ries

Compost 1 - PBD 100 -- Mean PARM = 0001 [mgkg]

-200 -100 000 100 200

h-values

26L

10L

46L

12L

Labo

rato

ries

Mandels h statistics(Compost 1 - PBD 100)

Compost 1-PBD 100

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 100)Mandels h statistics(Sludge 1 - PBD 100)

Sample Sludge 1 Sludge 1 - PBD 100 -- Mean PARM = 0005 [mgkg]

Element PBD 100

General calcparmT1= 852065E-02T2= 412762E-04T3= 18T4= 68T5= 78914E-07

n= variabelp= 5

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00039 0000 4 -042 007 Fail 00039 00002 4 3 000

12L 00044 0000 4 -041 005 Fail 00044 00001 4 3 00010L 00046 0000 4 -041 013 Fail 00046 00003 4 3 00046L 00056 0000 4 -040 012 Fail 00056 00003 4 3 00026L 00059 0000 2 -040 013 Fail 00059 00003 2 1 00038L 02168 0006 4 204 244 Fail - - 38L - - 021

Totgem 0040 0001 mgkg 1-level 187 (177) 5 00049 (38L) 5 4Totstd= 0087 0002 5-level 166 (154) 1

RESULTS Mean = 000486 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000025 --gt 507 r = 00007Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000084 --gt 1731 R = 00024Remarks 1 Lab rejected (38L)

000 050 100 150 200 250

k-values

4L

12L

10L

46L

26L

38L

Mandels k statistics(Sludge 1 - PBD 100)

-01 00 01 01 02 02 03

Deviation from Mean

4L

12L

10L

46L

26L

38L

Labo

rato

ries

Sludge 1 - PBD 100 -- Mean PARM = 0005 [mgkg]

-100 000 100 200 300

h-values

4L

12L

10L

46L

26L

38L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 100)

Sludge 1-PBD 100

Unit mgkg

Mandels k statistics(Soil 3 - PBD 100)Mandels h statistics(Soil 3 - PBD 100)

Sample Soil 3 NUM

Element PBD 100

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00003 0000 4 -050 000 Fail - - 10L - - NUM46L 00003 0000 4 -050 000 Fail NUM - 46L - - NUM3L 305500 2051 2 150 200 Fail - - 3L - - NUM

26L 00005 0000 2 -050 000 Fail - - 26L - - NUM

Totgem 7638 0513 mgkg 1-level 149 (177) NUM (10L46L3L26L) -1Totstd= 15275 1025 5-level 142 (159) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (10L46L3L26L)

000 050 100 150 200

k-values

10L

46L

3L

26L

Mandels k statistics(Soil 3 - PBD 100)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

10L

46L

3L

26L

Labo

rato

ries

NUM

-100 000 100 200

h-values

10L

46L

3L

26L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 100)

Soil 3-PBD 100

Unit mgkg

Mandels k statistics(Compost 1 - PBD 153)Mandels h statistics(Compost 1 - PBD 153)

Sample Compost 1 NUM

Element PBD 153

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean44L 00053 0001 3 150 157 Fail - - 44L - - NUM46L 00007 0000 4 -044 111 Fail - - 46L - - NUM12L 00005 0000 4 -051 055 Fail - - 12L - - NUM26L 00005 0000 2 -054 001 Fail NUM - 26L - - NUM

Totgem 0002 0000 mgkg 1-level 149 (177) NUM (44L46L12L26L) -1Totstd= 0002 0000 5-level 142 (159) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (44L46L12L26L)

000 050 100 150 200

k-values

44L

46L

12L

26L

Mandels k statistics(Compost 1 - PBD 153)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

44L

46L

12L

26L

Labo

rato

ries

NUM

-100 000 100 200

h-values

44L

46L

12L

26L

Labo

rato

ries

Mandels h statistics(Compost 1 - PBD 153)

Compost 1-PBD 153

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 153)Mandels h statistics(Sludge 1 - PBD 153)

Sample Sludge 1 Sludge 1 - PBD 153 -- Mean PARM = 0004 [mgkg]

Element PBD 153

General calcparmT1= 676738E-02T2= 267609E-04T3= 18T4= 68T5= 19626E-05

n= variabelp= 5

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00024 0000 4 -157 017 00024 00002 4 3 000

12L 00038 0002 4 006 154 00038 00018 4 3 00046L 00039 0000 4 011 026 00039 00003 4 3 00026L 00039 0000 2 018 004 00039 00000 2 1 00064L 00049 0002 4 122 159 00049 00018 4 3 000

Totgem 0004 0001 mgkg 1-level 172 (173) 5 00038 () 5 4Totstd= 0001 0001 5-level 157 (153)

RESULTS Mean = 000378 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000123 --gt 3252 r = 00034Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000142 --gt 3754 R = 00040Remarks none

000 050 100 150 200

k-values

4L

12L

46L

26L

64L

Mandels k statistics(Sludge 1 - PBD 153)

00 00 00 00 00 00 00

Deviation from Mean

4L

12L

46L

26L

64L

Labo

rato

ries

Sludge 1 - PBD 153 -- Mean PARM = 0004 [mgkg]

-200 -100 000 100 200

h-values

4L

12L

46L

26L

64L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 153)

Sludge 1-PBD 153

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 154)Mandels h statistics(Sludge 1 - PBD 154)

Sample Sludge 1 NA

Element PBD 154

General calcparmT1= NAT2= NAT3=T4=T5=

n= variabelp=

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00021 0000 3 -100 021 NA - 4L - - NA

46L 00025 0000 4 115 018 NA - 46L - - NA64L 00021 0001 4 -066 179 - - 64L - - NA12L 00023 0000 4 050 085 - - 12L - - NA

Totgem 0002 0000 mgkg 1-level 149 (167) NA (4L46L64L12L) -1Totstd= 0000 0000 5-level 142 (15) 4

RESULTS Mean = NA mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NAReproducibility var S2R = NAReproducibility std SR = NA --gt NA R = NARemarks 4 Labs rejected (4L46L64L12L)

000 050 100 150 200

k-values

4L

46L

64L

12L

Mandels k statistics(Sludge 1 - PBD 154)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

4L

46L

64L

12L

Labo

rato

ries

NA

-100 000 100 200

h-values

4L

46L

64L

12L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 154)

Sludge 1-PBD 154

Unit mgkg

Mandels k statistics(Soil 3 - PBD 154)Mandels h statistics(Soil 3 - PBD 154)

Sample Soil 3 NUM

Element PBD 154

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

4L 00010 - 1 150 Fail - - 4L - - NUM46L 00001 0000 4 -053 096 Fail - - 46L - - NUM64L 00001 0000 4 -056 105 Fail NUM - 64L - - NUM12L 00002 0000 4 -040 099 Fail - - 12L - - NUM

Totgem 000037 0000 mgkg 1-level 149 (164) NUM (4L46L64L12L) -1Totstd= 000042 0000 5-level 142 (153) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (4L46L64L12L)

000 050 100 150

k-values

4L

46L

64L

12L

Mandels k statistics(Soil 3 - PBD 154)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

4L

46L

64L

12L

Labo

rato

ries

NUM

-100 000 100 200

h-values

4L

46L

64L

12L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 154)

Soil 3-PBD 154

Unit mgkg

Mandels k statistics(Compost 1 - PBD 209)Mandels h statistics(Compost 1 - PBD 209)

Sample Compost 1 NUM

Element PBD 209

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00065 0003 2 -049 032 - - 4L - - NUM

44L 00573 0021 4 150 197 Fail - - 44L - - NUM12L 00078 0001 4 -045 011 - - 12L - - NUM26L 00049 0000 2 -056 000 NUM - 26L - - NUM

Totgem 0019 0006 mgkg 1-level 149 (177) NUM (4L44L12L26L) -1Totstd= 0025 0010 5-level 142 (159) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (4L44L12L26L)

000 050 100 150 200

k-values

4L

44L

12L

26L

Mandels k statistics(Compost 1 - PBD 209)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

4L

44L

12L

26L

Labo

rato

ries

NUM

-100 000 100 200

h-values

4L

44L

12L

26L

Labo

rato

ries

Mandels h statistics(Compost 1 - PBD 209)

Compost 1-PBD 209

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 209)Mandels h statistics(Sludge 1 - PBD 209)

Sample Sludge 1 Sludge 1 - PBD 209 -- Mean PARM = 0249 [mgkg]

Element PBD 209

General calcparmT1= 394542E+00T2= 107296E+00T3= 16T4= 56T5= 19723E-02

n= variabelp= 5

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 01550 0055 4 -112 148 Fail 01550 00551 4 3 -009

46L 02050 0007 2 -053 019 02050 00071 2 1 -00412L 02137 0058 4 -042 155 02137 00576 4 3 -00426L 03149 0021 2 078 057 Fail 03149 00210 2 1 00764L 03577 0007 4 129 020 Fail 03577 00074 4 3 011

Totgem 0249 0030 mgkg 1-level 172 (185) 5 02493 () 5 4Totstd= 0084 0025 5-level 157 (162)

RESULTS Mean = 024926 mgkg

Repeatability variance S2r = 000179Repeatability std Sr = 004234 --gt 1699 r = 01186Between lab variance S2L = 000743Reproducibility var S2R = 000922Reproducibility std SR = 009604 --gt 3853 R = 02689Remarks none

000 050 100 150 200

k-values

4L

46L

12L

26L

64L

Mandels k statistics(Sludge 1 - PBD 209)

-01 -01 00 01 01 02

Deviation from Mean

4L

46L

12L

26L

64L

Labo

rato

ries

Sludge 1 - PBD 209 -- Mean PARM = 0249 [mgkg]

-200 -100 000 100 200

h-values

4L

46L

12L

26L

64L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 209)

Sludge 1-PBD 209

Unit mgkg

Mandels k statistics(Soil 3 - PBD 209)Mandels h statistics(Soil 3 - PBD 209)

Sample Soil 3 Soil 3 - PBD 209 -- Mean PARM = 0258 [mgkg]

Element PBD 209

General calcparmT1= 596398E+00T2= 191917E+00T3= 22T4= 84T5= 13249E-02

n= variabelp= 6

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean26L 01162 0021 2 -108 074 Fail 01162 00207 2 1 -0144L 01303 0031 4 -097 111 Fail 01303 00312 4 3 -013

46L 01975 0036 4 -046 128 Fail 01975 00359 4 3 -00644L 02898 0035 4 024 124 Fail 02898 00346 4 3 00312L 03895 0018 4 100 065 Fail 03895 00181 4 3 01364L 04260 0022 4 127 078 Fail 04260 00219 4 3 017

Totgem 0258 0027 mgkg 1-level 187 (177) 6 02582 () 6 5Totstd= 0132 0008 5-level 166 (154)

RESULTS Mean = 025818 mgkg

Repeatability variance S2r = 000083Repeatability std Sr = 002878 --gt 1115 r = 00806Between lab variance S2L = 001640Reproducibility var S2R = 001723Reproducibility std SR = 013127 --gt 5084 R = 03676Remarks none

000 050 100 150

k-values

26L

4L

46L

44L

12L

64L

Mandels k statistics(Soil 3 - PBD 209)

-02 -01 -01 00 01 01 02 02

Deviation from Mean

26L

4L

46L

44L

12L

64L

Labo

rato

ries

Soil 3 - PBD 209 -- Mean PARM = 0258 [mgkg]

-200 -100 000 100 200

h-values

26L

4L

46L

44L

12L

64L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 209)

Soil 3-PBD 209

Unit mgkg

Mandels k statistics(Compost 1 - Sum PBD)Mandels h statistics(Compost 1 - Sum PBD)

Sample Compost 1 Compost 1 - Sum PBD -- Mean PARM = 0009 [mgkg]

Element Sum PBD

General calcparmT1= 154064E-01T2= 169065E-03T3= 18T4= 68T5= 11354E-04

n= variabelp= 5

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00031 0002 4 -067 016 00031 00016 4 3 -0014L 00055 0005 4 -056 048 00055 00047 4 3 000

46L 00085 0003 4 -042 031 00085 00030 4 3 00026L 00123 0000 2 -024 003 00123 00002 2 1 00012L 00154 0002 4 -011 021 00154 00021 4 3 00144L 00613 0023 4 200 237 Fail - - 44L - - 005

Totgem 0018 0006 mgkg 1-level 187 (177) 5 00089 (44L) 5 4Totstd= 0022 0009 5-level 166 (154) 1

RESULTS Mean = 000893 mgkg

Repeatability variance S2r = 000001Repeatability std Sr = 000296 --gt 3308 r = 00083Between lab variance S2L = 000002Reproducibility var S2R = 000003Reproducibility std SR = 000570 --gt 6374 R = 00159Remarks 1 Lab rejected (44L)

000 050 100 150 200 250

k-values

10L

4L

46L

26L

12L

44L

Mandels k statistics(Compost 1 - Sum PBD)

00 00 00 00 00 00 01 01

Deviation from Mean

10L

4L

46L

26L

12L

44L

Labo

rato

ries

Compost 1 - Sum PBD -- Mean PARM = 0009 [mgkg]

-100 000 100 200

h-values

10L

4L

46L

26L

12L

44L

Labo

rato

ries

Mandels h statistics(Compost 1 - Sum PBD)

Compost 1-Sum PBD

Unit mgkg

Mandels k statistics(Sludge 1 - Sum PBD)Mandels h statistics(Sludge 1 - Sum PBD)

Sample Sludge 1 Sludge 1 - Sum PBD -- Mean PARM = 0256 [mgkg]

Element Sum PBD

General calcparmT1= 531806E+00T2= 162188E+00T3= 22T4= 84T5= 25223E-02

n= variabelp= 6

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00423 0025 4 -156 044 Fail 00423 00252 4 3 -02146L 01808 0118 4 -049 205 - - 46L - - -0074L 01810 0056 4 -049 097 01810 00558 4 3 -007

38L 02168 0006 4 -022 010 02168 00059 4 3 -00412L 02890 0065 4 034 113 02890 00647 4 3 00364L 03958 0008 4 116 014 Fail 03958 00079 4 3 01426L 04094 0034 2 126 059 Fail 04094 00337 2 1 015

Totgem 0245 0044 mgkg 1-level 198 (179) 6 02557 (46L) 6 5Totstd= 0130 0039 5-level 171 (155) 1

RESULTS Mean = 025570 mgkg

Repeatability variance S2r = 000158Repeatability std Sr = 003970 --gt 1553 r = 01112Between lab variance S2L = 001807Reproducibility var S2R = 001964Reproducibility std SR = 014015 --gt 5481 R = 03924Remarks 1 Lab rejected (46L)

000 050 100 150 200 250

k-values

10L

46L

4L

38L

12L

64L

26L

Mandels k statistics(Sludge 1 - Sum PBD)

-03 -02 -02 -01 -01 00 01 01 02 02

Deviation from Mean

10L

46L

4L

38L

12L

64L

26L

Labo

rato

ries

Sludge 1 - Sum PBD -- Mean PARM = 0256 [mgkg]

-200 -100 000 100 200

h-values

10L

46L

4L

38L

12L

64L

26L

Labo

rato

ries

Mandels h statistics(Sludge 1 - Sum PBD)

Sludge 1-Sum PBD

Unit mgkg

Mandels k statistics(Soil 3 - Sum PBD)Mandels h statistics(Soil 3 - Sum PBD)

Sample Soil 3 Soil 3 - Sum PBD -- Mean PARM = 0227 [mgkg]

Element Sum PBD

General calcparmT1= 610980E+00T2= 200876E+00T3= 26T4= 100T5= 13106E-02

n= variabelp= 7

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00028 0001 4 -037 000 Fail 00028 00005 4 3 -02226L 01179 0021 2 -036 003 Fail 01179 00208 2 1 -0114L 01305 0031 4 -036 004 Fail 01305 00308 4 3 -010

46L 02065 0035 4 -036 005 Fail 02065 00350 4 3 -00244L 02923 0037 4 -035 005 Fail 02923 00365 4 3 00712L 04051 0015 4 -034 002 Fail 04051 00149 4 3 01864L 04314 0022 4 -033 003 Fail 04314 00223 4 3 0203L 305500 2051 2 247 283 Fail - - 3L - - 3032

Totgem 4017 0276 mgkg 1-level 206 (181) 7 02266 (3L) 7 6Totstd= 10722 0717 5-level 175 (156) 1

RESULTS Mean = 022663 mgkg

Repeatability variance S2r = 000069Repeatability std Sr = 002626 --gt 1159 r = 00735Between lab variance S2L = 002568Reproducibility var S2R = 002637Reproducibility std SR = 016238 --gt 7165 R = 04547Remarks 1 Lab rejected (3L)

000 050 100 150 200 250 300

k-values

10L

26L

4L

46L

44L

12L

64L

3L

Mandels k statistics(Soil 3 - Sum PBD)

-50 00 50 100 150 200 250 300 350

Deviation from Mean

10L

26L

4L

46L

44L

12L

64L

3L

Labo

rato

ries

Soil 3 - Sum PBD -- Mean PARM = 0227 [mgkg]

-100 000 100 200 300

h-values

10L

26L

4L

46L

44L

12L

64L

3L

Labo

rato

ries

Mandels h statistics(Soil 3 - Sum PBD)

Soil 3-Sum PBD

19

Annex 4

Raw data submitted

Sample Compost1 Sample Compost 1 Sample Compost 1Element PBD 99 Element PBD 100 Element PBD 153

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]4L 00021 10L 00008 44L 000504L 00024 10L 00008 44L 000604L 00014 10L 00007 44L 000504L 00020 10L 00011 46L 00004

10L 00029 46L 00007 46L 0001210L 00027 46L 00012 46L 0000410L 00032 46L 00009 46L 0000946L 00025 46L 00007 12L 0000446L 00052 12L 00008 12L 0000846L 00029 12L 00012 12L 0000446L 00026 12L 00008 12L 0000712L 00026 12L 00014 26L 0000512L 00043 26L 00007 26L 0000512L 00026 26L 0000612L 0004726L 0002626L 00024

Sample Compost 1 Sample Compost 1 Sample Compost 1Element PBD 154 Element PBD 183 Element PBD 196

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]4L 00010 46L 00002 46L 00011

46L 00003 46L 00024 46L 0000846L 00007 46L 00021 12L 0000246L 00003 46L 00003 12L 0000346L 00004 12L 00003 12L 0000112L 00003 12L 00011 12L 0000212L 00005 12L 0000312L 00031 12L 0000312L 00006

Sample Compost 1 Sample Compost 1 Sample Compost 1Element PBD 197 Element PBD 203 Element PBD 209

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00002 46L 00010 4L 0004146L 00023 12L 00002 4L 0008946L 00022 12L 00003 44L 0041012L 00004 12L 00002 44L 0084012L 00006 12L 00002 44L 0064012L 00003 44L 0040012L 00004 12L 00079

12L 0007312L 0006512L 0009326L 0004926L 00049

Sample Compost 1Element PBD 47

LAB PARM [mgkg]26L 0003826L 00039

Element PBD 99 Element PBD 47 Element PBD 209LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]

4L 00170 10L 00210 4L 010004L 00200 10L 00220 4L 018004L 00170 10L 00210 4L 012004L 00190 46L 00300 4L 0220010L 00280 46L 00280 46L 0210010L 00300 46L 00250 46L 0200010L 00290 46L 00260 64L 0351846L 00340 64L 00059 64L 0363846L 00330 64L 00057 64L 0364546L 00300 64L 00062 64L 0350846L 00310 64L 00060 12L 0220964L 00194 12L 00191 12L 0177164L 00154 12L 00187 12L 0292264L 00185 12L 00190 12L 0164664L 00159 12L 00186 26L 0329712L 00242 26L 00666 26L 0300012L 00223 26L 0033212L 0022112L 0022226L 0024626L 00400

Element PBD 203 Element PBD 197 Element PBD 196LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00022 46L 00027 46L 0002446L 00014 46L 00024 46L 0002264L 00036 12L 00161 64L 0005864L 00058 12L 00060 64L 0006512L 00063 12L 00061 12L 0004812L 00034 12L 00036 12L 0002512L 00038 12L 0003212L 00027 12L 00022

Element PBD 183 Element PBD 154 Element PBD 153LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00049 4L 00020 4L 0002246L 00035 4L 00022 4L 0002446L 00036 4L 00020 4L 0002246L 00034 46L 00025 4L 0002664L 00027 46L 00025 46L 0004064L 00023 46L 00025 46L 0004264L 00024 46L 00023 46L 0003564L 00020 64L 00034 46L 0003812L 00230 64L 00023 64L 0007412L 00032 64L 00017 64L 0004712L 00031 64L 00011 64L 0004612L 00030 12L 00030 64L 0003026L 00007 12L 00021 12L 0006526L 00008 12L 00021 12L 00029

12L 00021 12L 0003226L 00015 12L 0002926L 00019 26L 00039

26L 00040

Element PBD 100LAB PARM [mgkg]

4L 000384L 000414L 000374L 00038

38L 0219038L 0220038L 0208038L 0220010L 0004410L 0005010L 0004310L 0004646L 0005746L 0005946L 0005346L 0005312L 0004312L 0004512L 0004312L 0004326L 0006226L 00057

Sample Soil 3 Sample Soil 3 Sample Soil 3Element PBD 99 Element PBD 47 Element PBD 100

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]10L 00016 10L 00011 10L 0000310L 00019 10L 00010 10L 0000410L 00013 10L 00012 10L 0000410L 00019 46L 00007 10L 0000246L 00025 46L 00022 46L 0000246L 00025 46L 00005 46L 0000646L 00008 46L 00007 46L 0000246L 00011 12L 00010 46L 0000264L 00005 12L 00017 3L 29100064L 00005 12L 00010 3L 32000064L 00006 12L 00009 26L 0000564L 00007 26L 00007 26L 0000512L 00012 26L 0000712L 0001312L 0001312L 0001226L 0000526L 00006

Sample Soil 3 Sample Soil 3 Sample Soil 3Element PBD 153 Element PBD 154 Element PBD 196

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]44L 00050 4L 00010 46L 0000744L 00050 46L 00001 46L 0001146L 00002 46L 00002 46L 0000846L 00003 46L 00001 46L 0001146L 00002 46L 00002 64L 0002646L 00002 64L 00001 64L 0002664L 00001 64L 00001 64L 0002964L 00001 64L 00001 64L 0003464L 00001 64L 00002 12L 0004564L 00002 12L 00003 12L 00032

12L 00002 12L 0002212L 00002 12L 0002112L 00002

Sample Soil 3 Sample Soil 3 Sample Soil 3Element PBD 197 Element PBD 203 Element PBD 209

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00006 46L 00011 4L 0091046L 00013 46L 00017 4L 0150046L 00011 46L 00015 4L 0120046L 00013 46L 00018 4L 0160012L 00090 64L 00013 44L 0337012L 00056 64L 00014 44L 0281012L 00033 64L 00016 44L 0287012L 00032 64L 00015 44L 02540

12L 00055 46L 0230012L 00041 46L 0220012L 00027 46L 0150012L 00026 46L 01900

64L 0438164L 0401664L 0414464L 0449812L 0367112L 0397812L 0409112L 03838

Sample Soil 3 26L 0102Element PBD 183 26L 0131

LAB PARM [mgkg]46L 0000746L 0000846L 0005846L 0000764L 0000264L 0000364L 0000364L 0000312L 0001512L 0001112L 0000712L 00007

European Commission EUR 23003 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on polybrominated diphenylethers Author(s) E Sobiecka H van der Sloot D Barcelo B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 68 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07403-5 Abstract Project HORIZONTAL is interdisciplinary aiming at a harmonisation and horizontal standardisation of test procedures in particular for sludge soils and biowastes In the context of this standardization project a series of draft technical specification were designed upon an extensive desk study fine-tuned after expert consultations and finally validated in international intercomparisons exercise This report summarises the work performed within the validation study of the draft standard for the determination of polybrominated diphenylethers (PBDE) in soils sludge and treated bio-waste using gas-chromatography method with mass selective detection (GC-MS) It further explains the underlying statistical concept for the calculation of reproducibility and repeatability from intercomparisons data In addition all single values results of the statistical evaluation as well as background information on the validation materials used are described and explained

The mission of the JRC is to provide customer-driven scientific and technical support for the conception development implementation and monitoring of EU policies As a service of the European Commission the JRC functions as a reference centre of science and technology for the Union Close to the policy-making process it serves the common interest of the Member States while being independent of special interests whether private or national

LB

-NA

-23003-EN

-C

12

Table 1 - Results of the interlaboratory comparison studies of the determination of selected polybrominated diphenyl ethers (PBDE) by gaschromatography with mass spectrometric detection (GC-MS) in soil sludge and treated biowaste All concentrations are expressed in mgkg dm

Matrix Parameter Mean sr sR r R p Outliers Used No of data

No of data reported below

detection

Total no of data

Sludge 1 PBD 47 00181 461 4 15 5 20 Compost 1 00039 94 3 12 0 12 Soil 3 00010 50 50 00014 00014 4 0 13 10 23 Sludge 1 PBD 99 00239 64 28 00043 00186 5 1 19 0 23 Compost 1 00029 31 35 00025 00028 5 0 17 4 21 Soil 3 00013 499 4 16 8 24 Sludge 1 PBD 100 00049 51 17 00007 00024 5 1 18 2 24 Compost 1 00009 25 29 00006 00007 4 0 14 7 21 Soil 3 61103 211 3 10 15 25 Sludge 1 PBD 153 00038 33 38 00034 0004 5 0 18 0 18 Compost 1 00019 116 3 11 3 14 Soil 3 00011 177 2 10 10 20 Sludge 1 PBD 154 00023 234 4 15 2 17 Compost 1 00008 1118 3 9 5 14

13

Matrix Parameter Mean sr sR r R p Outliers Used No of data

No of data reported below

detection

Total no of data

Soil 3 00002 1049 4 13 6 19 Sludge 1 PBD 183 00048 1217 3 12 2 14 Compost 1 00009 1048 2 8 5 13 Soil 3 00011 1395 3 12 6 18 Sludge 1 PBD 196 00037 470 2 8 7 15 Compost 1 00004 950 2 6 4 10 Soil 3 00023 519 3 12 2 14 Sludge 1 PBD 197 00062 834 2 6 8 14 Compost 1 00009 1001 2 7 7 14 Soil 3 00032 904 2 8 6 14 Sludge 1 PBD 203 00037 461 2 8 4 12 Compost 1 00004 978 2 5 3 8 Soil 3 00022 598 3 12 0 12 Sludge 1 PBD 209 02493 170 39 01186 02689 5 0 16 2 18 Compost 1 00273 104 3 10 5 15 Soil 3 02582 1115 51 00806 03676 6 0 22 0 22

14

Matrix Parameter Mean sr sR r R p Outliers Used No of data

No of data reported below

detection

Total no of data

Sludge 1 Sum PBD 0256 155 548 0111 0392 6 1 22 Compost 1 0009 331 637 0008 0016 5 1 18 Soil 3 0227 116 717 0074 0455 7 1 26 Abbreviations sr Repeatability standard deviation SR Reproducibility standard deviation r Repeatability limit (comparing two measurements) R Reproducibility limit (comparing two measurements) p Number of labs determination not possible

15

14 Annexes Annex 1 Model questionnaire to be filled by the participating laboratories Annex 3 Report on the validation materials used Annex 2 Statistical calculations Annex 3 Data submitted

16

Annex 1

Model questionnaire to be filled by the participating laboratories

Model questionnaire to be filled by the participating laboratories Name of laboratory Contact person Contact details email Phone Fax Mail address of lab Dispatch address of lab for shipment of samples (no PO boxes) Title of measurement method (copy attached) Our laboratory is willing to participate in the precision experiment for this draft standard method

Yes No As participant we understand that

bull All essential apparatus chemicals and other requirements specified in the method must be available in our laboratory when the programme begins

bull Specified timing requirements such as starting and finishing date of the programme must be rigidly met

bull The method must be strictly adhered to bull Samples must be handled in accordance with instructions bull A qualified operator must perform the measurements

Having studied the method and having made a fair appraisal of our capabilities and facilities we feel that we will be adequately prepared for cooperative testing of this method Comments helliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphellip Signature Date

17

Annex 2

Report on the validation materials used

VI

Abstract This report gives an overview on the available analytical information on the following raw materials to be used for the production of validation materials of the so-called Project HORIZONTAL

bull Four sludge materials from Duumlsseldorf Germany

bull An agricultural soil material from Reading United Kingdom

bull A compost material from Vienna Austria

bull A compost material from Korschenbroich Germany

bull A sludge-amended agricultural soil from Pavia Province Italy

bull A sludge-amended soil from Barcelona Spain

bull A sludge-amended soil from Essen Germany

bull A long-term sludge exposed soil from Hohenheim Germany

VII

List of Abbreviations Throughout this report the following abbreviations are used

AOX absorbable organic halogens

Corg organic carbon content

Ctotal total carbon content

CAT cation exchangeable

CDD chlorinated dibenzodioxin

CDF chlorinated dibenzofuran

DEHP di(2-ethylhexyl)phthalate

DM dry matter

EPA Environment Protection Agency

EU European Union

FM fresh matter

Hp hepta

Hx hexa

IES Institute for Environment and Sustainability

IRMM Institute for Reference Materials and Measurements

JRC Joint Research Centre

LAS linear alkylsulfonates

LoD limit of detection

LUA Landesumweltamt

Ntotal total nitrogen content

NH4-N Ammonium nitrogen

NO3-N Nitrate nitrogen

NP nonylphenol

NRW North Rhine Westphalia

O octa

P poly

PAH polycyclic aromatic hydrocarbon

PCB polychlorinated biphenyl

Pe penta

T tetra

TEQ toxicity equivalent

UBA Umweltbundesamt

WHO World Health Organization

WWTP waste water treatment plant

6

1 Introduction This report gives an overview on the available analytical information on the following raw materials to be used for the production of validation materials of the so-called Project HORIZONTAL

bull Four sludge materials from Duumlsseldorf Germany

bull An agricultural soil material from Reading United Kingdom

bull A compost material from Vienna Austria

bull A compost material from Korschenbroich Germany

bull A sludge-amended agricultural soil from Pavia Province Italy

bull A sludge-amended soil from Barcelona Spain

bull A sludge-amended soil from Essen Germany

bull A long-term sludge exposed soil from Hohenheim Germany

The following analytical information was gathered partly before and during the sampling of the raw materials to be used for the production of the HORIZONTAL validation materials The material were sampled by IES and shipped to IRMM in the course of the year 2005 The information gathered was then completed by various analytical screenings for PAHs and PCBs done by the Institute for Reference Materials and Measurements Geel Belgium for phthalates done by UBA Berlin Germany for PBDE done by IIQAB-CSIC Barcelona Spain for trace elements and some selected major and minor elements by the Institute for Environment and Sustainability Ispra Italy

The work compiled hereafter is based on the numerous additional efforts of the scientists working at various members of the consortium Project HORIZONTAL-Org and contributing organisations

This work is gratefully acknowledged

2 Overview on property values

21 Sludge materials from Duumlsseldorf Germany

The various sewage sludge materials originate from various installations in the North Rhine Westphalia and were produced and sampled by staff from the Landesumweltamt (LUA) NRW under the responsibility from Dr K Furtmann

In total four sludge materials (Sludge A and D from a major municipal WWTP Sludge B from a municipal WWTP with industrial input and Sludge C from a municipal WWTP with high PCB-Content) were obtained and will be blended to two final materials Before sampling the following analytical data for a typical sample were received

7

Table 1 ndash Analytical data obtained on an average sludge sample in LUA NRW (with courtesy of K Furtmann LUA Duumlsseldorf)

Parameter Concentration PCB 120 ugkg DEHP 110 mgkg PAH 5 mgkg (EPA) PCDDF 15 ng TEkg PBDE 400 ugkg NP 40 mgkg LAS 3 gkg AOX 300 mgkg

Subsequent screening led to the information displayed hereafter It should be stressed that the data were obtained as SCREENING information on the UNTREATED or partially treated raw materials Therefore the final target values which are relevant for the validation intercomparison can be different

Table 2 ndash Analytical data obtained on a first screening on the sludge samples from LUA NRW

Sewage sludge A

Dusseldorf

sewage sludge D

Dusseldorf PCB (ngg) 28 62 35 52 101 65 101 31 38 118 49 40 153 30 33 105 24 11 138 46 38 156 lt1 lt1 180 34 23 170 23 19 PAH (ngg) Naphtalene 34 381 Acenaphtylene 15 43 Acenaphthene 81 108 Fluorene 94 1167 Phenantrene 3440 Anthracene 22 344 Flouranthene 316 4817 Pyrene 235 3011 Benz(a)anthracene 473 791 Chrysene 691 1078 Benz(b)fluoranthene 538 1688 Benz(k)fluoranthene 228 635 Benz(a)pyrene 383 1114 Indeno(123-cd)pyrene 92 229 Dibenzo(ah)anthracene 71 70 Benzo(ghi)perylene 80 185

8

Table 3 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Sludge D (1) 0135 41474 385 Sludge B (2) 0538 0034 30634 547 Sludge A (3) 0184 0037 31399 146 Sludge C (4) 0354 1528 6678 229

Table 4 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Sludge 2

(B)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

554

959

694

591

772

509

nq

nq

970

2216

2379

Table 5 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena IES Ispra Spain) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Sludge 1 (D) 265 290 533 359 1231 338 784 438 lt 005 232 786 Sludge 2 (B) 119 311 626 202 278 299 722 251 lt 005 118 625 Sludge 3 (A) 168 360 621 332 847 416 119 451 lt 005 116 1237 Sludge 4 (C) 563 198 116 273 726 511 473 618 lt 005 444 2015

Table 6 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Sludge 1 (D) 2154 58 844 099 103 101 4367 lt15 50448 Sludge 2 (B) 1067 366 692 046 1491 077 5217 lt15 57633 Sludge 3 (A) 731 663 684 035 1287 068 3733 lt15 60369 Sludge 4 (C) 4379 965 527 163 522 107 5628 lt15 23945

Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM)Sludge 1 (D) 03 2403 101 1002 350 15 1944 132Sludge 2 (B) 031 315 97 879 172 12 514 180Sludge 3 (A) 031 1281 153 1567 265 16 1440 168Sludge 4 (C) 055 231 628 2625 371 81 1101 244

9

22 Agricultural soil material from Reading United Kingdom

The material was proposed by the University of Reading (S Nortcliff) and was sampled from a site called ldquoFrogmore Farmrdquo which was featured in the ldquoMetalsrdquo Report for HORIZONTAL This site is close to Reading with soils developed on flintyloamy periglacial materials over Chalk has a long and well documented history of sludge application The focus of the work of Nortcliff et al undertook at this site and the monitoring and control at the site (by Thames Water and the subsequent subsidiary bodies dealing with sludge application to soil) was on metals (and metal loads) with no analysis or indeed any form of investigation in to organics in the broadest sense

The analytical information produced in the context of the screening of the raw material is displayed below

Table 7 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 3

(Reading) 0032 0119 669

Table 8 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 3 (Reading) 015 706 279 138 152 901 267 300 lt 005 258 931

Table 9 ndash Analytical data obtained on a first screening on the sludge-amended soil from Reading (courtesy of IRMM)

Parameter Concentration

PCB ngg 28 lt1 52 lt1 101 lt1 118 lt1 153 lt1 105 lt1 138 lt1 156 lt1 180 lt1 170 lt1 PAH ngg Naphtalene lt10 Acenaphtylene 21 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene lt10 Flouranthene 818 Pyrene 776 Benz(a)anthracene 565

10

Parameter Concentration

Chrysene 608 Benz(b)fluoranthene 824 Benz(k)fluoranthene 329 Benz(a)pyrene 799 Indeno(123-cd)pyrene

779

Dibenzo(ah)anthracene 118 Benzo(ghi)perylene 394

Table 10 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 3

(Reading)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

103

003

nq

nq

nq

nd

nd

272

273

Table 11 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 3 (Reading) 015 706 279 138 152 901 267 300 lt 005 258 931

Table 12 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 3 (Reading) 7936 477 112 096 194 017 4107 443 2102 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 3 (Reading) 042 13 45 69 69 69 216 92

Table 13 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 3 (Reading) 012

11

23 Compost from Vienna Austria

The fresh compost material was obtained from the Austrian Federal Environment Agency (UBA Vienna) which had used a sub-batch of the raw material for national intercomparson The remainder of the material was stored at 4degC until shipment to IRMM for further processing The following analytical information was provided by UBA Austria and completed with various screenings

Table 14 ndash Analytical data on compost material received from UBA Austria Inorganic and sum parameters

Parameter Unit Sample fraction used Observed mean B CAT mgl FM Fresh sample lt10mm 61 K CAT mgl FM Fresh sample lt10mm 2624 Mg CAT mgl FM Fresh sample lt10mm 242 P CAT mgl FM Fresh sample lt10mm 49 B CAT DM Fresh sample lt10mm 00017 K CAT DM Fresh sample lt10mm 072 Mg CAT DM Fresh sample lt10mm 007 P CAT DM Fresh sample lt10mm 001 NO3-N mgkg FM Fresh sample lt10mm 35 NH4-N mgkg FM Fresh sample lt10mm 230 Ctotal DM lt45degdry milled 29 Corg DM lt45degdry milled 27 Ntotal DM lt45degdry milled 17 P mgkg DM lt45degdry milled 2596 K mgkg DM lt45degdry milled 11019 K DM lt45degdry milled 110 B mgkg DM lt45degdry milled 60 Cd mgkg DM lt45degdry milled 046 Cr mgkg DM lt45degdry milled 25 Cu mgkg DM lt45degdry milled 46 Hg mgkg DM lt45degdry milled 020 Ni mgkg DM lt45degdry milled 18 Pb mgkg DM lt45degdry milled 45 Zn mgkg DM lt45degdry milled 198 Ca mgkg DM lt45degdry milled 68776 Ca DM lt45degdry milled 69 Mo mgkg DM lt45degdry milled 08 S mgkg DM lt45degdry milled 2137 Fe mgkg DM lt45degdry milled 9959 Mn mgkg DM lt45degdry milled 418 Na mgkg DM lt45degdry milled 742 Co mgkg DM lt45degdry milled 41 AOX mgkg DM lt30deg dry milled 62

Table 15 ndash Analytical data on compost material received from UBA Austria Polycyclic aromatic hydrocarbons

PAH Unit Result Naphthaline microgkg DM 93 Acenaphthylene microgkg DM 86 Acenaphthene microgkg DM 5 Fluorene microgkg DM 80 Phenanthrene microgkg DM 89 Anthracene microgkg DM 27 Fluoranthene microgkg DM 487 Pyrene microgkg DM 380

12

PAH Unit Result Benzo(a)anthracene microgkg DM 278 Chrysene microgkg DM 317 Benzo(b)fluoranthene microgkg DM 365 Benzo(k)fluoranthene microgkg DM 193 Benz(a)pyrene microgkg DM 320 Indeno(123-cd)pyrene microgkg DM 233 Dibenz(ah)anthracene microgkg DM 67 Benzo(ghi)perylene microgkg DM 225 Sum EPA microgkg DM 3013 Sum EPA mgkg DM 30

Table 16 ndash Analytical data on compost material received from UBA Austria Sum PCDDs and PCBs

Parameter

Dioxine TEQ (ITEF) ngkg DM 73 TEQ (WHO) ngkg DM 35 PCB Σ Ballschmiter mgkg DM 005

Table 17 ndash Analytical data on compost material obtained by screening in IRMM

Parameter Result in ngg

PCB 28 2 52 2 101 4 118 3 153 10 105 1 138 8 156 1 180 5 170 lt1 PAH Naphtalene lt10 Acenaphtylene lt10 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene 26 Fluoranthene 611 Pyrene 510 Benz(a)anthracene 888 Chrysene 957 Benz(b)fluoranthene 1531 Benz(k)fluoranthene 547 Benz(a)pyrene 1101 Indeno(123-cd)pyrene 416 Dibenzo(ah)anthracene 81 Benzo(ghi)perylene 295

13

Table 18 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Compost 1

(Vienna)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

402

019

259

nq

023

004

nq

nq

144

174

259

Table 19 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Compost 1

(Vienna) 0058 1426 557

Table 20 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Compost 1 (Vienna) 039 736 319 410 365 127 495 004 079 013 208

Table 21 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Compost 1 (Vienna) 2063 431 617 426 199 249 1602 lt15 10521

Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Compost 1 (Vienna) 035 3496 81 375 79 55 653 60

Table 22 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Compost 1 (Vienna) 017

14

24 Agricultural soil sludge amended soil from Pavia Italy

This sludge-amended soil material was obtained during a monitoring campaign which aimed at a generic description of the over-all soil quality in Pavia Province Italy The material which was collected from the upper horizon originates from a small farm called ldquoCascina Novellordquo During the characterisation of the site the following analytical information was obtained on a pooled sample of a sub-area of the farm of 20 X 20 m2

Table 23 ndash Analytical data on Pavia soil

Parameter Result Al 713 Wgt As 224 mgkg Cd 079 mgkg Cr 59 mgkg Cu 308 mgkg Hg 008 mgkg Ni 344 mgkg Pb 246 mgkg Zn 95 mgkg C 091 Wgt 2378-TCDD 0047 pgg 12378-PeCDD 015 pgg 123478-HxCDD 019 pgg 123678-HxCDD 15 pgg 123789-HxCDD 074 pgg 1234678-HpCDD 26 pgg OCDD 382 pgg 2378-TCDF 068 pgg 12378-PeCDF 053 pgg 23478-PeCDF 071 pgg 123478-HxDF 100 pgg 123678-HxDF 066 pgg 234678-HxDF 16 pgg 123789-HxDF 027 pgg 1234678-HpDF 12 pgg 1234789-HpDF 068 pgg OCDF 33 pgg I-TEQ 20 pgg WHO-TEQ 17 pgg

In addition the screening performed at IRMM did not reveal significant quantities of PCBs and PAHs which were all below the LoDs (1 ngg for PCBs and 10 ngg for PAHs respectively)

Table 24 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 5 (Pavia) 0005 0011 154

15

Table 25 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 5

(Pavia)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

039

nq

nq

008

nq

nd

nd

670

671

Table 26 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 5 (Pavia) 033 184 573 225 426 305 206 200 lt 005 381 878

Table 27 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 5 (Pavia) 6939 129 145 224 425 116 6118 255 1789 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 5 (Pavia) 184 62 38 108 55 66 597 110

Table 28 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 5 (Pavia) 006

16

25 Sludge-amended-soil from Barcelona Spain

The sludge-amended soil material from Barcelona sampled upon indication from the Barcelorsquo- Group in Barcelona

Table 29 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 2 (Lleida T) 0015 0183 1138

Table 30 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 2

(Lleida T)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

159

045

nq

048

160

nq

nq

1000

1004

Table 31 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 2 (Lleida T) 059 141 327 536 405 186 184 224 lt 005 318 111

Table 32 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 2 (Lleida T) 4443 1067 1429 253 344 204 4116 780 3396 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 2 (Lleida T) 064 65 26 125 59 17 547 65

Table 33 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 2 (Lleida T) 010

17

26 Sludge amended soil from Essen Germany

The German sludge-amended soil from Essen which was provided as the three sludge materials by LUA NRW did not feature significant concentrations of the PCB congeners 28 52 101 118 153 105 138 156 180 170 but had detectable amounts of some PAHs

Table 34 ndash Analytical screening data on the German sludge-amended soil

Parameter Concentration(ngg)

Naphtalene lt10 Acenaphtylene lt10 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene lt10 Fluoranthene 28 Pyrene 20 Benz(a)anthracene 24 Chrysene 47 Benz(b)fluoranthene 76 Benz(k)fluoranthene 20 Benz(a)pyrene 35 Indeno(123-cd)pyrene 35 Dibenzo(ah)anthracene 10 Benzo(ghi)perylene 26

Table 35 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 4 (Essen) 0011 0302 055

Table 36 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 4

(Essen)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

nq

nq

nq

nq

nq

nq

128

191

203

18

Table 37 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 4 (Essen) 052 545 261 805 320 403 273 273 lt 005 295 781

Table 38 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 4 (Essen) 7947 442 085 06 086 007 2163 189 2019 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 4 (Essen) 045 19 42 87 683 60 462 61

Table 39 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 4 (Essen) 004

27 Long-term sludge exposed soil from Hohenheim-Stuttgart Germany

Similarly an additional sludge exposed soil was sampled at the University of Hohenheim Stuttgart were a test soil was long-term exposed to elevated concentrations of sewage sludge

Table 40 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 1 (Stuttgart) 0045 0263 1765

Table 41 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 1

(Stuttgart)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

230

006

004

004

nq

nd

nd

498

500

19

Table 42 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 1 (Stuttgart) 069 127 361 262 504 183 252 262 lt 005 266 142

Table 43 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 1 (Stuttgart) 7194 1006 133 186 366 088 7874 275 3571 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 1 (Stuttgart) 123 50 47 212 85 69 991 129

Table 44 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 1 (Stuttgart) 177

18

Annex 3

Statistical calculations

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 47)Mandels h statistics(Sludge 1 - PBD 47)

Sample Sludge 1 NUM

Element PBD 47

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00213 0001 3 -021 005 - - 10L - - NUM46L 00273 0002 4 016 021 - - 46L - - NUM64L 00059 0000 4 -116 002 NUM - 64L - - NUM12L 00188 0000 4 -036 002 - - 12L - - NUM26L 00499 0024 2 157 223 Fail - - 26L - - NUM

Totgem 0025 0005 mgkg 1-level 172 (185) NUM (10L46L64L12L26L) -1Totstd= 0016 0010 5-level 157 (162) 5

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 5 Labs rejected (10L46L64L12L26L)

000 050 100 150 200 250

k-values

10L

46L

64L

12L

26L

Mandels k statistics(Sludge 1 - PBD 47)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

10L

46L

64L

12L

26L

Labo

rato

ries

NUM

-200 -100 000 100 200

h-values

10L

46L

64L

12L

26L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 47)

Sludge 1-PBD 47

Unit mgkg

Mandels k statistics(Soil 3 - PBD 47)Mandels h statistics(Soil 3 - PBD 47)

Sample Soil 3 Soil 3 - PBD 47 -- Mean PARM = 0001 [mgkg]

Element PBD 47

General calcparmT1= 134814E-02T2= 142830E-05T3= 13T4= 45T5= 22767E-06

n= variabelp= 4

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean26L 00007 0000 2 -143 001 00007 00000 2 1 00046L 00010 0001 4 010 181 00010 00008 4 3 00010L 00011 0000 3 049 023 00011 00001 3 2 00012L 00012 0000 4 084 081 00012 00004 4 3 000

Totgem 0001 0000 mgkg 1-level 149 (177) 4 00010 () 4 3Totstd= 0000 0000 5-level 142 (159)

RESULTS Mean = 000100 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000050 --gt 5031 r = 00014Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000050 --gt 5031 R = 00014Remarks none

000 050 100 150 200

k-values

26L

46L

10L

12L

Mandels k statistics(Soil 3 - PBD 47)

00 00 00 00 00 00 00 00 00 00 00

Deviation from Mean

26L

46L

10L

12L

Labo

rato

ries

Soil 3 - PBD 47 -- Mean PARM = 0001 [mgkg]

-200 -100 000 100

h-values

26L

46L

10L

12L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 47)

Soil 3-PBD 47

Unit mgkg

Mandels k statistics(Compost 1 - PBD 99)Mandels h statistics(Compost 1 - PBD 99)

Sample Compost 1 Compost 1 - PBD 99 -- Mean PARM = 0003 [mgkg]

Element PBD 99

General calcparmT1= 492124E-02T2= 148747E-04T3= 17T4= 61T5= 93196E-06

n= variabelp= 5

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00020 0000 4 -137 053 00020 00004 4 3 000

26L 00025 0000 2 -058 024 00025 00002 2 1 00010L 00029 0000 3 012 032 00029 00003 3 2 00046L 00033 0001 4 069 161 00033 00013 4 3 00012L 00036 0001 4 114 140 00036 00011 4 3 000

Totgem 0003 0001 mgkg 1-level 172 (185) 5 00029 () 5 4Totstd= 0001 0001 5-level 157 (162)

RESULTS Mean = 000286 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000088 --gt 3086 r = 00025Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000101 --gt 3525 R = 00028Remarks none

000 050 100 150 200

k-values

4L

26L

10L

46L

12L

Mandels k statistics(Compost 1 - PBD 99)

00 00 00 00 00 00 00 00 00 00

Deviation from Mean

4L

26L

10L

46L

12L

Labo

rato

ries

Compost 1 - PBD 99 -- Mean PARM = 0003 [mgkg]

-200 -100 000 100 200

h-values

4L

26L

10L

46L

12L

Labo

rato

ries

Mandels h statistics(Compost 1 - PBD 99)

Compost 1-PBD 99

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 99)Mandels h statistics(Sludge 1 - PBD 99)

Sample Sludge 1 Sludge 1 - PBD 99 -- Mean PARM = 0024 [mgkg]

Element PBD 99

General calcparmT1= 448050E-01T2= 112113E-02T3= 19T4= 73T5= 32972E-05

n= variabelp= 5

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean64L 00173 0002 4 -118 041 Fail 00173 00019 4 3 -0014L 00183 0002 4 -104 032 00183 00015 4 3 -001

12L 00227 0001 4 -038 022 00227 00010 4 3 00010L 00290 0001 3 055 021 00290 00010 3 2 00146L 00320 0002 4 100 039 00320 00018 4 3 00126L 00323 0011 2 105 234 - - 26L - - 001

Totgem 0025 0003 mgkg 1-level 187 (177) 5 00239 (26L) 5 4Totstd= 0007 0004 5-level 166 (154) 1

RESULTS Mean = 002385 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000153 --gt 643 r = 00043Between lab variance S2L = 000004Reproducibility var S2R = 000004Reproducibility std SR = 000666 --gt 2791 R = 00186Remarks 1 Lab rejected (26L)

000 050 100 150 200 250

k-values

64L

4L

12L

10L

46L

26L

Mandels k statistics(Sludge 1 - PBD 99)

00 00 00 00 00 00 00 00 00 00

Deviation from Mean

64L

4L

12L

10L

46L

26L

Labo

rato

ries

Sludge 1 - PBD 99 -- Mean PARM = 0024 [mgkg]

-200 -100 000 100 200

h-values

64L

4L

12L

10L

46L

26L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 99)

Sludge 1-PBD 99

Unit mgkg

Mandels k statistics(Soil 3 - PBD 99)Mandels h statistics(Soil 3 - PBD 99)

Sample Soil 3 NUM

Element PBD 99

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00017 0000 4 091 068 - - 10L - - NUM46L 00017 0001 4 100 211 - - 46L - - NUM64L 00005 0000 4 -106 023 NUM - 64L - - NUM12L 00012 0000 4 015 014 - - 12L - - NUM26L 00006 0000 2 -101 012 - - 26L - - NUM

Totgem 0001 0000 mgkg 1-level 172 (173) NUM (10L46L64L12L26L) -1Totstd= 0001 0000 5-level 157 (153) 5

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 5 Labs rejected (10L46L64L12L26L)

000 050 100 150 200 250

k-values

10L

46L

64L

12L

26L

Mandels k statistics(Soil 3 - PBD 99)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

10L

46L

64L

12L

26L

Labo

rato

ries

NUM

-200 -100 000 100 200

h-values

10L

46L

64L

12L

26L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 99)

Soil 3-PBD 99

Unit mgkg

Mandels k statistics(Compost 1 - PBD 100)Mandels h statistics(Compost 1 - PBD 100)

Sample Compost 1 Compost 1 - PBD 100 -- Mean PARM = 0001 [mgkg]

Element PBD 100

General calcparmT1= 124272E-02T2= 113129E-05T3= 14T4= 52T5= 46584E-07

n= variabelp= 4

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean26L 00006 0000 2 -131 037 Fail 00006 00001 2 1 00010L 00009 0000 4 003 083 00009 00002 4 3 00046L 00009 0000 4 016 115 00009 00002 4 3 00012L 00011 0000 4 112 136 Fail 00011 00003 4 3 000

Totgem 0001 0000 mgkg 1-level 149 (167) 4 00009 () 4 3Totstd= 0000 0000 5-level 142 (15)

RESULTS Mean = 000085 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000022 --gt 2531 r = 00006Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000025 --gt 2882 R = 00007Remarks none

000 050 100 150

k-values

26L

10L

46L

12L

Mandels k statistics(Compost 1 - PBD 100)

00 00 00 00 00 00 00 00 00 00 00

Deviation from Mean

26L

10L

46L

12L

Labo

rato

ries

Compost 1 - PBD 100 -- Mean PARM = 0001 [mgkg]

-200 -100 000 100 200

h-values

26L

10L

46L

12L

Labo

rato

ries

Mandels h statistics(Compost 1 - PBD 100)

Compost 1-PBD 100

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 100)Mandels h statistics(Sludge 1 - PBD 100)

Sample Sludge 1 Sludge 1 - PBD 100 -- Mean PARM = 0005 [mgkg]

Element PBD 100

General calcparmT1= 852065E-02T2= 412762E-04T3= 18T4= 68T5= 78914E-07

n= variabelp= 5

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00039 0000 4 -042 007 Fail 00039 00002 4 3 000

12L 00044 0000 4 -041 005 Fail 00044 00001 4 3 00010L 00046 0000 4 -041 013 Fail 00046 00003 4 3 00046L 00056 0000 4 -040 012 Fail 00056 00003 4 3 00026L 00059 0000 2 -040 013 Fail 00059 00003 2 1 00038L 02168 0006 4 204 244 Fail - - 38L - - 021

Totgem 0040 0001 mgkg 1-level 187 (177) 5 00049 (38L) 5 4Totstd= 0087 0002 5-level 166 (154) 1

RESULTS Mean = 000486 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000025 --gt 507 r = 00007Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000084 --gt 1731 R = 00024Remarks 1 Lab rejected (38L)

000 050 100 150 200 250

k-values

4L

12L

10L

46L

26L

38L

Mandels k statistics(Sludge 1 - PBD 100)

-01 00 01 01 02 02 03

Deviation from Mean

4L

12L

10L

46L

26L

38L

Labo

rato

ries

Sludge 1 - PBD 100 -- Mean PARM = 0005 [mgkg]

-100 000 100 200 300

h-values

4L

12L

10L

46L

26L

38L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 100)

Sludge 1-PBD 100

Unit mgkg

Mandels k statistics(Soil 3 - PBD 100)Mandels h statistics(Soil 3 - PBD 100)

Sample Soil 3 NUM

Element PBD 100

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00003 0000 4 -050 000 Fail - - 10L - - NUM46L 00003 0000 4 -050 000 Fail NUM - 46L - - NUM3L 305500 2051 2 150 200 Fail - - 3L - - NUM

26L 00005 0000 2 -050 000 Fail - - 26L - - NUM

Totgem 7638 0513 mgkg 1-level 149 (177) NUM (10L46L3L26L) -1Totstd= 15275 1025 5-level 142 (159) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (10L46L3L26L)

000 050 100 150 200

k-values

10L

46L

3L

26L

Mandels k statistics(Soil 3 - PBD 100)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

10L

46L

3L

26L

Labo

rato

ries

NUM

-100 000 100 200

h-values

10L

46L

3L

26L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 100)

Soil 3-PBD 100

Unit mgkg

Mandels k statistics(Compost 1 - PBD 153)Mandels h statistics(Compost 1 - PBD 153)

Sample Compost 1 NUM

Element PBD 153

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean44L 00053 0001 3 150 157 Fail - - 44L - - NUM46L 00007 0000 4 -044 111 Fail - - 46L - - NUM12L 00005 0000 4 -051 055 Fail - - 12L - - NUM26L 00005 0000 2 -054 001 Fail NUM - 26L - - NUM

Totgem 0002 0000 mgkg 1-level 149 (177) NUM (44L46L12L26L) -1Totstd= 0002 0000 5-level 142 (159) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (44L46L12L26L)

000 050 100 150 200

k-values

44L

46L

12L

26L

Mandels k statistics(Compost 1 - PBD 153)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

44L

46L

12L

26L

Labo

rato

ries

NUM

-100 000 100 200

h-values

44L

46L

12L

26L

Labo

rato

ries

Mandels h statistics(Compost 1 - PBD 153)

Compost 1-PBD 153

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 153)Mandels h statistics(Sludge 1 - PBD 153)

Sample Sludge 1 Sludge 1 - PBD 153 -- Mean PARM = 0004 [mgkg]

Element PBD 153

General calcparmT1= 676738E-02T2= 267609E-04T3= 18T4= 68T5= 19626E-05

n= variabelp= 5

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00024 0000 4 -157 017 00024 00002 4 3 000

12L 00038 0002 4 006 154 00038 00018 4 3 00046L 00039 0000 4 011 026 00039 00003 4 3 00026L 00039 0000 2 018 004 00039 00000 2 1 00064L 00049 0002 4 122 159 00049 00018 4 3 000

Totgem 0004 0001 mgkg 1-level 172 (173) 5 00038 () 5 4Totstd= 0001 0001 5-level 157 (153)

RESULTS Mean = 000378 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000123 --gt 3252 r = 00034Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000142 --gt 3754 R = 00040Remarks none

000 050 100 150 200

k-values

4L

12L

46L

26L

64L

Mandels k statistics(Sludge 1 - PBD 153)

00 00 00 00 00 00 00

Deviation from Mean

4L

12L

46L

26L

64L

Labo

rato

ries

Sludge 1 - PBD 153 -- Mean PARM = 0004 [mgkg]

-200 -100 000 100 200

h-values

4L

12L

46L

26L

64L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 153)

Sludge 1-PBD 153

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 154)Mandels h statistics(Sludge 1 - PBD 154)

Sample Sludge 1 NA

Element PBD 154

General calcparmT1= NAT2= NAT3=T4=T5=

n= variabelp=

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00021 0000 3 -100 021 NA - 4L - - NA

46L 00025 0000 4 115 018 NA - 46L - - NA64L 00021 0001 4 -066 179 - - 64L - - NA12L 00023 0000 4 050 085 - - 12L - - NA

Totgem 0002 0000 mgkg 1-level 149 (167) NA (4L46L64L12L) -1Totstd= 0000 0000 5-level 142 (15) 4

RESULTS Mean = NA mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NAReproducibility var S2R = NAReproducibility std SR = NA --gt NA R = NARemarks 4 Labs rejected (4L46L64L12L)

000 050 100 150 200

k-values

4L

46L

64L

12L

Mandels k statistics(Sludge 1 - PBD 154)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

4L

46L

64L

12L

Labo

rato

ries

NA

-100 000 100 200

h-values

4L

46L

64L

12L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 154)

Sludge 1-PBD 154

Unit mgkg

Mandels k statistics(Soil 3 - PBD 154)Mandels h statistics(Soil 3 - PBD 154)

Sample Soil 3 NUM

Element PBD 154

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

4L 00010 - 1 150 Fail - - 4L - - NUM46L 00001 0000 4 -053 096 Fail - - 46L - - NUM64L 00001 0000 4 -056 105 Fail NUM - 64L - - NUM12L 00002 0000 4 -040 099 Fail - - 12L - - NUM

Totgem 000037 0000 mgkg 1-level 149 (164) NUM (4L46L64L12L) -1Totstd= 000042 0000 5-level 142 (153) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (4L46L64L12L)

000 050 100 150

k-values

4L

46L

64L

12L

Mandels k statistics(Soil 3 - PBD 154)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

4L

46L

64L

12L

Labo

rato

ries

NUM

-100 000 100 200

h-values

4L

46L

64L

12L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 154)

Soil 3-PBD 154

Unit mgkg

Mandels k statistics(Compost 1 - PBD 209)Mandels h statistics(Compost 1 - PBD 209)

Sample Compost 1 NUM

Element PBD 209

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00065 0003 2 -049 032 - - 4L - - NUM

44L 00573 0021 4 150 197 Fail - - 44L - - NUM12L 00078 0001 4 -045 011 - - 12L - - NUM26L 00049 0000 2 -056 000 NUM - 26L - - NUM

Totgem 0019 0006 mgkg 1-level 149 (177) NUM (4L44L12L26L) -1Totstd= 0025 0010 5-level 142 (159) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (4L44L12L26L)

000 050 100 150 200

k-values

4L

44L

12L

26L

Mandels k statistics(Compost 1 - PBD 209)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

4L

44L

12L

26L

Labo

rato

ries

NUM

-100 000 100 200

h-values

4L

44L

12L

26L

Labo

rato

ries

Mandels h statistics(Compost 1 - PBD 209)

Compost 1-PBD 209

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 209)Mandels h statistics(Sludge 1 - PBD 209)

Sample Sludge 1 Sludge 1 - PBD 209 -- Mean PARM = 0249 [mgkg]

Element PBD 209

General calcparmT1= 394542E+00T2= 107296E+00T3= 16T4= 56T5= 19723E-02

n= variabelp= 5

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 01550 0055 4 -112 148 Fail 01550 00551 4 3 -009

46L 02050 0007 2 -053 019 02050 00071 2 1 -00412L 02137 0058 4 -042 155 02137 00576 4 3 -00426L 03149 0021 2 078 057 Fail 03149 00210 2 1 00764L 03577 0007 4 129 020 Fail 03577 00074 4 3 011

Totgem 0249 0030 mgkg 1-level 172 (185) 5 02493 () 5 4Totstd= 0084 0025 5-level 157 (162)

RESULTS Mean = 024926 mgkg

Repeatability variance S2r = 000179Repeatability std Sr = 004234 --gt 1699 r = 01186Between lab variance S2L = 000743Reproducibility var S2R = 000922Reproducibility std SR = 009604 --gt 3853 R = 02689Remarks none

000 050 100 150 200

k-values

4L

46L

12L

26L

64L

Mandels k statistics(Sludge 1 - PBD 209)

-01 -01 00 01 01 02

Deviation from Mean

4L

46L

12L

26L

64L

Labo

rato

ries

Sludge 1 - PBD 209 -- Mean PARM = 0249 [mgkg]

-200 -100 000 100 200

h-values

4L

46L

12L

26L

64L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 209)

Sludge 1-PBD 209

Unit mgkg

Mandels k statistics(Soil 3 - PBD 209)Mandels h statistics(Soil 3 - PBD 209)

Sample Soil 3 Soil 3 - PBD 209 -- Mean PARM = 0258 [mgkg]

Element PBD 209

General calcparmT1= 596398E+00T2= 191917E+00T3= 22T4= 84T5= 13249E-02

n= variabelp= 6

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean26L 01162 0021 2 -108 074 Fail 01162 00207 2 1 -0144L 01303 0031 4 -097 111 Fail 01303 00312 4 3 -013

46L 01975 0036 4 -046 128 Fail 01975 00359 4 3 -00644L 02898 0035 4 024 124 Fail 02898 00346 4 3 00312L 03895 0018 4 100 065 Fail 03895 00181 4 3 01364L 04260 0022 4 127 078 Fail 04260 00219 4 3 017

Totgem 0258 0027 mgkg 1-level 187 (177) 6 02582 () 6 5Totstd= 0132 0008 5-level 166 (154)

RESULTS Mean = 025818 mgkg

Repeatability variance S2r = 000083Repeatability std Sr = 002878 --gt 1115 r = 00806Between lab variance S2L = 001640Reproducibility var S2R = 001723Reproducibility std SR = 013127 --gt 5084 R = 03676Remarks none

000 050 100 150

k-values

26L

4L

46L

44L

12L

64L

Mandels k statistics(Soil 3 - PBD 209)

-02 -01 -01 00 01 01 02 02

Deviation from Mean

26L

4L

46L

44L

12L

64L

Labo

rato

ries

Soil 3 - PBD 209 -- Mean PARM = 0258 [mgkg]

-200 -100 000 100 200

h-values

26L

4L

46L

44L

12L

64L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 209)

Soil 3-PBD 209

Unit mgkg

Mandels k statistics(Compost 1 - Sum PBD)Mandels h statistics(Compost 1 - Sum PBD)

Sample Compost 1 Compost 1 - Sum PBD -- Mean PARM = 0009 [mgkg]

Element Sum PBD

General calcparmT1= 154064E-01T2= 169065E-03T3= 18T4= 68T5= 11354E-04

n= variabelp= 5

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00031 0002 4 -067 016 00031 00016 4 3 -0014L 00055 0005 4 -056 048 00055 00047 4 3 000

46L 00085 0003 4 -042 031 00085 00030 4 3 00026L 00123 0000 2 -024 003 00123 00002 2 1 00012L 00154 0002 4 -011 021 00154 00021 4 3 00144L 00613 0023 4 200 237 Fail - - 44L - - 005

Totgem 0018 0006 mgkg 1-level 187 (177) 5 00089 (44L) 5 4Totstd= 0022 0009 5-level 166 (154) 1

RESULTS Mean = 000893 mgkg

Repeatability variance S2r = 000001Repeatability std Sr = 000296 --gt 3308 r = 00083Between lab variance S2L = 000002Reproducibility var S2R = 000003Reproducibility std SR = 000570 --gt 6374 R = 00159Remarks 1 Lab rejected (44L)

000 050 100 150 200 250

k-values

10L

4L

46L

26L

12L

44L

Mandels k statistics(Compost 1 - Sum PBD)

00 00 00 00 00 00 01 01

Deviation from Mean

10L

4L

46L

26L

12L

44L

Labo

rato

ries

Compost 1 - Sum PBD -- Mean PARM = 0009 [mgkg]

-100 000 100 200

h-values

10L

4L

46L

26L

12L

44L

Labo

rato

ries

Mandels h statistics(Compost 1 - Sum PBD)

Compost 1-Sum PBD

Unit mgkg

Mandels k statistics(Sludge 1 - Sum PBD)Mandels h statistics(Sludge 1 - Sum PBD)

Sample Sludge 1 Sludge 1 - Sum PBD -- Mean PARM = 0256 [mgkg]

Element Sum PBD

General calcparmT1= 531806E+00T2= 162188E+00T3= 22T4= 84T5= 25223E-02

n= variabelp= 6

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00423 0025 4 -156 044 Fail 00423 00252 4 3 -02146L 01808 0118 4 -049 205 - - 46L - - -0074L 01810 0056 4 -049 097 01810 00558 4 3 -007

38L 02168 0006 4 -022 010 02168 00059 4 3 -00412L 02890 0065 4 034 113 02890 00647 4 3 00364L 03958 0008 4 116 014 Fail 03958 00079 4 3 01426L 04094 0034 2 126 059 Fail 04094 00337 2 1 015

Totgem 0245 0044 mgkg 1-level 198 (179) 6 02557 (46L) 6 5Totstd= 0130 0039 5-level 171 (155) 1

RESULTS Mean = 025570 mgkg

Repeatability variance S2r = 000158Repeatability std Sr = 003970 --gt 1553 r = 01112Between lab variance S2L = 001807Reproducibility var S2R = 001964Reproducibility std SR = 014015 --gt 5481 R = 03924Remarks 1 Lab rejected (46L)

000 050 100 150 200 250

k-values

10L

46L

4L

38L

12L

64L

26L

Mandels k statistics(Sludge 1 - Sum PBD)

-03 -02 -02 -01 -01 00 01 01 02 02

Deviation from Mean

10L

46L

4L

38L

12L

64L

26L

Labo

rato

ries

Sludge 1 - Sum PBD -- Mean PARM = 0256 [mgkg]

-200 -100 000 100 200

h-values

10L

46L

4L

38L

12L

64L

26L

Labo

rato

ries

Mandels h statistics(Sludge 1 - Sum PBD)

Sludge 1-Sum PBD

Unit mgkg

Mandels k statistics(Soil 3 - Sum PBD)Mandels h statistics(Soil 3 - Sum PBD)

Sample Soil 3 Soil 3 - Sum PBD -- Mean PARM = 0227 [mgkg]

Element Sum PBD

General calcparmT1= 610980E+00T2= 200876E+00T3= 26T4= 100T5= 13106E-02

n= variabelp= 7

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00028 0001 4 -037 000 Fail 00028 00005 4 3 -02226L 01179 0021 2 -036 003 Fail 01179 00208 2 1 -0114L 01305 0031 4 -036 004 Fail 01305 00308 4 3 -010

46L 02065 0035 4 -036 005 Fail 02065 00350 4 3 -00244L 02923 0037 4 -035 005 Fail 02923 00365 4 3 00712L 04051 0015 4 -034 002 Fail 04051 00149 4 3 01864L 04314 0022 4 -033 003 Fail 04314 00223 4 3 0203L 305500 2051 2 247 283 Fail - - 3L - - 3032

Totgem 4017 0276 mgkg 1-level 206 (181) 7 02266 (3L) 7 6Totstd= 10722 0717 5-level 175 (156) 1

RESULTS Mean = 022663 mgkg

Repeatability variance S2r = 000069Repeatability std Sr = 002626 --gt 1159 r = 00735Between lab variance S2L = 002568Reproducibility var S2R = 002637Reproducibility std SR = 016238 --gt 7165 R = 04547Remarks 1 Lab rejected (3L)

000 050 100 150 200 250 300

k-values

10L

26L

4L

46L

44L

12L

64L

3L

Mandels k statistics(Soil 3 - Sum PBD)

-50 00 50 100 150 200 250 300 350

Deviation from Mean

10L

26L

4L

46L

44L

12L

64L

3L

Labo

rato

ries

Soil 3 - Sum PBD -- Mean PARM = 0227 [mgkg]

-100 000 100 200 300

h-values

10L

26L

4L

46L

44L

12L

64L

3L

Labo

rato

ries

Mandels h statistics(Soil 3 - Sum PBD)

Soil 3-Sum PBD

19

Annex 4

Raw data submitted

Sample Compost1 Sample Compost 1 Sample Compost 1Element PBD 99 Element PBD 100 Element PBD 153

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]4L 00021 10L 00008 44L 000504L 00024 10L 00008 44L 000604L 00014 10L 00007 44L 000504L 00020 10L 00011 46L 00004

10L 00029 46L 00007 46L 0001210L 00027 46L 00012 46L 0000410L 00032 46L 00009 46L 0000946L 00025 46L 00007 12L 0000446L 00052 12L 00008 12L 0000846L 00029 12L 00012 12L 0000446L 00026 12L 00008 12L 0000712L 00026 12L 00014 26L 0000512L 00043 26L 00007 26L 0000512L 00026 26L 0000612L 0004726L 0002626L 00024

Sample Compost 1 Sample Compost 1 Sample Compost 1Element PBD 154 Element PBD 183 Element PBD 196

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]4L 00010 46L 00002 46L 00011

46L 00003 46L 00024 46L 0000846L 00007 46L 00021 12L 0000246L 00003 46L 00003 12L 0000346L 00004 12L 00003 12L 0000112L 00003 12L 00011 12L 0000212L 00005 12L 0000312L 00031 12L 0000312L 00006

Sample Compost 1 Sample Compost 1 Sample Compost 1Element PBD 197 Element PBD 203 Element PBD 209

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00002 46L 00010 4L 0004146L 00023 12L 00002 4L 0008946L 00022 12L 00003 44L 0041012L 00004 12L 00002 44L 0084012L 00006 12L 00002 44L 0064012L 00003 44L 0040012L 00004 12L 00079

12L 0007312L 0006512L 0009326L 0004926L 00049

Sample Compost 1Element PBD 47

LAB PARM [mgkg]26L 0003826L 00039

Element PBD 99 Element PBD 47 Element PBD 209LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]

4L 00170 10L 00210 4L 010004L 00200 10L 00220 4L 018004L 00170 10L 00210 4L 012004L 00190 46L 00300 4L 0220010L 00280 46L 00280 46L 0210010L 00300 46L 00250 46L 0200010L 00290 46L 00260 64L 0351846L 00340 64L 00059 64L 0363846L 00330 64L 00057 64L 0364546L 00300 64L 00062 64L 0350846L 00310 64L 00060 12L 0220964L 00194 12L 00191 12L 0177164L 00154 12L 00187 12L 0292264L 00185 12L 00190 12L 0164664L 00159 12L 00186 26L 0329712L 00242 26L 00666 26L 0300012L 00223 26L 0033212L 0022112L 0022226L 0024626L 00400

Element PBD 203 Element PBD 197 Element PBD 196LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00022 46L 00027 46L 0002446L 00014 46L 00024 46L 0002264L 00036 12L 00161 64L 0005864L 00058 12L 00060 64L 0006512L 00063 12L 00061 12L 0004812L 00034 12L 00036 12L 0002512L 00038 12L 0003212L 00027 12L 00022

Element PBD 183 Element PBD 154 Element PBD 153LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00049 4L 00020 4L 0002246L 00035 4L 00022 4L 0002446L 00036 4L 00020 4L 0002246L 00034 46L 00025 4L 0002664L 00027 46L 00025 46L 0004064L 00023 46L 00025 46L 0004264L 00024 46L 00023 46L 0003564L 00020 64L 00034 46L 0003812L 00230 64L 00023 64L 0007412L 00032 64L 00017 64L 0004712L 00031 64L 00011 64L 0004612L 00030 12L 00030 64L 0003026L 00007 12L 00021 12L 0006526L 00008 12L 00021 12L 00029

12L 00021 12L 0003226L 00015 12L 0002926L 00019 26L 00039

26L 00040

Element PBD 100LAB PARM [mgkg]

4L 000384L 000414L 000374L 00038

38L 0219038L 0220038L 0208038L 0220010L 0004410L 0005010L 0004310L 0004646L 0005746L 0005946L 0005346L 0005312L 0004312L 0004512L 0004312L 0004326L 0006226L 00057

Sample Soil 3 Sample Soil 3 Sample Soil 3Element PBD 99 Element PBD 47 Element PBD 100

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]10L 00016 10L 00011 10L 0000310L 00019 10L 00010 10L 0000410L 00013 10L 00012 10L 0000410L 00019 46L 00007 10L 0000246L 00025 46L 00022 46L 0000246L 00025 46L 00005 46L 0000646L 00008 46L 00007 46L 0000246L 00011 12L 00010 46L 0000264L 00005 12L 00017 3L 29100064L 00005 12L 00010 3L 32000064L 00006 12L 00009 26L 0000564L 00007 26L 00007 26L 0000512L 00012 26L 0000712L 0001312L 0001312L 0001226L 0000526L 00006

Sample Soil 3 Sample Soil 3 Sample Soil 3Element PBD 153 Element PBD 154 Element PBD 196

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]44L 00050 4L 00010 46L 0000744L 00050 46L 00001 46L 0001146L 00002 46L 00002 46L 0000846L 00003 46L 00001 46L 0001146L 00002 46L 00002 64L 0002646L 00002 64L 00001 64L 0002664L 00001 64L 00001 64L 0002964L 00001 64L 00001 64L 0003464L 00001 64L 00002 12L 0004564L 00002 12L 00003 12L 00032

12L 00002 12L 0002212L 00002 12L 0002112L 00002

Sample Soil 3 Sample Soil 3 Sample Soil 3Element PBD 197 Element PBD 203 Element PBD 209

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00006 46L 00011 4L 0091046L 00013 46L 00017 4L 0150046L 00011 46L 00015 4L 0120046L 00013 46L 00018 4L 0160012L 00090 64L 00013 44L 0337012L 00056 64L 00014 44L 0281012L 00033 64L 00016 44L 0287012L 00032 64L 00015 44L 02540

12L 00055 46L 0230012L 00041 46L 0220012L 00027 46L 0150012L 00026 46L 01900

64L 0438164L 0401664L 0414464L 0449812L 0367112L 0397812L 0409112L 03838

Sample Soil 3 26L 0102Element PBD 183 26L 0131

LAB PARM [mgkg]46L 0000746L 0000846L 0005846L 0000764L 0000264L 0000364L 0000364L 0000312L 0001512L 0001112L 0000712L 00007

European Commission EUR 23003 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on polybrominated diphenylethers Author(s) E Sobiecka H van der Sloot D Barcelo B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 68 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07403-5 Abstract Project HORIZONTAL is interdisciplinary aiming at a harmonisation and horizontal standardisation of test procedures in particular for sludge soils and biowastes In the context of this standardization project a series of draft technical specification were designed upon an extensive desk study fine-tuned after expert consultations and finally validated in international intercomparisons exercise This report summarises the work performed within the validation study of the draft standard for the determination of polybrominated diphenylethers (PBDE) in soils sludge and treated bio-waste using gas-chromatography method with mass selective detection (GC-MS) It further explains the underlying statistical concept for the calculation of reproducibility and repeatability from intercomparisons data In addition all single values results of the statistical evaluation as well as background information on the validation materials used are described and explained

The mission of the JRC is to provide customer-driven scientific and technical support for the conception development implementation and monitoring of EU policies As a service of the European Commission the JRC functions as a reference centre of science and technology for the Union Close to the policy-making process it serves the common interest of the Member States while being independent of special interests whether private or national

LB

-NA

-23003-EN

-C

13

Matrix Parameter Mean sr sR r R p Outliers Used No of data

No of data reported below

detection

Total no of data

Soil 3 00002 1049 4 13 6 19 Sludge 1 PBD 183 00048 1217 3 12 2 14 Compost 1 00009 1048 2 8 5 13 Soil 3 00011 1395 3 12 6 18 Sludge 1 PBD 196 00037 470 2 8 7 15 Compost 1 00004 950 2 6 4 10 Soil 3 00023 519 3 12 2 14 Sludge 1 PBD 197 00062 834 2 6 8 14 Compost 1 00009 1001 2 7 7 14 Soil 3 00032 904 2 8 6 14 Sludge 1 PBD 203 00037 461 2 8 4 12 Compost 1 00004 978 2 5 3 8 Soil 3 00022 598 3 12 0 12 Sludge 1 PBD 209 02493 170 39 01186 02689 5 0 16 2 18 Compost 1 00273 104 3 10 5 15 Soil 3 02582 1115 51 00806 03676 6 0 22 0 22

14

Matrix Parameter Mean sr sR r R p Outliers Used No of data

No of data reported below

detection

Total no of data

Sludge 1 Sum PBD 0256 155 548 0111 0392 6 1 22 Compost 1 0009 331 637 0008 0016 5 1 18 Soil 3 0227 116 717 0074 0455 7 1 26 Abbreviations sr Repeatability standard deviation SR Reproducibility standard deviation r Repeatability limit (comparing two measurements) R Reproducibility limit (comparing two measurements) p Number of labs determination not possible

15

14 Annexes Annex 1 Model questionnaire to be filled by the participating laboratories Annex 3 Report on the validation materials used Annex 2 Statistical calculations Annex 3 Data submitted

16

Annex 1

Model questionnaire to be filled by the participating laboratories

Model questionnaire to be filled by the participating laboratories Name of laboratory Contact person Contact details email Phone Fax Mail address of lab Dispatch address of lab for shipment of samples (no PO boxes) Title of measurement method (copy attached) Our laboratory is willing to participate in the precision experiment for this draft standard method

Yes No As participant we understand that

bull All essential apparatus chemicals and other requirements specified in the method must be available in our laboratory when the programme begins

bull Specified timing requirements such as starting and finishing date of the programme must be rigidly met

bull The method must be strictly adhered to bull Samples must be handled in accordance with instructions bull A qualified operator must perform the measurements

Having studied the method and having made a fair appraisal of our capabilities and facilities we feel that we will be adequately prepared for cooperative testing of this method Comments helliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphellip Signature Date

17

Annex 2

Report on the validation materials used

VI

Abstract This report gives an overview on the available analytical information on the following raw materials to be used for the production of validation materials of the so-called Project HORIZONTAL

bull Four sludge materials from Duumlsseldorf Germany

bull An agricultural soil material from Reading United Kingdom

bull A compost material from Vienna Austria

bull A compost material from Korschenbroich Germany

bull A sludge-amended agricultural soil from Pavia Province Italy

bull A sludge-amended soil from Barcelona Spain

bull A sludge-amended soil from Essen Germany

bull A long-term sludge exposed soil from Hohenheim Germany

VII

List of Abbreviations Throughout this report the following abbreviations are used

AOX absorbable organic halogens

Corg organic carbon content

Ctotal total carbon content

CAT cation exchangeable

CDD chlorinated dibenzodioxin

CDF chlorinated dibenzofuran

DEHP di(2-ethylhexyl)phthalate

DM dry matter

EPA Environment Protection Agency

EU European Union

FM fresh matter

Hp hepta

Hx hexa

IES Institute for Environment and Sustainability

IRMM Institute for Reference Materials and Measurements

JRC Joint Research Centre

LAS linear alkylsulfonates

LoD limit of detection

LUA Landesumweltamt

Ntotal total nitrogen content

NH4-N Ammonium nitrogen

NO3-N Nitrate nitrogen

NP nonylphenol

NRW North Rhine Westphalia

O octa

P poly

PAH polycyclic aromatic hydrocarbon

PCB polychlorinated biphenyl

Pe penta

T tetra

TEQ toxicity equivalent

UBA Umweltbundesamt

WHO World Health Organization

WWTP waste water treatment plant

6

1 Introduction This report gives an overview on the available analytical information on the following raw materials to be used for the production of validation materials of the so-called Project HORIZONTAL

bull Four sludge materials from Duumlsseldorf Germany

bull An agricultural soil material from Reading United Kingdom

bull A compost material from Vienna Austria

bull A compost material from Korschenbroich Germany

bull A sludge-amended agricultural soil from Pavia Province Italy

bull A sludge-amended soil from Barcelona Spain

bull A sludge-amended soil from Essen Germany

bull A long-term sludge exposed soil from Hohenheim Germany

The following analytical information was gathered partly before and during the sampling of the raw materials to be used for the production of the HORIZONTAL validation materials The material were sampled by IES and shipped to IRMM in the course of the year 2005 The information gathered was then completed by various analytical screenings for PAHs and PCBs done by the Institute for Reference Materials and Measurements Geel Belgium for phthalates done by UBA Berlin Germany for PBDE done by IIQAB-CSIC Barcelona Spain for trace elements and some selected major and minor elements by the Institute for Environment and Sustainability Ispra Italy

The work compiled hereafter is based on the numerous additional efforts of the scientists working at various members of the consortium Project HORIZONTAL-Org and contributing organisations

This work is gratefully acknowledged

2 Overview on property values

21 Sludge materials from Duumlsseldorf Germany

The various sewage sludge materials originate from various installations in the North Rhine Westphalia and were produced and sampled by staff from the Landesumweltamt (LUA) NRW under the responsibility from Dr K Furtmann

In total four sludge materials (Sludge A and D from a major municipal WWTP Sludge B from a municipal WWTP with industrial input and Sludge C from a municipal WWTP with high PCB-Content) were obtained and will be blended to two final materials Before sampling the following analytical data for a typical sample were received

7

Table 1 ndash Analytical data obtained on an average sludge sample in LUA NRW (with courtesy of K Furtmann LUA Duumlsseldorf)

Parameter Concentration PCB 120 ugkg DEHP 110 mgkg PAH 5 mgkg (EPA) PCDDF 15 ng TEkg PBDE 400 ugkg NP 40 mgkg LAS 3 gkg AOX 300 mgkg

Subsequent screening led to the information displayed hereafter It should be stressed that the data were obtained as SCREENING information on the UNTREATED or partially treated raw materials Therefore the final target values which are relevant for the validation intercomparison can be different

Table 2 ndash Analytical data obtained on a first screening on the sludge samples from LUA NRW

Sewage sludge A

Dusseldorf

sewage sludge D

Dusseldorf PCB (ngg) 28 62 35 52 101 65 101 31 38 118 49 40 153 30 33 105 24 11 138 46 38 156 lt1 lt1 180 34 23 170 23 19 PAH (ngg) Naphtalene 34 381 Acenaphtylene 15 43 Acenaphthene 81 108 Fluorene 94 1167 Phenantrene 3440 Anthracene 22 344 Flouranthene 316 4817 Pyrene 235 3011 Benz(a)anthracene 473 791 Chrysene 691 1078 Benz(b)fluoranthene 538 1688 Benz(k)fluoranthene 228 635 Benz(a)pyrene 383 1114 Indeno(123-cd)pyrene 92 229 Dibenzo(ah)anthracene 71 70 Benzo(ghi)perylene 80 185

8

Table 3 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Sludge D (1) 0135 41474 385 Sludge B (2) 0538 0034 30634 547 Sludge A (3) 0184 0037 31399 146 Sludge C (4) 0354 1528 6678 229

Table 4 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Sludge 2

(B)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

554

959

694

591

772

509

nq

nq

970

2216

2379

Table 5 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena IES Ispra Spain) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Sludge 1 (D) 265 290 533 359 1231 338 784 438 lt 005 232 786 Sludge 2 (B) 119 311 626 202 278 299 722 251 lt 005 118 625 Sludge 3 (A) 168 360 621 332 847 416 119 451 lt 005 116 1237 Sludge 4 (C) 563 198 116 273 726 511 473 618 lt 005 444 2015

Table 6 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Sludge 1 (D) 2154 58 844 099 103 101 4367 lt15 50448 Sludge 2 (B) 1067 366 692 046 1491 077 5217 lt15 57633 Sludge 3 (A) 731 663 684 035 1287 068 3733 lt15 60369 Sludge 4 (C) 4379 965 527 163 522 107 5628 lt15 23945

Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM)Sludge 1 (D) 03 2403 101 1002 350 15 1944 132Sludge 2 (B) 031 315 97 879 172 12 514 180Sludge 3 (A) 031 1281 153 1567 265 16 1440 168Sludge 4 (C) 055 231 628 2625 371 81 1101 244

9

22 Agricultural soil material from Reading United Kingdom

The material was proposed by the University of Reading (S Nortcliff) and was sampled from a site called ldquoFrogmore Farmrdquo which was featured in the ldquoMetalsrdquo Report for HORIZONTAL This site is close to Reading with soils developed on flintyloamy periglacial materials over Chalk has a long and well documented history of sludge application The focus of the work of Nortcliff et al undertook at this site and the monitoring and control at the site (by Thames Water and the subsequent subsidiary bodies dealing with sludge application to soil) was on metals (and metal loads) with no analysis or indeed any form of investigation in to organics in the broadest sense

The analytical information produced in the context of the screening of the raw material is displayed below

Table 7 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 3

(Reading) 0032 0119 669

Table 8 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 3 (Reading) 015 706 279 138 152 901 267 300 lt 005 258 931

Table 9 ndash Analytical data obtained on a first screening on the sludge-amended soil from Reading (courtesy of IRMM)

Parameter Concentration

PCB ngg 28 lt1 52 lt1 101 lt1 118 lt1 153 lt1 105 lt1 138 lt1 156 lt1 180 lt1 170 lt1 PAH ngg Naphtalene lt10 Acenaphtylene 21 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene lt10 Flouranthene 818 Pyrene 776 Benz(a)anthracene 565

10

Parameter Concentration

Chrysene 608 Benz(b)fluoranthene 824 Benz(k)fluoranthene 329 Benz(a)pyrene 799 Indeno(123-cd)pyrene

779

Dibenzo(ah)anthracene 118 Benzo(ghi)perylene 394

Table 10 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 3

(Reading)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

103

003

nq

nq

nq

nd

nd

272

273

Table 11 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 3 (Reading) 015 706 279 138 152 901 267 300 lt 005 258 931

Table 12 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 3 (Reading) 7936 477 112 096 194 017 4107 443 2102 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 3 (Reading) 042 13 45 69 69 69 216 92

Table 13 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 3 (Reading) 012

11

23 Compost from Vienna Austria

The fresh compost material was obtained from the Austrian Federal Environment Agency (UBA Vienna) which had used a sub-batch of the raw material for national intercomparson The remainder of the material was stored at 4degC until shipment to IRMM for further processing The following analytical information was provided by UBA Austria and completed with various screenings

Table 14 ndash Analytical data on compost material received from UBA Austria Inorganic and sum parameters

Parameter Unit Sample fraction used Observed mean B CAT mgl FM Fresh sample lt10mm 61 K CAT mgl FM Fresh sample lt10mm 2624 Mg CAT mgl FM Fresh sample lt10mm 242 P CAT mgl FM Fresh sample lt10mm 49 B CAT DM Fresh sample lt10mm 00017 K CAT DM Fresh sample lt10mm 072 Mg CAT DM Fresh sample lt10mm 007 P CAT DM Fresh sample lt10mm 001 NO3-N mgkg FM Fresh sample lt10mm 35 NH4-N mgkg FM Fresh sample lt10mm 230 Ctotal DM lt45degdry milled 29 Corg DM lt45degdry milled 27 Ntotal DM lt45degdry milled 17 P mgkg DM lt45degdry milled 2596 K mgkg DM lt45degdry milled 11019 K DM lt45degdry milled 110 B mgkg DM lt45degdry milled 60 Cd mgkg DM lt45degdry milled 046 Cr mgkg DM lt45degdry milled 25 Cu mgkg DM lt45degdry milled 46 Hg mgkg DM lt45degdry milled 020 Ni mgkg DM lt45degdry milled 18 Pb mgkg DM lt45degdry milled 45 Zn mgkg DM lt45degdry milled 198 Ca mgkg DM lt45degdry milled 68776 Ca DM lt45degdry milled 69 Mo mgkg DM lt45degdry milled 08 S mgkg DM lt45degdry milled 2137 Fe mgkg DM lt45degdry milled 9959 Mn mgkg DM lt45degdry milled 418 Na mgkg DM lt45degdry milled 742 Co mgkg DM lt45degdry milled 41 AOX mgkg DM lt30deg dry milled 62

Table 15 ndash Analytical data on compost material received from UBA Austria Polycyclic aromatic hydrocarbons

PAH Unit Result Naphthaline microgkg DM 93 Acenaphthylene microgkg DM 86 Acenaphthene microgkg DM 5 Fluorene microgkg DM 80 Phenanthrene microgkg DM 89 Anthracene microgkg DM 27 Fluoranthene microgkg DM 487 Pyrene microgkg DM 380

12

PAH Unit Result Benzo(a)anthracene microgkg DM 278 Chrysene microgkg DM 317 Benzo(b)fluoranthene microgkg DM 365 Benzo(k)fluoranthene microgkg DM 193 Benz(a)pyrene microgkg DM 320 Indeno(123-cd)pyrene microgkg DM 233 Dibenz(ah)anthracene microgkg DM 67 Benzo(ghi)perylene microgkg DM 225 Sum EPA microgkg DM 3013 Sum EPA mgkg DM 30

Table 16 ndash Analytical data on compost material received from UBA Austria Sum PCDDs and PCBs

Parameter

Dioxine TEQ (ITEF) ngkg DM 73 TEQ (WHO) ngkg DM 35 PCB Σ Ballschmiter mgkg DM 005

Table 17 ndash Analytical data on compost material obtained by screening in IRMM

Parameter Result in ngg

PCB 28 2 52 2 101 4 118 3 153 10 105 1 138 8 156 1 180 5 170 lt1 PAH Naphtalene lt10 Acenaphtylene lt10 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene 26 Fluoranthene 611 Pyrene 510 Benz(a)anthracene 888 Chrysene 957 Benz(b)fluoranthene 1531 Benz(k)fluoranthene 547 Benz(a)pyrene 1101 Indeno(123-cd)pyrene 416 Dibenzo(ah)anthracene 81 Benzo(ghi)perylene 295

13

Table 18 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Compost 1

(Vienna)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

402

019

259

nq

023

004

nq

nq

144

174

259

Table 19 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Compost 1

(Vienna) 0058 1426 557

Table 20 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Compost 1 (Vienna) 039 736 319 410 365 127 495 004 079 013 208

Table 21 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Compost 1 (Vienna) 2063 431 617 426 199 249 1602 lt15 10521

Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Compost 1 (Vienna) 035 3496 81 375 79 55 653 60

Table 22 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Compost 1 (Vienna) 017

14

24 Agricultural soil sludge amended soil from Pavia Italy

This sludge-amended soil material was obtained during a monitoring campaign which aimed at a generic description of the over-all soil quality in Pavia Province Italy The material which was collected from the upper horizon originates from a small farm called ldquoCascina Novellordquo During the characterisation of the site the following analytical information was obtained on a pooled sample of a sub-area of the farm of 20 X 20 m2

Table 23 ndash Analytical data on Pavia soil

Parameter Result Al 713 Wgt As 224 mgkg Cd 079 mgkg Cr 59 mgkg Cu 308 mgkg Hg 008 mgkg Ni 344 mgkg Pb 246 mgkg Zn 95 mgkg C 091 Wgt 2378-TCDD 0047 pgg 12378-PeCDD 015 pgg 123478-HxCDD 019 pgg 123678-HxCDD 15 pgg 123789-HxCDD 074 pgg 1234678-HpCDD 26 pgg OCDD 382 pgg 2378-TCDF 068 pgg 12378-PeCDF 053 pgg 23478-PeCDF 071 pgg 123478-HxDF 100 pgg 123678-HxDF 066 pgg 234678-HxDF 16 pgg 123789-HxDF 027 pgg 1234678-HpDF 12 pgg 1234789-HpDF 068 pgg OCDF 33 pgg I-TEQ 20 pgg WHO-TEQ 17 pgg

In addition the screening performed at IRMM did not reveal significant quantities of PCBs and PAHs which were all below the LoDs (1 ngg for PCBs and 10 ngg for PAHs respectively)

Table 24 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 5 (Pavia) 0005 0011 154

15

Table 25 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 5

(Pavia)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

039

nq

nq

008

nq

nd

nd

670

671

Table 26 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 5 (Pavia) 033 184 573 225 426 305 206 200 lt 005 381 878

Table 27 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 5 (Pavia) 6939 129 145 224 425 116 6118 255 1789 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 5 (Pavia) 184 62 38 108 55 66 597 110

Table 28 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 5 (Pavia) 006

16

25 Sludge-amended-soil from Barcelona Spain

The sludge-amended soil material from Barcelona sampled upon indication from the Barcelorsquo- Group in Barcelona

Table 29 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 2 (Lleida T) 0015 0183 1138

Table 30 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 2

(Lleida T)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

159

045

nq

048

160

nq

nq

1000

1004

Table 31 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 2 (Lleida T) 059 141 327 536 405 186 184 224 lt 005 318 111

Table 32 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 2 (Lleida T) 4443 1067 1429 253 344 204 4116 780 3396 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 2 (Lleida T) 064 65 26 125 59 17 547 65

Table 33 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 2 (Lleida T) 010

17

26 Sludge amended soil from Essen Germany

The German sludge-amended soil from Essen which was provided as the three sludge materials by LUA NRW did not feature significant concentrations of the PCB congeners 28 52 101 118 153 105 138 156 180 170 but had detectable amounts of some PAHs

Table 34 ndash Analytical screening data on the German sludge-amended soil

Parameter Concentration(ngg)

Naphtalene lt10 Acenaphtylene lt10 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene lt10 Fluoranthene 28 Pyrene 20 Benz(a)anthracene 24 Chrysene 47 Benz(b)fluoranthene 76 Benz(k)fluoranthene 20 Benz(a)pyrene 35 Indeno(123-cd)pyrene 35 Dibenzo(ah)anthracene 10 Benzo(ghi)perylene 26

Table 35 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 4 (Essen) 0011 0302 055

Table 36 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 4

(Essen)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

nq

nq

nq

nq

nq

nq

128

191

203

18

Table 37 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 4 (Essen) 052 545 261 805 320 403 273 273 lt 005 295 781

Table 38 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 4 (Essen) 7947 442 085 06 086 007 2163 189 2019 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 4 (Essen) 045 19 42 87 683 60 462 61

Table 39 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 4 (Essen) 004

27 Long-term sludge exposed soil from Hohenheim-Stuttgart Germany

Similarly an additional sludge exposed soil was sampled at the University of Hohenheim Stuttgart were a test soil was long-term exposed to elevated concentrations of sewage sludge

Table 40 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 1 (Stuttgart) 0045 0263 1765

Table 41 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 1

(Stuttgart)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

230

006

004

004

nq

nd

nd

498

500

19

Table 42 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 1 (Stuttgart) 069 127 361 262 504 183 252 262 lt 005 266 142

Table 43 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 1 (Stuttgart) 7194 1006 133 186 366 088 7874 275 3571 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 1 (Stuttgart) 123 50 47 212 85 69 991 129

Table 44 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 1 (Stuttgart) 177

18

Annex 3

Statistical calculations

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 47)Mandels h statistics(Sludge 1 - PBD 47)

Sample Sludge 1 NUM

Element PBD 47

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00213 0001 3 -021 005 - - 10L - - NUM46L 00273 0002 4 016 021 - - 46L - - NUM64L 00059 0000 4 -116 002 NUM - 64L - - NUM12L 00188 0000 4 -036 002 - - 12L - - NUM26L 00499 0024 2 157 223 Fail - - 26L - - NUM

Totgem 0025 0005 mgkg 1-level 172 (185) NUM (10L46L64L12L26L) -1Totstd= 0016 0010 5-level 157 (162) 5

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 5 Labs rejected (10L46L64L12L26L)

000 050 100 150 200 250

k-values

10L

46L

64L

12L

26L

Mandels k statistics(Sludge 1 - PBD 47)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

10L

46L

64L

12L

26L

Labo

rato

ries

NUM

-200 -100 000 100 200

h-values

10L

46L

64L

12L

26L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 47)

Sludge 1-PBD 47

Unit mgkg

Mandels k statistics(Soil 3 - PBD 47)Mandels h statistics(Soil 3 - PBD 47)

Sample Soil 3 Soil 3 - PBD 47 -- Mean PARM = 0001 [mgkg]

Element PBD 47

General calcparmT1= 134814E-02T2= 142830E-05T3= 13T4= 45T5= 22767E-06

n= variabelp= 4

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean26L 00007 0000 2 -143 001 00007 00000 2 1 00046L 00010 0001 4 010 181 00010 00008 4 3 00010L 00011 0000 3 049 023 00011 00001 3 2 00012L 00012 0000 4 084 081 00012 00004 4 3 000

Totgem 0001 0000 mgkg 1-level 149 (177) 4 00010 () 4 3Totstd= 0000 0000 5-level 142 (159)

RESULTS Mean = 000100 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000050 --gt 5031 r = 00014Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000050 --gt 5031 R = 00014Remarks none

000 050 100 150 200

k-values

26L

46L

10L

12L

Mandels k statistics(Soil 3 - PBD 47)

00 00 00 00 00 00 00 00 00 00 00

Deviation from Mean

26L

46L

10L

12L

Labo

rato

ries

Soil 3 - PBD 47 -- Mean PARM = 0001 [mgkg]

-200 -100 000 100

h-values

26L

46L

10L

12L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 47)

Soil 3-PBD 47

Unit mgkg

Mandels k statistics(Compost 1 - PBD 99)Mandels h statistics(Compost 1 - PBD 99)

Sample Compost 1 Compost 1 - PBD 99 -- Mean PARM = 0003 [mgkg]

Element PBD 99

General calcparmT1= 492124E-02T2= 148747E-04T3= 17T4= 61T5= 93196E-06

n= variabelp= 5

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00020 0000 4 -137 053 00020 00004 4 3 000

26L 00025 0000 2 -058 024 00025 00002 2 1 00010L 00029 0000 3 012 032 00029 00003 3 2 00046L 00033 0001 4 069 161 00033 00013 4 3 00012L 00036 0001 4 114 140 00036 00011 4 3 000

Totgem 0003 0001 mgkg 1-level 172 (185) 5 00029 () 5 4Totstd= 0001 0001 5-level 157 (162)

RESULTS Mean = 000286 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000088 --gt 3086 r = 00025Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000101 --gt 3525 R = 00028Remarks none

000 050 100 150 200

k-values

4L

26L

10L

46L

12L

Mandels k statistics(Compost 1 - PBD 99)

00 00 00 00 00 00 00 00 00 00

Deviation from Mean

4L

26L

10L

46L

12L

Labo

rato

ries

Compost 1 - PBD 99 -- Mean PARM = 0003 [mgkg]

-200 -100 000 100 200

h-values

4L

26L

10L

46L

12L

Labo

rato

ries

Mandels h statistics(Compost 1 - PBD 99)

Compost 1-PBD 99

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 99)Mandels h statistics(Sludge 1 - PBD 99)

Sample Sludge 1 Sludge 1 - PBD 99 -- Mean PARM = 0024 [mgkg]

Element PBD 99

General calcparmT1= 448050E-01T2= 112113E-02T3= 19T4= 73T5= 32972E-05

n= variabelp= 5

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean64L 00173 0002 4 -118 041 Fail 00173 00019 4 3 -0014L 00183 0002 4 -104 032 00183 00015 4 3 -001

12L 00227 0001 4 -038 022 00227 00010 4 3 00010L 00290 0001 3 055 021 00290 00010 3 2 00146L 00320 0002 4 100 039 00320 00018 4 3 00126L 00323 0011 2 105 234 - - 26L - - 001

Totgem 0025 0003 mgkg 1-level 187 (177) 5 00239 (26L) 5 4Totstd= 0007 0004 5-level 166 (154) 1

RESULTS Mean = 002385 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000153 --gt 643 r = 00043Between lab variance S2L = 000004Reproducibility var S2R = 000004Reproducibility std SR = 000666 --gt 2791 R = 00186Remarks 1 Lab rejected (26L)

000 050 100 150 200 250

k-values

64L

4L

12L

10L

46L

26L

Mandels k statistics(Sludge 1 - PBD 99)

00 00 00 00 00 00 00 00 00 00

Deviation from Mean

64L

4L

12L

10L

46L

26L

Labo

rato

ries

Sludge 1 - PBD 99 -- Mean PARM = 0024 [mgkg]

-200 -100 000 100 200

h-values

64L

4L

12L

10L

46L

26L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 99)

Sludge 1-PBD 99

Unit mgkg

Mandels k statistics(Soil 3 - PBD 99)Mandels h statistics(Soil 3 - PBD 99)

Sample Soil 3 NUM

Element PBD 99

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00017 0000 4 091 068 - - 10L - - NUM46L 00017 0001 4 100 211 - - 46L - - NUM64L 00005 0000 4 -106 023 NUM - 64L - - NUM12L 00012 0000 4 015 014 - - 12L - - NUM26L 00006 0000 2 -101 012 - - 26L - - NUM

Totgem 0001 0000 mgkg 1-level 172 (173) NUM (10L46L64L12L26L) -1Totstd= 0001 0000 5-level 157 (153) 5

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 5 Labs rejected (10L46L64L12L26L)

000 050 100 150 200 250

k-values

10L

46L

64L

12L

26L

Mandels k statistics(Soil 3 - PBD 99)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

10L

46L

64L

12L

26L

Labo

rato

ries

NUM

-200 -100 000 100 200

h-values

10L

46L

64L

12L

26L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 99)

Soil 3-PBD 99

Unit mgkg

Mandels k statistics(Compost 1 - PBD 100)Mandels h statistics(Compost 1 - PBD 100)

Sample Compost 1 Compost 1 - PBD 100 -- Mean PARM = 0001 [mgkg]

Element PBD 100

General calcparmT1= 124272E-02T2= 113129E-05T3= 14T4= 52T5= 46584E-07

n= variabelp= 4

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean26L 00006 0000 2 -131 037 Fail 00006 00001 2 1 00010L 00009 0000 4 003 083 00009 00002 4 3 00046L 00009 0000 4 016 115 00009 00002 4 3 00012L 00011 0000 4 112 136 Fail 00011 00003 4 3 000

Totgem 0001 0000 mgkg 1-level 149 (167) 4 00009 () 4 3Totstd= 0000 0000 5-level 142 (15)

RESULTS Mean = 000085 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000022 --gt 2531 r = 00006Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000025 --gt 2882 R = 00007Remarks none

000 050 100 150

k-values

26L

10L

46L

12L

Mandels k statistics(Compost 1 - PBD 100)

00 00 00 00 00 00 00 00 00 00 00

Deviation from Mean

26L

10L

46L

12L

Labo

rato

ries

Compost 1 - PBD 100 -- Mean PARM = 0001 [mgkg]

-200 -100 000 100 200

h-values

26L

10L

46L

12L

Labo

rato

ries

Mandels h statistics(Compost 1 - PBD 100)

Compost 1-PBD 100

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 100)Mandels h statistics(Sludge 1 - PBD 100)

Sample Sludge 1 Sludge 1 - PBD 100 -- Mean PARM = 0005 [mgkg]

Element PBD 100

General calcparmT1= 852065E-02T2= 412762E-04T3= 18T4= 68T5= 78914E-07

n= variabelp= 5

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00039 0000 4 -042 007 Fail 00039 00002 4 3 000

12L 00044 0000 4 -041 005 Fail 00044 00001 4 3 00010L 00046 0000 4 -041 013 Fail 00046 00003 4 3 00046L 00056 0000 4 -040 012 Fail 00056 00003 4 3 00026L 00059 0000 2 -040 013 Fail 00059 00003 2 1 00038L 02168 0006 4 204 244 Fail - - 38L - - 021

Totgem 0040 0001 mgkg 1-level 187 (177) 5 00049 (38L) 5 4Totstd= 0087 0002 5-level 166 (154) 1

RESULTS Mean = 000486 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000025 --gt 507 r = 00007Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000084 --gt 1731 R = 00024Remarks 1 Lab rejected (38L)

000 050 100 150 200 250

k-values

4L

12L

10L

46L

26L

38L

Mandels k statistics(Sludge 1 - PBD 100)

-01 00 01 01 02 02 03

Deviation from Mean

4L

12L

10L

46L

26L

38L

Labo

rato

ries

Sludge 1 - PBD 100 -- Mean PARM = 0005 [mgkg]

-100 000 100 200 300

h-values

4L

12L

10L

46L

26L

38L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 100)

Sludge 1-PBD 100

Unit mgkg

Mandels k statistics(Soil 3 - PBD 100)Mandels h statistics(Soil 3 - PBD 100)

Sample Soil 3 NUM

Element PBD 100

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00003 0000 4 -050 000 Fail - - 10L - - NUM46L 00003 0000 4 -050 000 Fail NUM - 46L - - NUM3L 305500 2051 2 150 200 Fail - - 3L - - NUM

26L 00005 0000 2 -050 000 Fail - - 26L - - NUM

Totgem 7638 0513 mgkg 1-level 149 (177) NUM (10L46L3L26L) -1Totstd= 15275 1025 5-level 142 (159) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (10L46L3L26L)

000 050 100 150 200

k-values

10L

46L

3L

26L

Mandels k statistics(Soil 3 - PBD 100)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

10L

46L

3L

26L

Labo

rato

ries

NUM

-100 000 100 200

h-values

10L

46L

3L

26L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 100)

Soil 3-PBD 100

Unit mgkg

Mandels k statistics(Compost 1 - PBD 153)Mandels h statistics(Compost 1 - PBD 153)

Sample Compost 1 NUM

Element PBD 153

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean44L 00053 0001 3 150 157 Fail - - 44L - - NUM46L 00007 0000 4 -044 111 Fail - - 46L - - NUM12L 00005 0000 4 -051 055 Fail - - 12L - - NUM26L 00005 0000 2 -054 001 Fail NUM - 26L - - NUM

Totgem 0002 0000 mgkg 1-level 149 (177) NUM (44L46L12L26L) -1Totstd= 0002 0000 5-level 142 (159) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (44L46L12L26L)

000 050 100 150 200

k-values

44L

46L

12L

26L

Mandels k statistics(Compost 1 - PBD 153)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

44L

46L

12L

26L

Labo

rato

ries

NUM

-100 000 100 200

h-values

44L

46L

12L

26L

Labo

rato

ries

Mandels h statistics(Compost 1 - PBD 153)

Compost 1-PBD 153

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 153)Mandels h statistics(Sludge 1 - PBD 153)

Sample Sludge 1 Sludge 1 - PBD 153 -- Mean PARM = 0004 [mgkg]

Element PBD 153

General calcparmT1= 676738E-02T2= 267609E-04T3= 18T4= 68T5= 19626E-05

n= variabelp= 5

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00024 0000 4 -157 017 00024 00002 4 3 000

12L 00038 0002 4 006 154 00038 00018 4 3 00046L 00039 0000 4 011 026 00039 00003 4 3 00026L 00039 0000 2 018 004 00039 00000 2 1 00064L 00049 0002 4 122 159 00049 00018 4 3 000

Totgem 0004 0001 mgkg 1-level 172 (173) 5 00038 () 5 4Totstd= 0001 0001 5-level 157 (153)

RESULTS Mean = 000378 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000123 --gt 3252 r = 00034Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000142 --gt 3754 R = 00040Remarks none

000 050 100 150 200

k-values

4L

12L

46L

26L

64L

Mandels k statistics(Sludge 1 - PBD 153)

00 00 00 00 00 00 00

Deviation from Mean

4L

12L

46L

26L

64L

Labo

rato

ries

Sludge 1 - PBD 153 -- Mean PARM = 0004 [mgkg]

-200 -100 000 100 200

h-values

4L

12L

46L

26L

64L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 153)

Sludge 1-PBD 153

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 154)Mandels h statistics(Sludge 1 - PBD 154)

Sample Sludge 1 NA

Element PBD 154

General calcparmT1= NAT2= NAT3=T4=T5=

n= variabelp=

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00021 0000 3 -100 021 NA - 4L - - NA

46L 00025 0000 4 115 018 NA - 46L - - NA64L 00021 0001 4 -066 179 - - 64L - - NA12L 00023 0000 4 050 085 - - 12L - - NA

Totgem 0002 0000 mgkg 1-level 149 (167) NA (4L46L64L12L) -1Totstd= 0000 0000 5-level 142 (15) 4

RESULTS Mean = NA mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NAReproducibility var S2R = NAReproducibility std SR = NA --gt NA R = NARemarks 4 Labs rejected (4L46L64L12L)

000 050 100 150 200

k-values

4L

46L

64L

12L

Mandels k statistics(Sludge 1 - PBD 154)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

4L

46L

64L

12L

Labo

rato

ries

NA

-100 000 100 200

h-values

4L

46L

64L

12L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 154)

Sludge 1-PBD 154

Unit mgkg

Mandels k statistics(Soil 3 - PBD 154)Mandels h statistics(Soil 3 - PBD 154)

Sample Soil 3 NUM

Element PBD 154

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

4L 00010 - 1 150 Fail - - 4L - - NUM46L 00001 0000 4 -053 096 Fail - - 46L - - NUM64L 00001 0000 4 -056 105 Fail NUM - 64L - - NUM12L 00002 0000 4 -040 099 Fail - - 12L - - NUM

Totgem 000037 0000 mgkg 1-level 149 (164) NUM (4L46L64L12L) -1Totstd= 000042 0000 5-level 142 (153) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (4L46L64L12L)

000 050 100 150

k-values

4L

46L

64L

12L

Mandels k statistics(Soil 3 - PBD 154)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

4L

46L

64L

12L

Labo

rato

ries

NUM

-100 000 100 200

h-values

4L

46L

64L

12L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 154)

Soil 3-PBD 154

Unit mgkg

Mandels k statistics(Compost 1 - PBD 209)Mandels h statistics(Compost 1 - PBD 209)

Sample Compost 1 NUM

Element PBD 209

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00065 0003 2 -049 032 - - 4L - - NUM

44L 00573 0021 4 150 197 Fail - - 44L - - NUM12L 00078 0001 4 -045 011 - - 12L - - NUM26L 00049 0000 2 -056 000 NUM - 26L - - NUM

Totgem 0019 0006 mgkg 1-level 149 (177) NUM (4L44L12L26L) -1Totstd= 0025 0010 5-level 142 (159) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (4L44L12L26L)

000 050 100 150 200

k-values

4L

44L

12L

26L

Mandels k statistics(Compost 1 - PBD 209)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

4L

44L

12L

26L

Labo

rato

ries

NUM

-100 000 100 200

h-values

4L

44L

12L

26L

Labo

rato

ries

Mandels h statistics(Compost 1 - PBD 209)

Compost 1-PBD 209

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 209)Mandels h statistics(Sludge 1 - PBD 209)

Sample Sludge 1 Sludge 1 - PBD 209 -- Mean PARM = 0249 [mgkg]

Element PBD 209

General calcparmT1= 394542E+00T2= 107296E+00T3= 16T4= 56T5= 19723E-02

n= variabelp= 5

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 01550 0055 4 -112 148 Fail 01550 00551 4 3 -009

46L 02050 0007 2 -053 019 02050 00071 2 1 -00412L 02137 0058 4 -042 155 02137 00576 4 3 -00426L 03149 0021 2 078 057 Fail 03149 00210 2 1 00764L 03577 0007 4 129 020 Fail 03577 00074 4 3 011

Totgem 0249 0030 mgkg 1-level 172 (185) 5 02493 () 5 4Totstd= 0084 0025 5-level 157 (162)

RESULTS Mean = 024926 mgkg

Repeatability variance S2r = 000179Repeatability std Sr = 004234 --gt 1699 r = 01186Between lab variance S2L = 000743Reproducibility var S2R = 000922Reproducibility std SR = 009604 --gt 3853 R = 02689Remarks none

000 050 100 150 200

k-values

4L

46L

12L

26L

64L

Mandels k statistics(Sludge 1 - PBD 209)

-01 -01 00 01 01 02

Deviation from Mean

4L

46L

12L

26L

64L

Labo

rato

ries

Sludge 1 - PBD 209 -- Mean PARM = 0249 [mgkg]

-200 -100 000 100 200

h-values

4L

46L

12L

26L

64L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 209)

Sludge 1-PBD 209

Unit mgkg

Mandels k statistics(Soil 3 - PBD 209)Mandels h statistics(Soil 3 - PBD 209)

Sample Soil 3 Soil 3 - PBD 209 -- Mean PARM = 0258 [mgkg]

Element PBD 209

General calcparmT1= 596398E+00T2= 191917E+00T3= 22T4= 84T5= 13249E-02

n= variabelp= 6

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean26L 01162 0021 2 -108 074 Fail 01162 00207 2 1 -0144L 01303 0031 4 -097 111 Fail 01303 00312 4 3 -013

46L 01975 0036 4 -046 128 Fail 01975 00359 4 3 -00644L 02898 0035 4 024 124 Fail 02898 00346 4 3 00312L 03895 0018 4 100 065 Fail 03895 00181 4 3 01364L 04260 0022 4 127 078 Fail 04260 00219 4 3 017

Totgem 0258 0027 mgkg 1-level 187 (177) 6 02582 () 6 5Totstd= 0132 0008 5-level 166 (154)

RESULTS Mean = 025818 mgkg

Repeatability variance S2r = 000083Repeatability std Sr = 002878 --gt 1115 r = 00806Between lab variance S2L = 001640Reproducibility var S2R = 001723Reproducibility std SR = 013127 --gt 5084 R = 03676Remarks none

000 050 100 150

k-values

26L

4L

46L

44L

12L

64L

Mandels k statistics(Soil 3 - PBD 209)

-02 -01 -01 00 01 01 02 02

Deviation from Mean

26L

4L

46L

44L

12L

64L

Labo

rato

ries

Soil 3 - PBD 209 -- Mean PARM = 0258 [mgkg]

-200 -100 000 100 200

h-values

26L

4L

46L

44L

12L

64L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 209)

Soil 3-PBD 209

Unit mgkg

Mandels k statistics(Compost 1 - Sum PBD)Mandels h statistics(Compost 1 - Sum PBD)

Sample Compost 1 Compost 1 - Sum PBD -- Mean PARM = 0009 [mgkg]

Element Sum PBD

General calcparmT1= 154064E-01T2= 169065E-03T3= 18T4= 68T5= 11354E-04

n= variabelp= 5

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00031 0002 4 -067 016 00031 00016 4 3 -0014L 00055 0005 4 -056 048 00055 00047 4 3 000

46L 00085 0003 4 -042 031 00085 00030 4 3 00026L 00123 0000 2 -024 003 00123 00002 2 1 00012L 00154 0002 4 -011 021 00154 00021 4 3 00144L 00613 0023 4 200 237 Fail - - 44L - - 005

Totgem 0018 0006 mgkg 1-level 187 (177) 5 00089 (44L) 5 4Totstd= 0022 0009 5-level 166 (154) 1

RESULTS Mean = 000893 mgkg

Repeatability variance S2r = 000001Repeatability std Sr = 000296 --gt 3308 r = 00083Between lab variance S2L = 000002Reproducibility var S2R = 000003Reproducibility std SR = 000570 --gt 6374 R = 00159Remarks 1 Lab rejected (44L)

000 050 100 150 200 250

k-values

10L

4L

46L

26L

12L

44L

Mandels k statistics(Compost 1 - Sum PBD)

00 00 00 00 00 00 01 01

Deviation from Mean

10L

4L

46L

26L

12L

44L

Labo

rato

ries

Compost 1 - Sum PBD -- Mean PARM = 0009 [mgkg]

-100 000 100 200

h-values

10L

4L

46L

26L

12L

44L

Labo

rato

ries

Mandels h statistics(Compost 1 - Sum PBD)

Compost 1-Sum PBD

Unit mgkg

Mandels k statistics(Sludge 1 - Sum PBD)Mandels h statistics(Sludge 1 - Sum PBD)

Sample Sludge 1 Sludge 1 - Sum PBD -- Mean PARM = 0256 [mgkg]

Element Sum PBD

General calcparmT1= 531806E+00T2= 162188E+00T3= 22T4= 84T5= 25223E-02

n= variabelp= 6

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00423 0025 4 -156 044 Fail 00423 00252 4 3 -02146L 01808 0118 4 -049 205 - - 46L - - -0074L 01810 0056 4 -049 097 01810 00558 4 3 -007

38L 02168 0006 4 -022 010 02168 00059 4 3 -00412L 02890 0065 4 034 113 02890 00647 4 3 00364L 03958 0008 4 116 014 Fail 03958 00079 4 3 01426L 04094 0034 2 126 059 Fail 04094 00337 2 1 015

Totgem 0245 0044 mgkg 1-level 198 (179) 6 02557 (46L) 6 5Totstd= 0130 0039 5-level 171 (155) 1

RESULTS Mean = 025570 mgkg

Repeatability variance S2r = 000158Repeatability std Sr = 003970 --gt 1553 r = 01112Between lab variance S2L = 001807Reproducibility var S2R = 001964Reproducibility std SR = 014015 --gt 5481 R = 03924Remarks 1 Lab rejected (46L)

000 050 100 150 200 250

k-values

10L

46L

4L

38L

12L

64L

26L

Mandels k statistics(Sludge 1 - Sum PBD)

-03 -02 -02 -01 -01 00 01 01 02 02

Deviation from Mean

10L

46L

4L

38L

12L

64L

26L

Labo

rato

ries

Sludge 1 - Sum PBD -- Mean PARM = 0256 [mgkg]

-200 -100 000 100 200

h-values

10L

46L

4L

38L

12L

64L

26L

Labo

rato

ries

Mandels h statistics(Sludge 1 - Sum PBD)

Sludge 1-Sum PBD

Unit mgkg

Mandels k statistics(Soil 3 - Sum PBD)Mandels h statistics(Soil 3 - Sum PBD)

Sample Soil 3 Soil 3 - Sum PBD -- Mean PARM = 0227 [mgkg]

Element Sum PBD

General calcparmT1= 610980E+00T2= 200876E+00T3= 26T4= 100T5= 13106E-02

n= variabelp= 7

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00028 0001 4 -037 000 Fail 00028 00005 4 3 -02226L 01179 0021 2 -036 003 Fail 01179 00208 2 1 -0114L 01305 0031 4 -036 004 Fail 01305 00308 4 3 -010

46L 02065 0035 4 -036 005 Fail 02065 00350 4 3 -00244L 02923 0037 4 -035 005 Fail 02923 00365 4 3 00712L 04051 0015 4 -034 002 Fail 04051 00149 4 3 01864L 04314 0022 4 -033 003 Fail 04314 00223 4 3 0203L 305500 2051 2 247 283 Fail - - 3L - - 3032

Totgem 4017 0276 mgkg 1-level 206 (181) 7 02266 (3L) 7 6Totstd= 10722 0717 5-level 175 (156) 1

RESULTS Mean = 022663 mgkg

Repeatability variance S2r = 000069Repeatability std Sr = 002626 --gt 1159 r = 00735Between lab variance S2L = 002568Reproducibility var S2R = 002637Reproducibility std SR = 016238 --gt 7165 R = 04547Remarks 1 Lab rejected (3L)

000 050 100 150 200 250 300

k-values

10L

26L

4L

46L

44L

12L

64L

3L

Mandels k statistics(Soil 3 - Sum PBD)

-50 00 50 100 150 200 250 300 350

Deviation from Mean

10L

26L

4L

46L

44L

12L

64L

3L

Labo

rato

ries

Soil 3 - Sum PBD -- Mean PARM = 0227 [mgkg]

-100 000 100 200 300

h-values

10L

26L

4L

46L

44L

12L

64L

3L

Labo

rato

ries

Mandels h statistics(Soil 3 - Sum PBD)

Soil 3-Sum PBD

19

Annex 4

Raw data submitted

Sample Compost1 Sample Compost 1 Sample Compost 1Element PBD 99 Element PBD 100 Element PBD 153

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]4L 00021 10L 00008 44L 000504L 00024 10L 00008 44L 000604L 00014 10L 00007 44L 000504L 00020 10L 00011 46L 00004

10L 00029 46L 00007 46L 0001210L 00027 46L 00012 46L 0000410L 00032 46L 00009 46L 0000946L 00025 46L 00007 12L 0000446L 00052 12L 00008 12L 0000846L 00029 12L 00012 12L 0000446L 00026 12L 00008 12L 0000712L 00026 12L 00014 26L 0000512L 00043 26L 00007 26L 0000512L 00026 26L 0000612L 0004726L 0002626L 00024

Sample Compost 1 Sample Compost 1 Sample Compost 1Element PBD 154 Element PBD 183 Element PBD 196

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]4L 00010 46L 00002 46L 00011

46L 00003 46L 00024 46L 0000846L 00007 46L 00021 12L 0000246L 00003 46L 00003 12L 0000346L 00004 12L 00003 12L 0000112L 00003 12L 00011 12L 0000212L 00005 12L 0000312L 00031 12L 0000312L 00006

Sample Compost 1 Sample Compost 1 Sample Compost 1Element PBD 197 Element PBD 203 Element PBD 209

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00002 46L 00010 4L 0004146L 00023 12L 00002 4L 0008946L 00022 12L 00003 44L 0041012L 00004 12L 00002 44L 0084012L 00006 12L 00002 44L 0064012L 00003 44L 0040012L 00004 12L 00079

12L 0007312L 0006512L 0009326L 0004926L 00049

Sample Compost 1Element PBD 47

LAB PARM [mgkg]26L 0003826L 00039

Element PBD 99 Element PBD 47 Element PBD 209LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]

4L 00170 10L 00210 4L 010004L 00200 10L 00220 4L 018004L 00170 10L 00210 4L 012004L 00190 46L 00300 4L 0220010L 00280 46L 00280 46L 0210010L 00300 46L 00250 46L 0200010L 00290 46L 00260 64L 0351846L 00340 64L 00059 64L 0363846L 00330 64L 00057 64L 0364546L 00300 64L 00062 64L 0350846L 00310 64L 00060 12L 0220964L 00194 12L 00191 12L 0177164L 00154 12L 00187 12L 0292264L 00185 12L 00190 12L 0164664L 00159 12L 00186 26L 0329712L 00242 26L 00666 26L 0300012L 00223 26L 0033212L 0022112L 0022226L 0024626L 00400

Element PBD 203 Element PBD 197 Element PBD 196LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00022 46L 00027 46L 0002446L 00014 46L 00024 46L 0002264L 00036 12L 00161 64L 0005864L 00058 12L 00060 64L 0006512L 00063 12L 00061 12L 0004812L 00034 12L 00036 12L 0002512L 00038 12L 0003212L 00027 12L 00022

Element PBD 183 Element PBD 154 Element PBD 153LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00049 4L 00020 4L 0002246L 00035 4L 00022 4L 0002446L 00036 4L 00020 4L 0002246L 00034 46L 00025 4L 0002664L 00027 46L 00025 46L 0004064L 00023 46L 00025 46L 0004264L 00024 46L 00023 46L 0003564L 00020 64L 00034 46L 0003812L 00230 64L 00023 64L 0007412L 00032 64L 00017 64L 0004712L 00031 64L 00011 64L 0004612L 00030 12L 00030 64L 0003026L 00007 12L 00021 12L 0006526L 00008 12L 00021 12L 00029

12L 00021 12L 0003226L 00015 12L 0002926L 00019 26L 00039

26L 00040

Element PBD 100LAB PARM [mgkg]

4L 000384L 000414L 000374L 00038

38L 0219038L 0220038L 0208038L 0220010L 0004410L 0005010L 0004310L 0004646L 0005746L 0005946L 0005346L 0005312L 0004312L 0004512L 0004312L 0004326L 0006226L 00057

Sample Soil 3 Sample Soil 3 Sample Soil 3Element PBD 99 Element PBD 47 Element PBD 100

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]10L 00016 10L 00011 10L 0000310L 00019 10L 00010 10L 0000410L 00013 10L 00012 10L 0000410L 00019 46L 00007 10L 0000246L 00025 46L 00022 46L 0000246L 00025 46L 00005 46L 0000646L 00008 46L 00007 46L 0000246L 00011 12L 00010 46L 0000264L 00005 12L 00017 3L 29100064L 00005 12L 00010 3L 32000064L 00006 12L 00009 26L 0000564L 00007 26L 00007 26L 0000512L 00012 26L 0000712L 0001312L 0001312L 0001226L 0000526L 00006

Sample Soil 3 Sample Soil 3 Sample Soil 3Element PBD 153 Element PBD 154 Element PBD 196

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]44L 00050 4L 00010 46L 0000744L 00050 46L 00001 46L 0001146L 00002 46L 00002 46L 0000846L 00003 46L 00001 46L 0001146L 00002 46L 00002 64L 0002646L 00002 64L 00001 64L 0002664L 00001 64L 00001 64L 0002964L 00001 64L 00001 64L 0003464L 00001 64L 00002 12L 0004564L 00002 12L 00003 12L 00032

12L 00002 12L 0002212L 00002 12L 0002112L 00002

Sample Soil 3 Sample Soil 3 Sample Soil 3Element PBD 197 Element PBD 203 Element PBD 209

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00006 46L 00011 4L 0091046L 00013 46L 00017 4L 0150046L 00011 46L 00015 4L 0120046L 00013 46L 00018 4L 0160012L 00090 64L 00013 44L 0337012L 00056 64L 00014 44L 0281012L 00033 64L 00016 44L 0287012L 00032 64L 00015 44L 02540

12L 00055 46L 0230012L 00041 46L 0220012L 00027 46L 0150012L 00026 46L 01900

64L 0438164L 0401664L 0414464L 0449812L 0367112L 0397812L 0409112L 03838

Sample Soil 3 26L 0102Element PBD 183 26L 0131

LAB PARM [mgkg]46L 0000746L 0000846L 0005846L 0000764L 0000264L 0000364L 0000364L 0000312L 0001512L 0001112L 0000712L 00007

European Commission EUR 23003 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on polybrominated diphenylethers Author(s) E Sobiecka H van der Sloot D Barcelo B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 68 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07403-5 Abstract Project HORIZONTAL is interdisciplinary aiming at a harmonisation and horizontal standardisation of test procedures in particular for sludge soils and biowastes In the context of this standardization project a series of draft technical specification were designed upon an extensive desk study fine-tuned after expert consultations and finally validated in international intercomparisons exercise This report summarises the work performed within the validation study of the draft standard for the determination of polybrominated diphenylethers (PBDE) in soils sludge and treated bio-waste using gas-chromatography method with mass selective detection (GC-MS) It further explains the underlying statistical concept for the calculation of reproducibility and repeatability from intercomparisons data In addition all single values results of the statistical evaluation as well as background information on the validation materials used are described and explained

The mission of the JRC is to provide customer-driven scientific and technical support for the conception development implementation and monitoring of EU policies As a service of the European Commission the JRC functions as a reference centre of science and technology for the Union Close to the policy-making process it serves the common interest of the Member States while being independent of special interests whether private or national

LB

-NA

-23003-EN

-C

14

Matrix Parameter Mean sr sR r R p Outliers Used No of data

No of data reported below

detection

Total no of data

Sludge 1 Sum PBD 0256 155 548 0111 0392 6 1 22 Compost 1 0009 331 637 0008 0016 5 1 18 Soil 3 0227 116 717 0074 0455 7 1 26 Abbreviations sr Repeatability standard deviation SR Reproducibility standard deviation r Repeatability limit (comparing two measurements) R Reproducibility limit (comparing two measurements) p Number of labs determination not possible

15

14 Annexes Annex 1 Model questionnaire to be filled by the participating laboratories Annex 3 Report on the validation materials used Annex 2 Statistical calculations Annex 3 Data submitted

16

Annex 1

Model questionnaire to be filled by the participating laboratories

Model questionnaire to be filled by the participating laboratories Name of laboratory Contact person Contact details email Phone Fax Mail address of lab Dispatch address of lab for shipment of samples (no PO boxes) Title of measurement method (copy attached) Our laboratory is willing to participate in the precision experiment for this draft standard method

Yes No As participant we understand that

bull All essential apparatus chemicals and other requirements specified in the method must be available in our laboratory when the programme begins

bull Specified timing requirements such as starting and finishing date of the programme must be rigidly met

bull The method must be strictly adhered to bull Samples must be handled in accordance with instructions bull A qualified operator must perform the measurements

Having studied the method and having made a fair appraisal of our capabilities and facilities we feel that we will be adequately prepared for cooperative testing of this method Comments helliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphellip Signature Date

17

Annex 2

Report on the validation materials used

VI

Abstract This report gives an overview on the available analytical information on the following raw materials to be used for the production of validation materials of the so-called Project HORIZONTAL

bull Four sludge materials from Duumlsseldorf Germany

bull An agricultural soil material from Reading United Kingdom

bull A compost material from Vienna Austria

bull A compost material from Korschenbroich Germany

bull A sludge-amended agricultural soil from Pavia Province Italy

bull A sludge-amended soil from Barcelona Spain

bull A sludge-amended soil from Essen Germany

bull A long-term sludge exposed soil from Hohenheim Germany

VII

List of Abbreviations Throughout this report the following abbreviations are used

AOX absorbable organic halogens

Corg organic carbon content

Ctotal total carbon content

CAT cation exchangeable

CDD chlorinated dibenzodioxin

CDF chlorinated dibenzofuran

DEHP di(2-ethylhexyl)phthalate

DM dry matter

EPA Environment Protection Agency

EU European Union

FM fresh matter

Hp hepta

Hx hexa

IES Institute for Environment and Sustainability

IRMM Institute for Reference Materials and Measurements

JRC Joint Research Centre

LAS linear alkylsulfonates

LoD limit of detection

LUA Landesumweltamt

Ntotal total nitrogen content

NH4-N Ammonium nitrogen

NO3-N Nitrate nitrogen

NP nonylphenol

NRW North Rhine Westphalia

O octa

P poly

PAH polycyclic aromatic hydrocarbon

PCB polychlorinated biphenyl

Pe penta

T tetra

TEQ toxicity equivalent

UBA Umweltbundesamt

WHO World Health Organization

WWTP waste water treatment plant

6

1 Introduction This report gives an overview on the available analytical information on the following raw materials to be used for the production of validation materials of the so-called Project HORIZONTAL

bull Four sludge materials from Duumlsseldorf Germany

bull An agricultural soil material from Reading United Kingdom

bull A compost material from Vienna Austria

bull A compost material from Korschenbroich Germany

bull A sludge-amended agricultural soil from Pavia Province Italy

bull A sludge-amended soil from Barcelona Spain

bull A sludge-amended soil from Essen Germany

bull A long-term sludge exposed soil from Hohenheim Germany

The following analytical information was gathered partly before and during the sampling of the raw materials to be used for the production of the HORIZONTAL validation materials The material were sampled by IES and shipped to IRMM in the course of the year 2005 The information gathered was then completed by various analytical screenings for PAHs and PCBs done by the Institute for Reference Materials and Measurements Geel Belgium for phthalates done by UBA Berlin Germany for PBDE done by IIQAB-CSIC Barcelona Spain for trace elements and some selected major and minor elements by the Institute for Environment and Sustainability Ispra Italy

The work compiled hereafter is based on the numerous additional efforts of the scientists working at various members of the consortium Project HORIZONTAL-Org and contributing organisations

This work is gratefully acknowledged

2 Overview on property values

21 Sludge materials from Duumlsseldorf Germany

The various sewage sludge materials originate from various installations in the North Rhine Westphalia and were produced and sampled by staff from the Landesumweltamt (LUA) NRW under the responsibility from Dr K Furtmann

In total four sludge materials (Sludge A and D from a major municipal WWTP Sludge B from a municipal WWTP with industrial input and Sludge C from a municipal WWTP with high PCB-Content) were obtained and will be blended to two final materials Before sampling the following analytical data for a typical sample were received

7

Table 1 ndash Analytical data obtained on an average sludge sample in LUA NRW (with courtesy of K Furtmann LUA Duumlsseldorf)

Parameter Concentration PCB 120 ugkg DEHP 110 mgkg PAH 5 mgkg (EPA) PCDDF 15 ng TEkg PBDE 400 ugkg NP 40 mgkg LAS 3 gkg AOX 300 mgkg

Subsequent screening led to the information displayed hereafter It should be stressed that the data were obtained as SCREENING information on the UNTREATED or partially treated raw materials Therefore the final target values which are relevant for the validation intercomparison can be different

Table 2 ndash Analytical data obtained on a first screening on the sludge samples from LUA NRW

Sewage sludge A

Dusseldorf

sewage sludge D

Dusseldorf PCB (ngg) 28 62 35 52 101 65 101 31 38 118 49 40 153 30 33 105 24 11 138 46 38 156 lt1 lt1 180 34 23 170 23 19 PAH (ngg) Naphtalene 34 381 Acenaphtylene 15 43 Acenaphthene 81 108 Fluorene 94 1167 Phenantrene 3440 Anthracene 22 344 Flouranthene 316 4817 Pyrene 235 3011 Benz(a)anthracene 473 791 Chrysene 691 1078 Benz(b)fluoranthene 538 1688 Benz(k)fluoranthene 228 635 Benz(a)pyrene 383 1114 Indeno(123-cd)pyrene 92 229 Dibenzo(ah)anthracene 71 70 Benzo(ghi)perylene 80 185

8

Table 3 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Sludge D (1) 0135 41474 385 Sludge B (2) 0538 0034 30634 547 Sludge A (3) 0184 0037 31399 146 Sludge C (4) 0354 1528 6678 229

Table 4 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Sludge 2

(B)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

554

959

694

591

772

509

nq

nq

970

2216

2379

Table 5 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena IES Ispra Spain) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Sludge 1 (D) 265 290 533 359 1231 338 784 438 lt 005 232 786 Sludge 2 (B) 119 311 626 202 278 299 722 251 lt 005 118 625 Sludge 3 (A) 168 360 621 332 847 416 119 451 lt 005 116 1237 Sludge 4 (C) 563 198 116 273 726 511 473 618 lt 005 444 2015

Table 6 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Sludge 1 (D) 2154 58 844 099 103 101 4367 lt15 50448 Sludge 2 (B) 1067 366 692 046 1491 077 5217 lt15 57633 Sludge 3 (A) 731 663 684 035 1287 068 3733 lt15 60369 Sludge 4 (C) 4379 965 527 163 522 107 5628 lt15 23945

Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM)Sludge 1 (D) 03 2403 101 1002 350 15 1944 132Sludge 2 (B) 031 315 97 879 172 12 514 180Sludge 3 (A) 031 1281 153 1567 265 16 1440 168Sludge 4 (C) 055 231 628 2625 371 81 1101 244

9

22 Agricultural soil material from Reading United Kingdom

The material was proposed by the University of Reading (S Nortcliff) and was sampled from a site called ldquoFrogmore Farmrdquo which was featured in the ldquoMetalsrdquo Report for HORIZONTAL This site is close to Reading with soils developed on flintyloamy periglacial materials over Chalk has a long and well documented history of sludge application The focus of the work of Nortcliff et al undertook at this site and the monitoring and control at the site (by Thames Water and the subsequent subsidiary bodies dealing with sludge application to soil) was on metals (and metal loads) with no analysis or indeed any form of investigation in to organics in the broadest sense

The analytical information produced in the context of the screening of the raw material is displayed below

Table 7 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 3

(Reading) 0032 0119 669

Table 8 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 3 (Reading) 015 706 279 138 152 901 267 300 lt 005 258 931

Table 9 ndash Analytical data obtained on a first screening on the sludge-amended soil from Reading (courtesy of IRMM)

Parameter Concentration

PCB ngg 28 lt1 52 lt1 101 lt1 118 lt1 153 lt1 105 lt1 138 lt1 156 lt1 180 lt1 170 lt1 PAH ngg Naphtalene lt10 Acenaphtylene 21 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene lt10 Flouranthene 818 Pyrene 776 Benz(a)anthracene 565

10

Parameter Concentration

Chrysene 608 Benz(b)fluoranthene 824 Benz(k)fluoranthene 329 Benz(a)pyrene 799 Indeno(123-cd)pyrene

779

Dibenzo(ah)anthracene 118 Benzo(ghi)perylene 394

Table 10 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 3

(Reading)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

103

003

nq

nq

nq

nd

nd

272

273

Table 11 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 3 (Reading) 015 706 279 138 152 901 267 300 lt 005 258 931

Table 12 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 3 (Reading) 7936 477 112 096 194 017 4107 443 2102 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 3 (Reading) 042 13 45 69 69 69 216 92

Table 13 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 3 (Reading) 012

11

23 Compost from Vienna Austria

The fresh compost material was obtained from the Austrian Federal Environment Agency (UBA Vienna) which had used a sub-batch of the raw material for national intercomparson The remainder of the material was stored at 4degC until shipment to IRMM for further processing The following analytical information was provided by UBA Austria and completed with various screenings

Table 14 ndash Analytical data on compost material received from UBA Austria Inorganic and sum parameters

Parameter Unit Sample fraction used Observed mean B CAT mgl FM Fresh sample lt10mm 61 K CAT mgl FM Fresh sample lt10mm 2624 Mg CAT mgl FM Fresh sample lt10mm 242 P CAT mgl FM Fresh sample lt10mm 49 B CAT DM Fresh sample lt10mm 00017 K CAT DM Fresh sample lt10mm 072 Mg CAT DM Fresh sample lt10mm 007 P CAT DM Fresh sample lt10mm 001 NO3-N mgkg FM Fresh sample lt10mm 35 NH4-N mgkg FM Fresh sample lt10mm 230 Ctotal DM lt45degdry milled 29 Corg DM lt45degdry milled 27 Ntotal DM lt45degdry milled 17 P mgkg DM lt45degdry milled 2596 K mgkg DM lt45degdry milled 11019 K DM lt45degdry milled 110 B mgkg DM lt45degdry milled 60 Cd mgkg DM lt45degdry milled 046 Cr mgkg DM lt45degdry milled 25 Cu mgkg DM lt45degdry milled 46 Hg mgkg DM lt45degdry milled 020 Ni mgkg DM lt45degdry milled 18 Pb mgkg DM lt45degdry milled 45 Zn mgkg DM lt45degdry milled 198 Ca mgkg DM lt45degdry milled 68776 Ca DM lt45degdry milled 69 Mo mgkg DM lt45degdry milled 08 S mgkg DM lt45degdry milled 2137 Fe mgkg DM lt45degdry milled 9959 Mn mgkg DM lt45degdry milled 418 Na mgkg DM lt45degdry milled 742 Co mgkg DM lt45degdry milled 41 AOX mgkg DM lt30deg dry milled 62

Table 15 ndash Analytical data on compost material received from UBA Austria Polycyclic aromatic hydrocarbons

PAH Unit Result Naphthaline microgkg DM 93 Acenaphthylene microgkg DM 86 Acenaphthene microgkg DM 5 Fluorene microgkg DM 80 Phenanthrene microgkg DM 89 Anthracene microgkg DM 27 Fluoranthene microgkg DM 487 Pyrene microgkg DM 380

12

PAH Unit Result Benzo(a)anthracene microgkg DM 278 Chrysene microgkg DM 317 Benzo(b)fluoranthene microgkg DM 365 Benzo(k)fluoranthene microgkg DM 193 Benz(a)pyrene microgkg DM 320 Indeno(123-cd)pyrene microgkg DM 233 Dibenz(ah)anthracene microgkg DM 67 Benzo(ghi)perylene microgkg DM 225 Sum EPA microgkg DM 3013 Sum EPA mgkg DM 30

Table 16 ndash Analytical data on compost material received from UBA Austria Sum PCDDs and PCBs

Parameter

Dioxine TEQ (ITEF) ngkg DM 73 TEQ (WHO) ngkg DM 35 PCB Σ Ballschmiter mgkg DM 005

Table 17 ndash Analytical data on compost material obtained by screening in IRMM

Parameter Result in ngg

PCB 28 2 52 2 101 4 118 3 153 10 105 1 138 8 156 1 180 5 170 lt1 PAH Naphtalene lt10 Acenaphtylene lt10 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene 26 Fluoranthene 611 Pyrene 510 Benz(a)anthracene 888 Chrysene 957 Benz(b)fluoranthene 1531 Benz(k)fluoranthene 547 Benz(a)pyrene 1101 Indeno(123-cd)pyrene 416 Dibenzo(ah)anthracene 81 Benzo(ghi)perylene 295

13

Table 18 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Compost 1

(Vienna)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

402

019

259

nq

023

004

nq

nq

144

174

259

Table 19 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Compost 1

(Vienna) 0058 1426 557

Table 20 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Compost 1 (Vienna) 039 736 319 410 365 127 495 004 079 013 208

Table 21 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Compost 1 (Vienna) 2063 431 617 426 199 249 1602 lt15 10521

Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Compost 1 (Vienna) 035 3496 81 375 79 55 653 60

Table 22 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Compost 1 (Vienna) 017

14

24 Agricultural soil sludge amended soil from Pavia Italy

This sludge-amended soil material was obtained during a monitoring campaign which aimed at a generic description of the over-all soil quality in Pavia Province Italy The material which was collected from the upper horizon originates from a small farm called ldquoCascina Novellordquo During the characterisation of the site the following analytical information was obtained on a pooled sample of a sub-area of the farm of 20 X 20 m2

Table 23 ndash Analytical data on Pavia soil

Parameter Result Al 713 Wgt As 224 mgkg Cd 079 mgkg Cr 59 mgkg Cu 308 mgkg Hg 008 mgkg Ni 344 mgkg Pb 246 mgkg Zn 95 mgkg C 091 Wgt 2378-TCDD 0047 pgg 12378-PeCDD 015 pgg 123478-HxCDD 019 pgg 123678-HxCDD 15 pgg 123789-HxCDD 074 pgg 1234678-HpCDD 26 pgg OCDD 382 pgg 2378-TCDF 068 pgg 12378-PeCDF 053 pgg 23478-PeCDF 071 pgg 123478-HxDF 100 pgg 123678-HxDF 066 pgg 234678-HxDF 16 pgg 123789-HxDF 027 pgg 1234678-HpDF 12 pgg 1234789-HpDF 068 pgg OCDF 33 pgg I-TEQ 20 pgg WHO-TEQ 17 pgg

In addition the screening performed at IRMM did not reveal significant quantities of PCBs and PAHs which were all below the LoDs (1 ngg for PCBs and 10 ngg for PAHs respectively)

Table 24 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 5 (Pavia) 0005 0011 154

15

Table 25 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 5

(Pavia)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

039

nq

nq

008

nq

nd

nd

670

671

Table 26 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 5 (Pavia) 033 184 573 225 426 305 206 200 lt 005 381 878

Table 27 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 5 (Pavia) 6939 129 145 224 425 116 6118 255 1789 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 5 (Pavia) 184 62 38 108 55 66 597 110

Table 28 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 5 (Pavia) 006

16

25 Sludge-amended-soil from Barcelona Spain

The sludge-amended soil material from Barcelona sampled upon indication from the Barcelorsquo- Group in Barcelona

Table 29 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 2 (Lleida T) 0015 0183 1138

Table 30 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 2

(Lleida T)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

159

045

nq

048

160

nq

nq

1000

1004

Table 31 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 2 (Lleida T) 059 141 327 536 405 186 184 224 lt 005 318 111

Table 32 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 2 (Lleida T) 4443 1067 1429 253 344 204 4116 780 3396 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 2 (Lleida T) 064 65 26 125 59 17 547 65

Table 33 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 2 (Lleida T) 010

17

26 Sludge amended soil from Essen Germany

The German sludge-amended soil from Essen which was provided as the three sludge materials by LUA NRW did not feature significant concentrations of the PCB congeners 28 52 101 118 153 105 138 156 180 170 but had detectable amounts of some PAHs

Table 34 ndash Analytical screening data on the German sludge-amended soil

Parameter Concentration(ngg)

Naphtalene lt10 Acenaphtylene lt10 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene lt10 Fluoranthene 28 Pyrene 20 Benz(a)anthracene 24 Chrysene 47 Benz(b)fluoranthene 76 Benz(k)fluoranthene 20 Benz(a)pyrene 35 Indeno(123-cd)pyrene 35 Dibenzo(ah)anthracene 10 Benzo(ghi)perylene 26

Table 35 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 4 (Essen) 0011 0302 055

Table 36 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 4

(Essen)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

nq

nq

nq

nq

nq

nq

128

191

203

18

Table 37 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 4 (Essen) 052 545 261 805 320 403 273 273 lt 005 295 781

Table 38 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 4 (Essen) 7947 442 085 06 086 007 2163 189 2019 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 4 (Essen) 045 19 42 87 683 60 462 61

Table 39 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 4 (Essen) 004

27 Long-term sludge exposed soil from Hohenheim-Stuttgart Germany

Similarly an additional sludge exposed soil was sampled at the University of Hohenheim Stuttgart were a test soil was long-term exposed to elevated concentrations of sewage sludge

Table 40 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 1 (Stuttgart) 0045 0263 1765

Table 41 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 1

(Stuttgart)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

230

006

004

004

nq

nd

nd

498

500

19

Table 42 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 1 (Stuttgart) 069 127 361 262 504 183 252 262 lt 005 266 142

Table 43 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 1 (Stuttgart) 7194 1006 133 186 366 088 7874 275 3571 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 1 (Stuttgart) 123 50 47 212 85 69 991 129

Table 44 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 1 (Stuttgart) 177

18

Annex 3

Statistical calculations

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 47)Mandels h statistics(Sludge 1 - PBD 47)

Sample Sludge 1 NUM

Element PBD 47

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00213 0001 3 -021 005 - - 10L - - NUM46L 00273 0002 4 016 021 - - 46L - - NUM64L 00059 0000 4 -116 002 NUM - 64L - - NUM12L 00188 0000 4 -036 002 - - 12L - - NUM26L 00499 0024 2 157 223 Fail - - 26L - - NUM

Totgem 0025 0005 mgkg 1-level 172 (185) NUM (10L46L64L12L26L) -1Totstd= 0016 0010 5-level 157 (162) 5

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 5 Labs rejected (10L46L64L12L26L)

000 050 100 150 200 250

k-values

10L

46L

64L

12L

26L

Mandels k statistics(Sludge 1 - PBD 47)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

10L

46L

64L

12L

26L

Labo

rato

ries

NUM

-200 -100 000 100 200

h-values

10L

46L

64L

12L

26L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 47)

Sludge 1-PBD 47

Unit mgkg

Mandels k statistics(Soil 3 - PBD 47)Mandels h statistics(Soil 3 - PBD 47)

Sample Soil 3 Soil 3 - PBD 47 -- Mean PARM = 0001 [mgkg]

Element PBD 47

General calcparmT1= 134814E-02T2= 142830E-05T3= 13T4= 45T5= 22767E-06

n= variabelp= 4

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean26L 00007 0000 2 -143 001 00007 00000 2 1 00046L 00010 0001 4 010 181 00010 00008 4 3 00010L 00011 0000 3 049 023 00011 00001 3 2 00012L 00012 0000 4 084 081 00012 00004 4 3 000

Totgem 0001 0000 mgkg 1-level 149 (177) 4 00010 () 4 3Totstd= 0000 0000 5-level 142 (159)

RESULTS Mean = 000100 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000050 --gt 5031 r = 00014Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000050 --gt 5031 R = 00014Remarks none

000 050 100 150 200

k-values

26L

46L

10L

12L

Mandels k statistics(Soil 3 - PBD 47)

00 00 00 00 00 00 00 00 00 00 00

Deviation from Mean

26L

46L

10L

12L

Labo

rato

ries

Soil 3 - PBD 47 -- Mean PARM = 0001 [mgkg]

-200 -100 000 100

h-values

26L

46L

10L

12L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 47)

Soil 3-PBD 47

Unit mgkg

Mandels k statistics(Compost 1 - PBD 99)Mandels h statistics(Compost 1 - PBD 99)

Sample Compost 1 Compost 1 - PBD 99 -- Mean PARM = 0003 [mgkg]

Element PBD 99

General calcparmT1= 492124E-02T2= 148747E-04T3= 17T4= 61T5= 93196E-06

n= variabelp= 5

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00020 0000 4 -137 053 00020 00004 4 3 000

26L 00025 0000 2 -058 024 00025 00002 2 1 00010L 00029 0000 3 012 032 00029 00003 3 2 00046L 00033 0001 4 069 161 00033 00013 4 3 00012L 00036 0001 4 114 140 00036 00011 4 3 000

Totgem 0003 0001 mgkg 1-level 172 (185) 5 00029 () 5 4Totstd= 0001 0001 5-level 157 (162)

RESULTS Mean = 000286 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000088 --gt 3086 r = 00025Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000101 --gt 3525 R = 00028Remarks none

000 050 100 150 200

k-values

4L

26L

10L

46L

12L

Mandels k statistics(Compost 1 - PBD 99)

00 00 00 00 00 00 00 00 00 00

Deviation from Mean

4L

26L

10L

46L

12L

Labo

rato

ries

Compost 1 - PBD 99 -- Mean PARM = 0003 [mgkg]

-200 -100 000 100 200

h-values

4L

26L

10L

46L

12L

Labo

rato

ries

Mandels h statistics(Compost 1 - PBD 99)

Compost 1-PBD 99

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 99)Mandels h statistics(Sludge 1 - PBD 99)

Sample Sludge 1 Sludge 1 - PBD 99 -- Mean PARM = 0024 [mgkg]

Element PBD 99

General calcparmT1= 448050E-01T2= 112113E-02T3= 19T4= 73T5= 32972E-05

n= variabelp= 5

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean64L 00173 0002 4 -118 041 Fail 00173 00019 4 3 -0014L 00183 0002 4 -104 032 00183 00015 4 3 -001

12L 00227 0001 4 -038 022 00227 00010 4 3 00010L 00290 0001 3 055 021 00290 00010 3 2 00146L 00320 0002 4 100 039 00320 00018 4 3 00126L 00323 0011 2 105 234 - - 26L - - 001

Totgem 0025 0003 mgkg 1-level 187 (177) 5 00239 (26L) 5 4Totstd= 0007 0004 5-level 166 (154) 1

RESULTS Mean = 002385 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000153 --gt 643 r = 00043Between lab variance S2L = 000004Reproducibility var S2R = 000004Reproducibility std SR = 000666 --gt 2791 R = 00186Remarks 1 Lab rejected (26L)

000 050 100 150 200 250

k-values

64L

4L

12L

10L

46L

26L

Mandels k statistics(Sludge 1 - PBD 99)

00 00 00 00 00 00 00 00 00 00

Deviation from Mean

64L

4L

12L

10L

46L

26L

Labo

rato

ries

Sludge 1 - PBD 99 -- Mean PARM = 0024 [mgkg]

-200 -100 000 100 200

h-values

64L

4L

12L

10L

46L

26L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 99)

Sludge 1-PBD 99

Unit mgkg

Mandels k statistics(Soil 3 - PBD 99)Mandels h statistics(Soil 3 - PBD 99)

Sample Soil 3 NUM

Element PBD 99

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00017 0000 4 091 068 - - 10L - - NUM46L 00017 0001 4 100 211 - - 46L - - NUM64L 00005 0000 4 -106 023 NUM - 64L - - NUM12L 00012 0000 4 015 014 - - 12L - - NUM26L 00006 0000 2 -101 012 - - 26L - - NUM

Totgem 0001 0000 mgkg 1-level 172 (173) NUM (10L46L64L12L26L) -1Totstd= 0001 0000 5-level 157 (153) 5

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 5 Labs rejected (10L46L64L12L26L)

000 050 100 150 200 250

k-values

10L

46L

64L

12L

26L

Mandels k statistics(Soil 3 - PBD 99)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

10L

46L

64L

12L

26L

Labo

rato

ries

NUM

-200 -100 000 100 200

h-values

10L

46L

64L

12L

26L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 99)

Soil 3-PBD 99

Unit mgkg

Mandels k statistics(Compost 1 - PBD 100)Mandels h statistics(Compost 1 - PBD 100)

Sample Compost 1 Compost 1 - PBD 100 -- Mean PARM = 0001 [mgkg]

Element PBD 100

General calcparmT1= 124272E-02T2= 113129E-05T3= 14T4= 52T5= 46584E-07

n= variabelp= 4

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean26L 00006 0000 2 -131 037 Fail 00006 00001 2 1 00010L 00009 0000 4 003 083 00009 00002 4 3 00046L 00009 0000 4 016 115 00009 00002 4 3 00012L 00011 0000 4 112 136 Fail 00011 00003 4 3 000

Totgem 0001 0000 mgkg 1-level 149 (167) 4 00009 () 4 3Totstd= 0000 0000 5-level 142 (15)

RESULTS Mean = 000085 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000022 --gt 2531 r = 00006Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000025 --gt 2882 R = 00007Remarks none

000 050 100 150

k-values

26L

10L

46L

12L

Mandels k statistics(Compost 1 - PBD 100)

00 00 00 00 00 00 00 00 00 00 00

Deviation from Mean

26L

10L

46L

12L

Labo

rato

ries

Compost 1 - PBD 100 -- Mean PARM = 0001 [mgkg]

-200 -100 000 100 200

h-values

26L

10L

46L

12L

Labo

rato

ries

Mandels h statistics(Compost 1 - PBD 100)

Compost 1-PBD 100

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 100)Mandels h statistics(Sludge 1 - PBD 100)

Sample Sludge 1 Sludge 1 - PBD 100 -- Mean PARM = 0005 [mgkg]

Element PBD 100

General calcparmT1= 852065E-02T2= 412762E-04T3= 18T4= 68T5= 78914E-07

n= variabelp= 5

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00039 0000 4 -042 007 Fail 00039 00002 4 3 000

12L 00044 0000 4 -041 005 Fail 00044 00001 4 3 00010L 00046 0000 4 -041 013 Fail 00046 00003 4 3 00046L 00056 0000 4 -040 012 Fail 00056 00003 4 3 00026L 00059 0000 2 -040 013 Fail 00059 00003 2 1 00038L 02168 0006 4 204 244 Fail - - 38L - - 021

Totgem 0040 0001 mgkg 1-level 187 (177) 5 00049 (38L) 5 4Totstd= 0087 0002 5-level 166 (154) 1

RESULTS Mean = 000486 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000025 --gt 507 r = 00007Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000084 --gt 1731 R = 00024Remarks 1 Lab rejected (38L)

000 050 100 150 200 250

k-values

4L

12L

10L

46L

26L

38L

Mandels k statistics(Sludge 1 - PBD 100)

-01 00 01 01 02 02 03

Deviation from Mean

4L

12L

10L

46L

26L

38L

Labo

rato

ries

Sludge 1 - PBD 100 -- Mean PARM = 0005 [mgkg]

-100 000 100 200 300

h-values

4L

12L

10L

46L

26L

38L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 100)

Sludge 1-PBD 100

Unit mgkg

Mandels k statistics(Soil 3 - PBD 100)Mandels h statistics(Soil 3 - PBD 100)

Sample Soil 3 NUM

Element PBD 100

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00003 0000 4 -050 000 Fail - - 10L - - NUM46L 00003 0000 4 -050 000 Fail NUM - 46L - - NUM3L 305500 2051 2 150 200 Fail - - 3L - - NUM

26L 00005 0000 2 -050 000 Fail - - 26L - - NUM

Totgem 7638 0513 mgkg 1-level 149 (177) NUM (10L46L3L26L) -1Totstd= 15275 1025 5-level 142 (159) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (10L46L3L26L)

000 050 100 150 200

k-values

10L

46L

3L

26L

Mandels k statistics(Soil 3 - PBD 100)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

10L

46L

3L

26L

Labo

rato

ries

NUM

-100 000 100 200

h-values

10L

46L

3L

26L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 100)

Soil 3-PBD 100

Unit mgkg

Mandels k statistics(Compost 1 - PBD 153)Mandels h statistics(Compost 1 - PBD 153)

Sample Compost 1 NUM

Element PBD 153

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean44L 00053 0001 3 150 157 Fail - - 44L - - NUM46L 00007 0000 4 -044 111 Fail - - 46L - - NUM12L 00005 0000 4 -051 055 Fail - - 12L - - NUM26L 00005 0000 2 -054 001 Fail NUM - 26L - - NUM

Totgem 0002 0000 mgkg 1-level 149 (177) NUM (44L46L12L26L) -1Totstd= 0002 0000 5-level 142 (159) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (44L46L12L26L)

000 050 100 150 200

k-values

44L

46L

12L

26L

Mandels k statistics(Compost 1 - PBD 153)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

44L

46L

12L

26L

Labo

rato

ries

NUM

-100 000 100 200

h-values

44L

46L

12L

26L

Labo

rato

ries

Mandels h statistics(Compost 1 - PBD 153)

Compost 1-PBD 153

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 153)Mandels h statistics(Sludge 1 - PBD 153)

Sample Sludge 1 Sludge 1 - PBD 153 -- Mean PARM = 0004 [mgkg]

Element PBD 153

General calcparmT1= 676738E-02T2= 267609E-04T3= 18T4= 68T5= 19626E-05

n= variabelp= 5

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00024 0000 4 -157 017 00024 00002 4 3 000

12L 00038 0002 4 006 154 00038 00018 4 3 00046L 00039 0000 4 011 026 00039 00003 4 3 00026L 00039 0000 2 018 004 00039 00000 2 1 00064L 00049 0002 4 122 159 00049 00018 4 3 000

Totgem 0004 0001 mgkg 1-level 172 (173) 5 00038 () 5 4Totstd= 0001 0001 5-level 157 (153)

RESULTS Mean = 000378 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000123 --gt 3252 r = 00034Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000142 --gt 3754 R = 00040Remarks none

000 050 100 150 200

k-values

4L

12L

46L

26L

64L

Mandels k statistics(Sludge 1 - PBD 153)

00 00 00 00 00 00 00

Deviation from Mean

4L

12L

46L

26L

64L

Labo

rato

ries

Sludge 1 - PBD 153 -- Mean PARM = 0004 [mgkg]

-200 -100 000 100 200

h-values

4L

12L

46L

26L

64L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 153)

Sludge 1-PBD 153

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 154)Mandels h statistics(Sludge 1 - PBD 154)

Sample Sludge 1 NA

Element PBD 154

General calcparmT1= NAT2= NAT3=T4=T5=

n= variabelp=

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00021 0000 3 -100 021 NA - 4L - - NA

46L 00025 0000 4 115 018 NA - 46L - - NA64L 00021 0001 4 -066 179 - - 64L - - NA12L 00023 0000 4 050 085 - - 12L - - NA

Totgem 0002 0000 mgkg 1-level 149 (167) NA (4L46L64L12L) -1Totstd= 0000 0000 5-level 142 (15) 4

RESULTS Mean = NA mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NAReproducibility var S2R = NAReproducibility std SR = NA --gt NA R = NARemarks 4 Labs rejected (4L46L64L12L)

000 050 100 150 200

k-values

4L

46L

64L

12L

Mandels k statistics(Sludge 1 - PBD 154)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

4L

46L

64L

12L

Labo

rato

ries

NA

-100 000 100 200

h-values

4L

46L

64L

12L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 154)

Sludge 1-PBD 154

Unit mgkg

Mandels k statistics(Soil 3 - PBD 154)Mandels h statistics(Soil 3 - PBD 154)

Sample Soil 3 NUM

Element PBD 154

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

4L 00010 - 1 150 Fail - - 4L - - NUM46L 00001 0000 4 -053 096 Fail - - 46L - - NUM64L 00001 0000 4 -056 105 Fail NUM - 64L - - NUM12L 00002 0000 4 -040 099 Fail - - 12L - - NUM

Totgem 000037 0000 mgkg 1-level 149 (164) NUM (4L46L64L12L) -1Totstd= 000042 0000 5-level 142 (153) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (4L46L64L12L)

000 050 100 150

k-values

4L

46L

64L

12L

Mandels k statistics(Soil 3 - PBD 154)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

4L

46L

64L

12L

Labo

rato

ries

NUM

-100 000 100 200

h-values

4L

46L

64L

12L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 154)

Soil 3-PBD 154

Unit mgkg

Mandels k statistics(Compost 1 - PBD 209)Mandels h statistics(Compost 1 - PBD 209)

Sample Compost 1 NUM

Element PBD 209

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00065 0003 2 -049 032 - - 4L - - NUM

44L 00573 0021 4 150 197 Fail - - 44L - - NUM12L 00078 0001 4 -045 011 - - 12L - - NUM26L 00049 0000 2 -056 000 NUM - 26L - - NUM

Totgem 0019 0006 mgkg 1-level 149 (177) NUM (4L44L12L26L) -1Totstd= 0025 0010 5-level 142 (159) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (4L44L12L26L)

000 050 100 150 200

k-values

4L

44L

12L

26L

Mandels k statistics(Compost 1 - PBD 209)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

4L

44L

12L

26L

Labo

rato

ries

NUM

-100 000 100 200

h-values

4L

44L

12L

26L

Labo

rato

ries

Mandels h statistics(Compost 1 - PBD 209)

Compost 1-PBD 209

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 209)Mandels h statistics(Sludge 1 - PBD 209)

Sample Sludge 1 Sludge 1 - PBD 209 -- Mean PARM = 0249 [mgkg]

Element PBD 209

General calcparmT1= 394542E+00T2= 107296E+00T3= 16T4= 56T5= 19723E-02

n= variabelp= 5

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 01550 0055 4 -112 148 Fail 01550 00551 4 3 -009

46L 02050 0007 2 -053 019 02050 00071 2 1 -00412L 02137 0058 4 -042 155 02137 00576 4 3 -00426L 03149 0021 2 078 057 Fail 03149 00210 2 1 00764L 03577 0007 4 129 020 Fail 03577 00074 4 3 011

Totgem 0249 0030 mgkg 1-level 172 (185) 5 02493 () 5 4Totstd= 0084 0025 5-level 157 (162)

RESULTS Mean = 024926 mgkg

Repeatability variance S2r = 000179Repeatability std Sr = 004234 --gt 1699 r = 01186Between lab variance S2L = 000743Reproducibility var S2R = 000922Reproducibility std SR = 009604 --gt 3853 R = 02689Remarks none

000 050 100 150 200

k-values

4L

46L

12L

26L

64L

Mandels k statistics(Sludge 1 - PBD 209)

-01 -01 00 01 01 02

Deviation from Mean

4L

46L

12L

26L

64L

Labo

rato

ries

Sludge 1 - PBD 209 -- Mean PARM = 0249 [mgkg]

-200 -100 000 100 200

h-values

4L

46L

12L

26L

64L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 209)

Sludge 1-PBD 209

Unit mgkg

Mandels k statistics(Soil 3 - PBD 209)Mandels h statistics(Soil 3 - PBD 209)

Sample Soil 3 Soil 3 - PBD 209 -- Mean PARM = 0258 [mgkg]

Element PBD 209

General calcparmT1= 596398E+00T2= 191917E+00T3= 22T4= 84T5= 13249E-02

n= variabelp= 6

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean26L 01162 0021 2 -108 074 Fail 01162 00207 2 1 -0144L 01303 0031 4 -097 111 Fail 01303 00312 4 3 -013

46L 01975 0036 4 -046 128 Fail 01975 00359 4 3 -00644L 02898 0035 4 024 124 Fail 02898 00346 4 3 00312L 03895 0018 4 100 065 Fail 03895 00181 4 3 01364L 04260 0022 4 127 078 Fail 04260 00219 4 3 017

Totgem 0258 0027 mgkg 1-level 187 (177) 6 02582 () 6 5Totstd= 0132 0008 5-level 166 (154)

RESULTS Mean = 025818 mgkg

Repeatability variance S2r = 000083Repeatability std Sr = 002878 --gt 1115 r = 00806Between lab variance S2L = 001640Reproducibility var S2R = 001723Reproducibility std SR = 013127 --gt 5084 R = 03676Remarks none

000 050 100 150

k-values

26L

4L

46L

44L

12L

64L

Mandels k statistics(Soil 3 - PBD 209)

-02 -01 -01 00 01 01 02 02

Deviation from Mean

26L

4L

46L

44L

12L

64L

Labo

rato

ries

Soil 3 - PBD 209 -- Mean PARM = 0258 [mgkg]

-200 -100 000 100 200

h-values

26L

4L

46L

44L

12L

64L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 209)

Soil 3-PBD 209

Unit mgkg

Mandels k statistics(Compost 1 - Sum PBD)Mandels h statistics(Compost 1 - Sum PBD)

Sample Compost 1 Compost 1 - Sum PBD -- Mean PARM = 0009 [mgkg]

Element Sum PBD

General calcparmT1= 154064E-01T2= 169065E-03T3= 18T4= 68T5= 11354E-04

n= variabelp= 5

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00031 0002 4 -067 016 00031 00016 4 3 -0014L 00055 0005 4 -056 048 00055 00047 4 3 000

46L 00085 0003 4 -042 031 00085 00030 4 3 00026L 00123 0000 2 -024 003 00123 00002 2 1 00012L 00154 0002 4 -011 021 00154 00021 4 3 00144L 00613 0023 4 200 237 Fail - - 44L - - 005

Totgem 0018 0006 mgkg 1-level 187 (177) 5 00089 (44L) 5 4Totstd= 0022 0009 5-level 166 (154) 1

RESULTS Mean = 000893 mgkg

Repeatability variance S2r = 000001Repeatability std Sr = 000296 --gt 3308 r = 00083Between lab variance S2L = 000002Reproducibility var S2R = 000003Reproducibility std SR = 000570 --gt 6374 R = 00159Remarks 1 Lab rejected (44L)

000 050 100 150 200 250

k-values

10L

4L

46L

26L

12L

44L

Mandels k statistics(Compost 1 - Sum PBD)

00 00 00 00 00 00 01 01

Deviation from Mean

10L

4L

46L

26L

12L

44L

Labo

rato

ries

Compost 1 - Sum PBD -- Mean PARM = 0009 [mgkg]

-100 000 100 200

h-values

10L

4L

46L

26L

12L

44L

Labo

rato

ries

Mandels h statistics(Compost 1 - Sum PBD)

Compost 1-Sum PBD

Unit mgkg

Mandels k statistics(Sludge 1 - Sum PBD)Mandels h statistics(Sludge 1 - Sum PBD)

Sample Sludge 1 Sludge 1 - Sum PBD -- Mean PARM = 0256 [mgkg]

Element Sum PBD

General calcparmT1= 531806E+00T2= 162188E+00T3= 22T4= 84T5= 25223E-02

n= variabelp= 6

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00423 0025 4 -156 044 Fail 00423 00252 4 3 -02146L 01808 0118 4 -049 205 - - 46L - - -0074L 01810 0056 4 -049 097 01810 00558 4 3 -007

38L 02168 0006 4 -022 010 02168 00059 4 3 -00412L 02890 0065 4 034 113 02890 00647 4 3 00364L 03958 0008 4 116 014 Fail 03958 00079 4 3 01426L 04094 0034 2 126 059 Fail 04094 00337 2 1 015

Totgem 0245 0044 mgkg 1-level 198 (179) 6 02557 (46L) 6 5Totstd= 0130 0039 5-level 171 (155) 1

RESULTS Mean = 025570 mgkg

Repeatability variance S2r = 000158Repeatability std Sr = 003970 --gt 1553 r = 01112Between lab variance S2L = 001807Reproducibility var S2R = 001964Reproducibility std SR = 014015 --gt 5481 R = 03924Remarks 1 Lab rejected (46L)

000 050 100 150 200 250

k-values

10L

46L

4L

38L

12L

64L

26L

Mandels k statistics(Sludge 1 - Sum PBD)

-03 -02 -02 -01 -01 00 01 01 02 02

Deviation from Mean

10L

46L

4L

38L

12L

64L

26L

Labo

rato

ries

Sludge 1 - Sum PBD -- Mean PARM = 0256 [mgkg]

-200 -100 000 100 200

h-values

10L

46L

4L

38L

12L

64L

26L

Labo

rato

ries

Mandels h statistics(Sludge 1 - Sum PBD)

Sludge 1-Sum PBD

Unit mgkg

Mandels k statistics(Soil 3 - Sum PBD)Mandels h statistics(Soil 3 - Sum PBD)

Sample Soil 3 Soil 3 - Sum PBD -- Mean PARM = 0227 [mgkg]

Element Sum PBD

General calcparmT1= 610980E+00T2= 200876E+00T3= 26T4= 100T5= 13106E-02

n= variabelp= 7

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00028 0001 4 -037 000 Fail 00028 00005 4 3 -02226L 01179 0021 2 -036 003 Fail 01179 00208 2 1 -0114L 01305 0031 4 -036 004 Fail 01305 00308 4 3 -010

46L 02065 0035 4 -036 005 Fail 02065 00350 4 3 -00244L 02923 0037 4 -035 005 Fail 02923 00365 4 3 00712L 04051 0015 4 -034 002 Fail 04051 00149 4 3 01864L 04314 0022 4 -033 003 Fail 04314 00223 4 3 0203L 305500 2051 2 247 283 Fail - - 3L - - 3032

Totgem 4017 0276 mgkg 1-level 206 (181) 7 02266 (3L) 7 6Totstd= 10722 0717 5-level 175 (156) 1

RESULTS Mean = 022663 mgkg

Repeatability variance S2r = 000069Repeatability std Sr = 002626 --gt 1159 r = 00735Between lab variance S2L = 002568Reproducibility var S2R = 002637Reproducibility std SR = 016238 --gt 7165 R = 04547Remarks 1 Lab rejected (3L)

000 050 100 150 200 250 300

k-values

10L

26L

4L

46L

44L

12L

64L

3L

Mandels k statistics(Soil 3 - Sum PBD)

-50 00 50 100 150 200 250 300 350

Deviation from Mean

10L

26L

4L

46L

44L

12L

64L

3L

Labo

rato

ries

Soil 3 - Sum PBD -- Mean PARM = 0227 [mgkg]

-100 000 100 200 300

h-values

10L

26L

4L

46L

44L

12L

64L

3L

Labo

rato

ries

Mandels h statistics(Soil 3 - Sum PBD)

Soil 3-Sum PBD

19

Annex 4

Raw data submitted

Sample Compost1 Sample Compost 1 Sample Compost 1Element PBD 99 Element PBD 100 Element PBD 153

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]4L 00021 10L 00008 44L 000504L 00024 10L 00008 44L 000604L 00014 10L 00007 44L 000504L 00020 10L 00011 46L 00004

10L 00029 46L 00007 46L 0001210L 00027 46L 00012 46L 0000410L 00032 46L 00009 46L 0000946L 00025 46L 00007 12L 0000446L 00052 12L 00008 12L 0000846L 00029 12L 00012 12L 0000446L 00026 12L 00008 12L 0000712L 00026 12L 00014 26L 0000512L 00043 26L 00007 26L 0000512L 00026 26L 0000612L 0004726L 0002626L 00024

Sample Compost 1 Sample Compost 1 Sample Compost 1Element PBD 154 Element PBD 183 Element PBD 196

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]4L 00010 46L 00002 46L 00011

46L 00003 46L 00024 46L 0000846L 00007 46L 00021 12L 0000246L 00003 46L 00003 12L 0000346L 00004 12L 00003 12L 0000112L 00003 12L 00011 12L 0000212L 00005 12L 0000312L 00031 12L 0000312L 00006

Sample Compost 1 Sample Compost 1 Sample Compost 1Element PBD 197 Element PBD 203 Element PBD 209

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00002 46L 00010 4L 0004146L 00023 12L 00002 4L 0008946L 00022 12L 00003 44L 0041012L 00004 12L 00002 44L 0084012L 00006 12L 00002 44L 0064012L 00003 44L 0040012L 00004 12L 00079

12L 0007312L 0006512L 0009326L 0004926L 00049

Sample Compost 1Element PBD 47

LAB PARM [mgkg]26L 0003826L 00039

Element PBD 99 Element PBD 47 Element PBD 209LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]

4L 00170 10L 00210 4L 010004L 00200 10L 00220 4L 018004L 00170 10L 00210 4L 012004L 00190 46L 00300 4L 0220010L 00280 46L 00280 46L 0210010L 00300 46L 00250 46L 0200010L 00290 46L 00260 64L 0351846L 00340 64L 00059 64L 0363846L 00330 64L 00057 64L 0364546L 00300 64L 00062 64L 0350846L 00310 64L 00060 12L 0220964L 00194 12L 00191 12L 0177164L 00154 12L 00187 12L 0292264L 00185 12L 00190 12L 0164664L 00159 12L 00186 26L 0329712L 00242 26L 00666 26L 0300012L 00223 26L 0033212L 0022112L 0022226L 0024626L 00400

Element PBD 203 Element PBD 197 Element PBD 196LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00022 46L 00027 46L 0002446L 00014 46L 00024 46L 0002264L 00036 12L 00161 64L 0005864L 00058 12L 00060 64L 0006512L 00063 12L 00061 12L 0004812L 00034 12L 00036 12L 0002512L 00038 12L 0003212L 00027 12L 00022

Element PBD 183 Element PBD 154 Element PBD 153LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00049 4L 00020 4L 0002246L 00035 4L 00022 4L 0002446L 00036 4L 00020 4L 0002246L 00034 46L 00025 4L 0002664L 00027 46L 00025 46L 0004064L 00023 46L 00025 46L 0004264L 00024 46L 00023 46L 0003564L 00020 64L 00034 46L 0003812L 00230 64L 00023 64L 0007412L 00032 64L 00017 64L 0004712L 00031 64L 00011 64L 0004612L 00030 12L 00030 64L 0003026L 00007 12L 00021 12L 0006526L 00008 12L 00021 12L 00029

12L 00021 12L 0003226L 00015 12L 0002926L 00019 26L 00039

26L 00040

Element PBD 100LAB PARM [mgkg]

4L 000384L 000414L 000374L 00038

38L 0219038L 0220038L 0208038L 0220010L 0004410L 0005010L 0004310L 0004646L 0005746L 0005946L 0005346L 0005312L 0004312L 0004512L 0004312L 0004326L 0006226L 00057

Sample Soil 3 Sample Soil 3 Sample Soil 3Element PBD 99 Element PBD 47 Element PBD 100

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]10L 00016 10L 00011 10L 0000310L 00019 10L 00010 10L 0000410L 00013 10L 00012 10L 0000410L 00019 46L 00007 10L 0000246L 00025 46L 00022 46L 0000246L 00025 46L 00005 46L 0000646L 00008 46L 00007 46L 0000246L 00011 12L 00010 46L 0000264L 00005 12L 00017 3L 29100064L 00005 12L 00010 3L 32000064L 00006 12L 00009 26L 0000564L 00007 26L 00007 26L 0000512L 00012 26L 0000712L 0001312L 0001312L 0001226L 0000526L 00006

Sample Soil 3 Sample Soil 3 Sample Soil 3Element PBD 153 Element PBD 154 Element PBD 196

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]44L 00050 4L 00010 46L 0000744L 00050 46L 00001 46L 0001146L 00002 46L 00002 46L 0000846L 00003 46L 00001 46L 0001146L 00002 46L 00002 64L 0002646L 00002 64L 00001 64L 0002664L 00001 64L 00001 64L 0002964L 00001 64L 00001 64L 0003464L 00001 64L 00002 12L 0004564L 00002 12L 00003 12L 00032

12L 00002 12L 0002212L 00002 12L 0002112L 00002

Sample Soil 3 Sample Soil 3 Sample Soil 3Element PBD 197 Element PBD 203 Element PBD 209

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00006 46L 00011 4L 0091046L 00013 46L 00017 4L 0150046L 00011 46L 00015 4L 0120046L 00013 46L 00018 4L 0160012L 00090 64L 00013 44L 0337012L 00056 64L 00014 44L 0281012L 00033 64L 00016 44L 0287012L 00032 64L 00015 44L 02540

12L 00055 46L 0230012L 00041 46L 0220012L 00027 46L 0150012L 00026 46L 01900

64L 0438164L 0401664L 0414464L 0449812L 0367112L 0397812L 0409112L 03838

Sample Soil 3 26L 0102Element PBD 183 26L 0131

LAB PARM [mgkg]46L 0000746L 0000846L 0005846L 0000764L 0000264L 0000364L 0000364L 0000312L 0001512L 0001112L 0000712L 00007

European Commission EUR 23003 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on polybrominated diphenylethers Author(s) E Sobiecka H van der Sloot D Barcelo B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 68 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07403-5 Abstract Project HORIZONTAL is interdisciplinary aiming at a harmonisation and horizontal standardisation of test procedures in particular for sludge soils and biowastes In the context of this standardization project a series of draft technical specification were designed upon an extensive desk study fine-tuned after expert consultations and finally validated in international intercomparisons exercise This report summarises the work performed within the validation study of the draft standard for the determination of polybrominated diphenylethers (PBDE) in soils sludge and treated bio-waste using gas-chromatography method with mass selective detection (GC-MS) It further explains the underlying statistical concept for the calculation of reproducibility and repeatability from intercomparisons data In addition all single values results of the statistical evaluation as well as background information on the validation materials used are described and explained

The mission of the JRC is to provide customer-driven scientific and technical support for the conception development implementation and monitoring of EU policies As a service of the European Commission the JRC functions as a reference centre of science and technology for the Union Close to the policy-making process it serves the common interest of the Member States while being independent of special interests whether private or national

LB

-NA

-23003-EN

-C

15

14 Annexes Annex 1 Model questionnaire to be filled by the participating laboratories Annex 3 Report on the validation materials used Annex 2 Statistical calculations Annex 3 Data submitted

16

Annex 1

Model questionnaire to be filled by the participating laboratories

Model questionnaire to be filled by the participating laboratories Name of laboratory Contact person Contact details email Phone Fax Mail address of lab Dispatch address of lab for shipment of samples (no PO boxes) Title of measurement method (copy attached) Our laboratory is willing to participate in the precision experiment for this draft standard method

Yes No As participant we understand that

bull All essential apparatus chemicals and other requirements specified in the method must be available in our laboratory when the programme begins

bull Specified timing requirements such as starting and finishing date of the programme must be rigidly met

bull The method must be strictly adhered to bull Samples must be handled in accordance with instructions bull A qualified operator must perform the measurements

Having studied the method and having made a fair appraisal of our capabilities and facilities we feel that we will be adequately prepared for cooperative testing of this method Comments helliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphellip Signature Date

17

Annex 2

Report on the validation materials used

VI

Abstract This report gives an overview on the available analytical information on the following raw materials to be used for the production of validation materials of the so-called Project HORIZONTAL

bull Four sludge materials from Duumlsseldorf Germany

bull An agricultural soil material from Reading United Kingdom

bull A compost material from Vienna Austria

bull A compost material from Korschenbroich Germany

bull A sludge-amended agricultural soil from Pavia Province Italy

bull A sludge-amended soil from Barcelona Spain

bull A sludge-amended soil from Essen Germany

bull A long-term sludge exposed soil from Hohenheim Germany

VII

List of Abbreviations Throughout this report the following abbreviations are used

AOX absorbable organic halogens

Corg organic carbon content

Ctotal total carbon content

CAT cation exchangeable

CDD chlorinated dibenzodioxin

CDF chlorinated dibenzofuran

DEHP di(2-ethylhexyl)phthalate

DM dry matter

EPA Environment Protection Agency

EU European Union

FM fresh matter

Hp hepta

Hx hexa

IES Institute for Environment and Sustainability

IRMM Institute for Reference Materials and Measurements

JRC Joint Research Centre

LAS linear alkylsulfonates

LoD limit of detection

LUA Landesumweltamt

Ntotal total nitrogen content

NH4-N Ammonium nitrogen

NO3-N Nitrate nitrogen

NP nonylphenol

NRW North Rhine Westphalia

O octa

P poly

PAH polycyclic aromatic hydrocarbon

PCB polychlorinated biphenyl

Pe penta

T tetra

TEQ toxicity equivalent

UBA Umweltbundesamt

WHO World Health Organization

WWTP waste water treatment plant

6

1 Introduction This report gives an overview on the available analytical information on the following raw materials to be used for the production of validation materials of the so-called Project HORIZONTAL

bull Four sludge materials from Duumlsseldorf Germany

bull An agricultural soil material from Reading United Kingdom

bull A compost material from Vienna Austria

bull A compost material from Korschenbroich Germany

bull A sludge-amended agricultural soil from Pavia Province Italy

bull A sludge-amended soil from Barcelona Spain

bull A sludge-amended soil from Essen Germany

bull A long-term sludge exposed soil from Hohenheim Germany

The following analytical information was gathered partly before and during the sampling of the raw materials to be used for the production of the HORIZONTAL validation materials The material were sampled by IES and shipped to IRMM in the course of the year 2005 The information gathered was then completed by various analytical screenings for PAHs and PCBs done by the Institute for Reference Materials and Measurements Geel Belgium for phthalates done by UBA Berlin Germany for PBDE done by IIQAB-CSIC Barcelona Spain for trace elements and some selected major and minor elements by the Institute for Environment and Sustainability Ispra Italy

The work compiled hereafter is based on the numerous additional efforts of the scientists working at various members of the consortium Project HORIZONTAL-Org and contributing organisations

This work is gratefully acknowledged

2 Overview on property values

21 Sludge materials from Duumlsseldorf Germany

The various sewage sludge materials originate from various installations in the North Rhine Westphalia and were produced and sampled by staff from the Landesumweltamt (LUA) NRW under the responsibility from Dr K Furtmann

In total four sludge materials (Sludge A and D from a major municipal WWTP Sludge B from a municipal WWTP with industrial input and Sludge C from a municipal WWTP with high PCB-Content) were obtained and will be blended to two final materials Before sampling the following analytical data for a typical sample were received

7

Table 1 ndash Analytical data obtained on an average sludge sample in LUA NRW (with courtesy of K Furtmann LUA Duumlsseldorf)

Parameter Concentration PCB 120 ugkg DEHP 110 mgkg PAH 5 mgkg (EPA) PCDDF 15 ng TEkg PBDE 400 ugkg NP 40 mgkg LAS 3 gkg AOX 300 mgkg

Subsequent screening led to the information displayed hereafter It should be stressed that the data were obtained as SCREENING information on the UNTREATED or partially treated raw materials Therefore the final target values which are relevant for the validation intercomparison can be different

Table 2 ndash Analytical data obtained on a first screening on the sludge samples from LUA NRW

Sewage sludge A

Dusseldorf

sewage sludge D

Dusseldorf PCB (ngg) 28 62 35 52 101 65 101 31 38 118 49 40 153 30 33 105 24 11 138 46 38 156 lt1 lt1 180 34 23 170 23 19 PAH (ngg) Naphtalene 34 381 Acenaphtylene 15 43 Acenaphthene 81 108 Fluorene 94 1167 Phenantrene 3440 Anthracene 22 344 Flouranthene 316 4817 Pyrene 235 3011 Benz(a)anthracene 473 791 Chrysene 691 1078 Benz(b)fluoranthene 538 1688 Benz(k)fluoranthene 228 635 Benz(a)pyrene 383 1114 Indeno(123-cd)pyrene 92 229 Dibenzo(ah)anthracene 71 70 Benzo(ghi)perylene 80 185

8

Table 3 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Sludge D (1) 0135 41474 385 Sludge B (2) 0538 0034 30634 547 Sludge A (3) 0184 0037 31399 146 Sludge C (4) 0354 1528 6678 229

Table 4 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Sludge 2

(B)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

554

959

694

591

772

509

nq

nq

970

2216

2379

Table 5 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena IES Ispra Spain) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Sludge 1 (D) 265 290 533 359 1231 338 784 438 lt 005 232 786 Sludge 2 (B) 119 311 626 202 278 299 722 251 lt 005 118 625 Sludge 3 (A) 168 360 621 332 847 416 119 451 lt 005 116 1237 Sludge 4 (C) 563 198 116 273 726 511 473 618 lt 005 444 2015

Table 6 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Sludge 1 (D) 2154 58 844 099 103 101 4367 lt15 50448 Sludge 2 (B) 1067 366 692 046 1491 077 5217 lt15 57633 Sludge 3 (A) 731 663 684 035 1287 068 3733 lt15 60369 Sludge 4 (C) 4379 965 527 163 522 107 5628 lt15 23945

Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM)Sludge 1 (D) 03 2403 101 1002 350 15 1944 132Sludge 2 (B) 031 315 97 879 172 12 514 180Sludge 3 (A) 031 1281 153 1567 265 16 1440 168Sludge 4 (C) 055 231 628 2625 371 81 1101 244

9

22 Agricultural soil material from Reading United Kingdom

The material was proposed by the University of Reading (S Nortcliff) and was sampled from a site called ldquoFrogmore Farmrdquo which was featured in the ldquoMetalsrdquo Report for HORIZONTAL This site is close to Reading with soils developed on flintyloamy periglacial materials over Chalk has a long and well documented history of sludge application The focus of the work of Nortcliff et al undertook at this site and the monitoring and control at the site (by Thames Water and the subsequent subsidiary bodies dealing with sludge application to soil) was on metals (and metal loads) with no analysis or indeed any form of investigation in to organics in the broadest sense

The analytical information produced in the context of the screening of the raw material is displayed below

Table 7 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 3

(Reading) 0032 0119 669

Table 8 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 3 (Reading) 015 706 279 138 152 901 267 300 lt 005 258 931

Table 9 ndash Analytical data obtained on a first screening on the sludge-amended soil from Reading (courtesy of IRMM)

Parameter Concentration

PCB ngg 28 lt1 52 lt1 101 lt1 118 lt1 153 lt1 105 lt1 138 lt1 156 lt1 180 lt1 170 lt1 PAH ngg Naphtalene lt10 Acenaphtylene 21 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene lt10 Flouranthene 818 Pyrene 776 Benz(a)anthracene 565

10

Parameter Concentration

Chrysene 608 Benz(b)fluoranthene 824 Benz(k)fluoranthene 329 Benz(a)pyrene 799 Indeno(123-cd)pyrene

779

Dibenzo(ah)anthracene 118 Benzo(ghi)perylene 394

Table 10 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 3

(Reading)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

103

003

nq

nq

nq

nd

nd

272

273

Table 11 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 3 (Reading) 015 706 279 138 152 901 267 300 lt 005 258 931

Table 12 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 3 (Reading) 7936 477 112 096 194 017 4107 443 2102 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 3 (Reading) 042 13 45 69 69 69 216 92

Table 13 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 3 (Reading) 012

11

23 Compost from Vienna Austria

The fresh compost material was obtained from the Austrian Federal Environment Agency (UBA Vienna) which had used a sub-batch of the raw material for national intercomparson The remainder of the material was stored at 4degC until shipment to IRMM for further processing The following analytical information was provided by UBA Austria and completed with various screenings

Table 14 ndash Analytical data on compost material received from UBA Austria Inorganic and sum parameters

Parameter Unit Sample fraction used Observed mean B CAT mgl FM Fresh sample lt10mm 61 K CAT mgl FM Fresh sample lt10mm 2624 Mg CAT mgl FM Fresh sample lt10mm 242 P CAT mgl FM Fresh sample lt10mm 49 B CAT DM Fresh sample lt10mm 00017 K CAT DM Fresh sample lt10mm 072 Mg CAT DM Fresh sample lt10mm 007 P CAT DM Fresh sample lt10mm 001 NO3-N mgkg FM Fresh sample lt10mm 35 NH4-N mgkg FM Fresh sample lt10mm 230 Ctotal DM lt45degdry milled 29 Corg DM lt45degdry milled 27 Ntotal DM lt45degdry milled 17 P mgkg DM lt45degdry milled 2596 K mgkg DM lt45degdry milled 11019 K DM lt45degdry milled 110 B mgkg DM lt45degdry milled 60 Cd mgkg DM lt45degdry milled 046 Cr mgkg DM lt45degdry milled 25 Cu mgkg DM lt45degdry milled 46 Hg mgkg DM lt45degdry milled 020 Ni mgkg DM lt45degdry milled 18 Pb mgkg DM lt45degdry milled 45 Zn mgkg DM lt45degdry milled 198 Ca mgkg DM lt45degdry milled 68776 Ca DM lt45degdry milled 69 Mo mgkg DM lt45degdry milled 08 S mgkg DM lt45degdry milled 2137 Fe mgkg DM lt45degdry milled 9959 Mn mgkg DM lt45degdry milled 418 Na mgkg DM lt45degdry milled 742 Co mgkg DM lt45degdry milled 41 AOX mgkg DM lt30deg dry milled 62

Table 15 ndash Analytical data on compost material received from UBA Austria Polycyclic aromatic hydrocarbons

PAH Unit Result Naphthaline microgkg DM 93 Acenaphthylene microgkg DM 86 Acenaphthene microgkg DM 5 Fluorene microgkg DM 80 Phenanthrene microgkg DM 89 Anthracene microgkg DM 27 Fluoranthene microgkg DM 487 Pyrene microgkg DM 380

12

PAH Unit Result Benzo(a)anthracene microgkg DM 278 Chrysene microgkg DM 317 Benzo(b)fluoranthene microgkg DM 365 Benzo(k)fluoranthene microgkg DM 193 Benz(a)pyrene microgkg DM 320 Indeno(123-cd)pyrene microgkg DM 233 Dibenz(ah)anthracene microgkg DM 67 Benzo(ghi)perylene microgkg DM 225 Sum EPA microgkg DM 3013 Sum EPA mgkg DM 30

Table 16 ndash Analytical data on compost material received from UBA Austria Sum PCDDs and PCBs

Parameter

Dioxine TEQ (ITEF) ngkg DM 73 TEQ (WHO) ngkg DM 35 PCB Σ Ballschmiter mgkg DM 005

Table 17 ndash Analytical data on compost material obtained by screening in IRMM

Parameter Result in ngg

PCB 28 2 52 2 101 4 118 3 153 10 105 1 138 8 156 1 180 5 170 lt1 PAH Naphtalene lt10 Acenaphtylene lt10 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene 26 Fluoranthene 611 Pyrene 510 Benz(a)anthracene 888 Chrysene 957 Benz(b)fluoranthene 1531 Benz(k)fluoranthene 547 Benz(a)pyrene 1101 Indeno(123-cd)pyrene 416 Dibenzo(ah)anthracene 81 Benzo(ghi)perylene 295

13

Table 18 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Compost 1

(Vienna)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

402

019

259

nq

023

004

nq

nq

144

174

259

Table 19 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Compost 1

(Vienna) 0058 1426 557

Table 20 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Compost 1 (Vienna) 039 736 319 410 365 127 495 004 079 013 208

Table 21 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Compost 1 (Vienna) 2063 431 617 426 199 249 1602 lt15 10521

Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Compost 1 (Vienna) 035 3496 81 375 79 55 653 60

Table 22 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Compost 1 (Vienna) 017

14

24 Agricultural soil sludge amended soil from Pavia Italy

This sludge-amended soil material was obtained during a monitoring campaign which aimed at a generic description of the over-all soil quality in Pavia Province Italy The material which was collected from the upper horizon originates from a small farm called ldquoCascina Novellordquo During the characterisation of the site the following analytical information was obtained on a pooled sample of a sub-area of the farm of 20 X 20 m2

Table 23 ndash Analytical data on Pavia soil

Parameter Result Al 713 Wgt As 224 mgkg Cd 079 mgkg Cr 59 mgkg Cu 308 mgkg Hg 008 mgkg Ni 344 mgkg Pb 246 mgkg Zn 95 mgkg C 091 Wgt 2378-TCDD 0047 pgg 12378-PeCDD 015 pgg 123478-HxCDD 019 pgg 123678-HxCDD 15 pgg 123789-HxCDD 074 pgg 1234678-HpCDD 26 pgg OCDD 382 pgg 2378-TCDF 068 pgg 12378-PeCDF 053 pgg 23478-PeCDF 071 pgg 123478-HxDF 100 pgg 123678-HxDF 066 pgg 234678-HxDF 16 pgg 123789-HxDF 027 pgg 1234678-HpDF 12 pgg 1234789-HpDF 068 pgg OCDF 33 pgg I-TEQ 20 pgg WHO-TEQ 17 pgg

In addition the screening performed at IRMM did not reveal significant quantities of PCBs and PAHs which were all below the LoDs (1 ngg for PCBs and 10 ngg for PAHs respectively)

Table 24 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 5 (Pavia) 0005 0011 154

15

Table 25 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 5

(Pavia)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

039

nq

nq

008

nq

nd

nd

670

671

Table 26 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 5 (Pavia) 033 184 573 225 426 305 206 200 lt 005 381 878

Table 27 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 5 (Pavia) 6939 129 145 224 425 116 6118 255 1789 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 5 (Pavia) 184 62 38 108 55 66 597 110

Table 28 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 5 (Pavia) 006

16

25 Sludge-amended-soil from Barcelona Spain

The sludge-amended soil material from Barcelona sampled upon indication from the Barcelorsquo- Group in Barcelona

Table 29 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 2 (Lleida T) 0015 0183 1138

Table 30 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 2

(Lleida T)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

159

045

nq

048

160

nq

nq

1000

1004

Table 31 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 2 (Lleida T) 059 141 327 536 405 186 184 224 lt 005 318 111

Table 32 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 2 (Lleida T) 4443 1067 1429 253 344 204 4116 780 3396 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 2 (Lleida T) 064 65 26 125 59 17 547 65

Table 33 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 2 (Lleida T) 010

17

26 Sludge amended soil from Essen Germany

The German sludge-amended soil from Essen which was provided as the three sludge materials by LUA NRW did not feature significant concentrations of the PCB congeners 28 52 101 118 153 105 138 156 180 170 but had detectable amounts of some PAHs

Table 34 ndash Analytical screening data on the German sludge-amended soil

Parameter Concentration(ngg)

Naphtalene lt10 Acenaphtylene lt10 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene lt10 Fluoranthene 28 Pyrene 20 Benz(a)anthracene 24 Chrysene 47 Benz(b)fluoranthene 76 Benz(k)fluoranthene 20 Benz(a)pyrene 35 Indeno(123-cd)pyrene 35 Dibenzo(ah)anthracene 10 Benzo(ghi)perylene 26

Table 35 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 4 (Essen) 0011 0302 055

Table 36 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 4

(Essen)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

nq

nq

nq

nq

nq

nq

128

191

203

18

Table 37 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 4 (Essen) 052 545 261 805 320 403 273 273 lt 005 295 781

Table 38 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 4 (Essen) 7947 442 085 06 086 007 2163 189 2019 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 4 (Essen) 045 19 42 87 683 60 462 61

Table 39 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 4 (Essen) 004

27 Long-term sludge exposed soil from Hohenheim-Stuttgart Germany

Similarly an additional sludge exposed soil was sampled at the University of Hohenheim Stuttgart were a test soil was long-term exposed to elevated concentrations of sewage sludge

Table 40 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 1 (Stuttgart) 0045 0263 1765

Table 41 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 1

(Stuttgart)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

230

006

004

004

nq

nd

nd

498

500

19

Table 42 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 1 (Stuttgart) 069 127 361 262 504 183 252 262 lt 005 266 142

Table 43 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 1 (Stuttgart) 7194 1006 133 186 366 088 7874 275 3571 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 1 (Stuttgart) 123 50 47 212 85 69 991 129

Table 44 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 1 (Stuttgart) 177

18

Annex 3

Statistical calculations

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 47)Mandels h statistics(Sludge 1 - PBD 47)

Sample Sludge 1 NUM

Element PBD 47

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00213 0001 3 -021 005 - - 10L - - NUM46L 00273 0002 4 016 021 - - 46L - - NUM64L 00059 0000 4 -116 002 NUM - 64L - - NUM12L 00188 0000 4 -036 002 - - 12L - - NUM26L 00499 0024 2 157 223 Fail - - 26L - - NUM

Totgem 0025 0005 mgkg 1-level 172 (185) NUM (10L46L64L12L26L) -1Totstd= 0016 0010 5-level 157 (162) 5

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 5 Labs rejected (10L46L64L12L26L)

000 050 100 150 200 250

k-values

10L

46L

64L

12L

26L

Mandels k statistics(Sludge 1 - PBD 47)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

10L

46L

64L

12L

26L

Labo

rato

ries

NUM

-200 -100 000 100 200

h-values

10L

46L

64L

12L

26L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 47)

Sludge 1-PBD 47

Unit mgkg

Mandels k statistics(Soil 3 - PBD 47)Mandels h statistics(Soil 3 - PBD 47)

Sample Soil 3 Soil 3 - PBD 47 -- Mean PARM = 0001 [mgkg]

Element PBD 47

General calcparmT1= 134814E-02T2= 142830E-05T3= 13T4= 45T5= 22767E-06

n= variabelp= 4

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean26L 00007 0000 2 -143 001 00007 00000 2 1 00046L 00010 0001 4 010 181 00010 00008 4 3 00010L 00011 0000 3 049 023 00011 00001 3 2 00012L 00012 0000 4 084 081 00012 00004 4 3 000

Totgem 0001 0000 mgkg 1-level 149 (177) 4 00010 () 4 3Totstd= 0000 0000 5-level 142 (159)

RESULTS Mean = 000100 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000050 --gt 5031 r = 00014Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000050 --gt 5031 R = 00014Remarks none

000 050 100 150 200

k-values

26L

46L

10L

12L

Mandels k statistics(Soil 3 - PBD 47)

00 00 00 00 00 00 00 00 00 00 00

Deviation from Mean

26L

46L

10L

12L

Labo

rato

ries

Soil 3 - PBD 47 -- Mean PARM = 0001 [mgkg]

-200 -100 000 100

h-values

26L

46L

10L

12L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 47)

Soil 3-PBD 47

Unit mgkg

Mandels k statistics(Compost 1 - PBD 99)Mandels h statistics(Compost 1 - PBD 99)

Sample Compost 1 Compost 1 - PBD 99 -- Mean PARM = 0003 [mgkg]

Element PBD 99

General calcparmT1= 492124E-02T2= 148747E-04T3= 17T4= 61T5= 93196E-06

n= variabelp= 5

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00020 0000 4 -137 053 00020 00004 4 3 000

26L 00025 0000 2 -058 024 00025 00002 2 1 00010L 00029 0000 3 012 032 00029 00003 3 2 00046L 00033 0001 4 069 161 00033 00013 4 3 00012L 00036 0001 4 114 140 00036 00011 4 3 000

Totgem 0003 0001 mgkg 1-level 172 (185) 5 00029 () 5 4Totstd= 0001 0001 5-level 157 (162)

RESULTS Mean = 000286 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000088 --gt 3086 r = 00025Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000101 --gt 3525 R = 00028Remarks none

000 050 100 150 200

k-values

4L

26L

10L

46L

12L

Mandels k statistics(Compost 1 - PBD 99)

00 00 00 00 00 00 00 00 00 00

Deviation from Mean

4L

26L

10L

46L

12L

Labo

rato

ries

Compost 1 - PBD 99 -- Mean PARM = 0003 [mgkg]

-200 -100 000 100 200

h-values

4L

26L

10L

46L

12L

Labo

rato

ries

Mandels h statistics(Compost 1 - PBD 99)

Compost 1-PBD 99

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 99)Mandels h statistics(Sludge 1 - PBD 99)

Sample Sludge 1 Sludge 1 - PBD 99 -- Mean PARM = 0024 [mgkg]

Element PBD 99

General calcparmT1= 448050E-01T2= 112113E-02T3= 19T4= 73T5= 32972E-05

n= variabelp= 5

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean64L 00173 0002 4 -118 041 Fail 00173 00019 4 3 -0014L 00183 0002 4 -104 032 00183 00015 4 3 -001

12L 00227 0001 4 -038 022 00227 00010 4 3 00010L 00290 0001 3 055 021 00290 00010 3 2 00146L 00320 0002 4 100 039 00320 00018 4 3 00126L 00323 0011 2 105 234 - - 26L - - 001

Totgem 0025 0003 mgkg 1-level 187 (177) 5 00239 (26L) 5 4Totstd= 0007 0004 5-level 166 (154) 1

RESULTS Mean = 002385 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000153 --gt 643 r = 00043Between lab variance S2L = 000004Reproducibility var S2R = 000004Reproducibility std SR = 000666 --gt 2791 R = 00186Remarks 1 Lab rejected (26L)

000 050 100 150 200 250

k-values

64L

4L

12L

10L

46L

26L

Mandels k statistics(Sludge 1 - PBD 99)

00 00 00 00 00 00 00 00 00 00

Deviation from Mean

64L

4L

12L

10L

46L

26L

Labo

rato

ries

Sludge 1 - PBD 99 -- Mean PARM = 0024 [mgkg]

-200 -100 000 100 200

h-values

64L

4L

12L

10L

46L

26L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 99)

Sludge 1-PBD 99

Unit mgkg

Mandels k statistics(Soil 3 - PBD 99)Mandels h statistics(Soil 3 - PBD 99)

Sample Soil 3 NUM

Element PBD 99

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00017 0000 4 091 068 - - 10L - - NUM46L 00017 0001 4 100 211 - - 46L - - NUM64L 00005 0000 4 -106 023 NUM - 64L - - NUM12L 00012 0000 4 015 014 - - 12L - - NUM26L 00006 0000 2 -101 012 - - 26L - - NUM

Totgem 0001 0000 mgkg 1-level 172 (173) NUM (10L46L64L12L26L) -1Totstd= 0001 0000 5-level 157 (153) 5

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 5 Labs rejected (10L46L64L12L26L)

000 050 100 150 200 250

k-values

10L

46L

64L

12L

26L

Mandels k statistics(Soil 3 - PBD 99)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

10L

46L

64L

12L

26L

Labo

rato

ries

NUM

-200 -100 000 100 200

h-values

10L

46L

64L

12L

26L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 99)

Soil 3-PBD 99

Unit mgkg

Mandels k statistics(Compost 1 - PBD 100)Mandels h statistics(Compost 1 - PBD 100)

Sample Compost 1 Compost 1 - PBD 100 -- Mean PARM = 0001 [mgkg]

Element PBD 100

General calcparmT1= 124272E-02T2= 113129E-05T3= 14T4= 52T5= 46584E-07

n= variabelp= 4

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean26L 00006 0000 2 -131 037 Fail 00006 00001 2 1 00010L 00009 0000 4 003 083 00009 00002 4 3 00046L 00009 0000 4 016 115 00009 00002 4 3 00012L 00011 0000 4 112 136 Fail 00011 00003 4 3 000

Totgem 0001 0000 mgkg 1-level 149 (167) 4 00009 () 4 3Totstd= 0000 0000 5-level 142 (15)

RESULTS Mean = 000085 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000022 --gt 2531 r = 00006Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000025 --gt 2882 R = 00007Remarks none

000 050 100 150

k-values

26L

10L

46L

12L

Mandels k statistics(Compost 1 - PBD 100)

00 00 00 00 00 00 00 00 00 00 00

Deviation from Mean

26L

10L

46L

12L

Labo

rato

ries

Compost 1 - PBD 100 -- Mean PARM = 0001 [mgkg]

-200 -100 000 100 200

h-values

26L

10L

46L

12L

Labo

rato

ries

Mandels h statistics(Compost 1 - PBD 100)

Compost 1-PBD 100

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 100)Mandels h statistics(Sludge 1 - PBD 100)

Sample Sludge 1 Sludge 1 - PBD 100 -- Mean PARM = 0005 [mgkg]

Element PBD 100

General calcparmT1= 852065E-02T2= 412762E-04T3= 18T4= 68T5= 78914E-07

n= variabelp= 5

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00039 0000 4 -042 007 Fail 00039 00002 4 3 000

12L 00044 0000 4 -041 005 Fail 00044 00001 4 3 00010L 00046 0000 4 -041 013 Fail 00046 00003 4 3 00046L 00056 0000 4 -040 012 Fail 00056 00003 4 3 00026L 00059 0000 2 -040 013 Fail 00059 00003 2 1 00038L 02168 0006 4 204 244 Fail - - 38L - - 021

Totgem 0040 0001 mgkg 1-level 187 (177) 5 00049 (38L) 5 4Totstd= 0087 0002 5-level 166 (154) 1

RESULTS Mean = 000486 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000025 --gt 507 r = 00007Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000084 --gt 1731 R = 00024Remarks 1 Lab rejected (38L)

000 050 100 150 200 250

k-values

4L

12L

10L

46L

26L

38L

Mandels k statistics(Sludge 1 - PBD 100)

-01 00 01 01 02 02 03

Deviation from Mean

4L

12L

10L

46L

26L

38L

Labo

rato

ries

Sludge 1 - PBD 100 -- Mean PARM = 0005 [mgkg]

-100 000 100 200 300

h-values

4L

12L

10L

46L

26L

38L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 100)

Sludge 1-PBD 100

Unit mgkg

Mandels k statistics(Soil 3 - PBD 100)Mandels h statistics(Soil 3 - PBD 100)

Sample Soil 3 NUM

Element PBD 100

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00003 0000 4 -050 000 Fail - - 10L - - NUM46L 00003 0000 4 -050 000 Fail NUM - 46L - - NUM3L 305500 2051 2 150 200 Fail - - 3L - - NUM

26L 00005 0000 2 -050 000 Fail - - 26L - - NUM

Totgem 7638 0513 mgkg 1-level 149 (177) NUM (10L46L3L26L) -1Totstd= 15275 1025 5-level 142 (159) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (10L46L3L26L)

000 050 100 150 200

k-values

10L

46L

3L

26L

Mandels k statistics(Soil 3 - PBD 100)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

10L

46L

3L

26L

Labo

rato

ries

NUM

-100 000 100 200

h-values

10L

46L

3L

26L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 100)

Soil 3-PBD 100

Unit mgkg

Mandels k statistics(Compost 1 - PBD 153)Mandels h statistics(Compost 1 - PBD 153)

Sample Compost 1 NUM

Element PBD 153

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean44L 00053 0001 3 150 157 Fail - - 44L - - NUM46L 00007 0000 4 -044 111 Fail - - 46L - - NUM12L 00005 0000 4 -051 055 Fail - - 12L - - NUM26L 00005 0000 2 -054 001 Fail NUM - 26L - - NUM

Totgem 0002 0000 mgkg 1-level 149 (177) NUM (44L46L12L26L) -1Totstd= 0002 0000 5-level 142 (159) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (44L46L12L26L)

000 050 100 150 200

k-values

44L

46L

12L

26L

Mandels k statistics(Compost 1 - PBD 153)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

44L

46L

12L

26L

Labo

rato

ries

NUM

-100 000 100 200

h-values

44L

46L

12L

26L

Labo

rato

ries

Mandels h statistics(Compost 1 - PBD 153)

Compost 1-PBD 153

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 153)Mandels h statistics(Sludge 1 - PBD 153)

Sample Sludge 1 Sludge 1 - PBD 153 -- Mean PARM = 0004 [mgkg]

Element PBD 153

General calcparmT1= 676738E-02T2= 267609E-04T3= 18T4= 68T5= 19626E-05

n= variabelp= 5

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00024 0000 4 -157 017 00024 00002 4 3 000

12L 00038 0002 4 006 154 00038 00018 4 3 00046L 00039 0000 4 011 026 00039 00003 4 3 00026L 00039 0000 2 018 004 00039 00000 2 1 00064L 00049 0002 4 122 159 00049 00018 4 3 000

Totgem 0004 0001 mgkg 1-level 172 (173) 5 00038 () 5 4Totstd= 0001 0001 5-level 157 (153)

RESULTS Mean = 000378 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000123 --gt 3252 r = 00034Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000142 --gt 3754 R = 00040Remarks none

000 050 100 150 200

k-values

4L

12L

46L

26L

64L

Mandels k statistics(Sludge 1 - PBD 153)

00 00 00 00 00 00 00

Deviation from Mean

4L

12L

46L

26L

64L

Labo

rato

ries

Sludge 1 - PBD 153 -- Mean PARM = 0004 [mgkg]

-200 -100 000 100 200

h-values

4L

12L

46L

26L

64L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 153)

Sludge 1-PBD 153

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 154)Mandels h statistics(Sludge 1 - PBD 154)

Sample Sludge 1 NA

Element PBD 154

General calcparmT1= NAT2= NAT3=T4=T5=

n= variabelp=

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00021 0000 3 -100 021 NA - 4L - - NA

46L 00025 0000 4 115 018 NA - 46L - - NA64L 00021 0001 4 -066 179 - - 64L - - NA12L 00023 0000 4 050 085 - - 12L - - NA

Totgem 0002 0000 mgkg 1-level 149 (167) NA (4L46L64L12L) -1Totstd= 0000 0000 5-level 142 (15) 4

RESULTS Mean = NA mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NAReproducibility var S2R = NAReproducibility std SR = NA --gt NA R = NARemarks 4 Labs rejected (4L46L64L12L)

000 050 100 150 200

k-values

4L

46L

64L

12L

Mandels k statistics(Sludge 1 - PBD 154)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

4L

46L

64L

12L

Labo

rato

ries

NA

-100 000 100 200

h-values

4L

46L

64L

12L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 154)

Sludge 1-PBD 154

Unit mgkg

Mandels k statistics(Soil 3 - PBD 154)Mandels h statistics(Soil 3 - PBD 154)

Sample Soil 3 NUM

Element PBD 154

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

4L 00010 - 1 150 Fail - - 4L - - NUM46L 00001 0000 4 -053 096 Fail - - 46L - - NUM64L 00001 0000 4 -056 105 Fail NUM - 64L - - NUM12L 00002 0000 4 -040 099 Fail - - 12L - - NUM

Totgem 000037 0000 mgkg 1-level 149 (164) NUM (4L46L64L12L) -1Totstd= 000042 0000 5-level 142 (153) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (4L46L64L12L)

000 050 100 150

k-values

4L

46L

64L

12L

Mandels k statistics(Soil 3 - PBD 154)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

4L

46L

64L

12L

Labo

rato

ries

NUM

-100 000 100 200

h-values

4L

46L

64L

12L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 154)

Soil 3-PBD 154

Unit mgkg

Mandels k statistics(Compost 1 - PBD 209)Mandels h statistics(Compost 1 - PBD 209)

Sample Compost 1 NUM

Element PBD 209

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00065 0003 2 -049 032 - - 4L - - NUM

44L 00573 0021 4 150 197 Fail - - 44L - - NUM12L 00078 0001 4 -045 011 - - 12L - - NUM26L 00049 0000 2 -056 000 NUM - 26L - - NUM

Totgem 0019 0006 mgkg 1-level 149 (177) NUM (4L44L12L26L) -1Totstd= 0025 0010 5-level 142 (159) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (4L44L12L26L)

000 050 100 150 200

k-values

4L

44L

12L

26L

Mandels k statistics(Compost 1 - PBD 209)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

4L

44L

12L

26L

Labo

rato

ries

NUM

-100 000 100 200

h-values

4L

44L

12L

26L

Labo

rato

ries

Mandels h statistics(Compost 1 - PBD 209)

Compost 1-PBD 209

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 209)Mandels h statistics(Sludge 1 - PBD 209)

Sample Sludge 1 Sludge 1 - PBD 209 -- Mean PARM = 0249 [mgkg]

Element PBD 209

General calcparmT1= 394542E+00T2= 107296E+00T3= 16T4= 56T5= 19723E-02

n= variabelp= 5

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 01550 0055 4 -112 148 Fail 01550 00551 4 3 -009

46L 02050 0007 2 -053 019 02050 00071 2 1 -00412L 02137 0058 4 -042 155 02137 00576 4 3 -00426L 03149 0021 2 078 057 Fail 03149 00210 2 1 00764L 03577 0007 4 129 020 Fail 03577 00074 4 3 011

Totgem 0249 0030 mgkg 1-level 172 (185) 5 02493 () 5 4Totstd= 0084 0025 5-level 157 (162)

RESULTS Mean = 024926 mgkg

Repeatability variance S2r = 000179Repeatability std Sr = 004234 --gt 1699 r = 01186Between lab variance S2L = 000743Reproducibility var S2R = 000922Reproducibility std SR = 009604 --gt 3853 R = 02689Remarks none

000 050 100 150 200

k-values

4L

46L

12L

26L

64L

Mandels k statistics(Sludge 1 - PBD 209)

-01 -01 00 01 01 02

Deviation from Mean

4L

46L

12L

26L

64L

Labo

rato

ries

Sludge 1 - PBD 209 -- Mean PARM = 0249 [mgkg]

-200 -100 000 100 200

h-values

4L

46L

12L

26L

64L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 209)

Sludge 1-PBD 209

Unit mgkg

Mandels k statistics(Soil 3 - PBD 209)Mandels h statistics(Soil 3 - PBD 209)

Sample Soil 3 Soil 3 - PBD 209 -- Mean PARM = 0258 [mgkg]

Element PBD 209

General calcparmT1= 596398E+00T2= 191917E+00T3= 22T4= 84T5= 13249E-02

n= variabelp= 6

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean26L 01162 0021 2 -108 074 Fail 01162 00207 2 1 -0144L 01303 0031 4 -097 111 Fail 01303 00312 4 3 -013

46L 01975 0036 4 -046 128 Fail 01975 00359 4 3 -00644L 02898 0035 4 024 124 Fail 02898 00346 4 3 00312L 03895 0018 4 100 065 Fail 03895 00181 4 3 01364L 04260 0022 4 127 078 Fail 04260 00219 4 3 017

Totgem 0258 0027 mgkg 1-level 187 (177) 6 02582 () 6 5Totstd= 0132 0008 5-level 166 (154)

RESULTS Mean = 025818 mgkg

Repeatability variance S2r = 000083Repeatability std Sr = 002878 --gt 1115 r = 00806Between lab variance S2L = 001640Reproducibility var S2R = 001723Reproducibility std SR = 013127 --gt 5084 R = 03676Remarks none

000 050 100 150

k-values

26L

4L

46L

44L

12L

64L

Mandels k statistics(Soil 3 - PBD 209)

-02 -01 -01 00 01 01 02 02

Deviation from Mean

26L

4L

46L

44L

12L

64L

Labo

rato

ries

Soil 3 - PBD 209 -- Mean PARM = 0258 [mgkg]

-200 -100 000 100 200

h-values

26L

4L

46L

44L

12L

64L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 209)

Soil 3-PBD 209

Unit mgkg

Mandels k statistics(Compost 1 - Sum PBD)Mandels h statistics(Compost 1 - Sum PBD)

Sample Compost 1 Compost 1 - Sum PBD -- Mean PARM = 0009 [mgkg]

Element Sum PBD

General calcparmT1= 154064E-01T2= 169065E-03T3= 18T4= 68T5= 11354E-04

n= variabelp= 5

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00031 0002 4 -067 016 00031 00016 4 3 -0014L 00055 0005 4 -056 048 00055 00047 4 3 000

46L 00085 0003 4 -042 031 00085 00030 4 3 00026L 00123 0000 2 -024 003 00123 00002 2 1 00012L 00154 0002 4 -011 021 00154 00021 4 3 00144L 00613 0023 4 200 237 Fail - - 44L - - 005

Totgem 0018 0006 mgkg 1-level 187 (177) 5 00089 (44L) 5 4Totstd= 0022 0009 5-level 166 (154) 1

RESULTS Mean = 000893 mgkg

Repeatability variance S2r = 000001Repeatability std Sr = 000296 --gt 3308 r = 00083Between lab variance S2L = 000002Reproducibility var S2R = 000003Reproducibility std SR = 000570 --gt 6374 R = 00159Remarks 1 Lab rejected (44L)

000 050 100 150 200 250

k-values

10L

4L

46L

26L

12L

44L

Mandels k statistics(Compost 1 - Sum PBD)

00 00 00 00 00 00 01 01

Deviation from Mean

10L

4L

46L

26L

12L

44L

Labo

rato

ries

Compost 1 - Sum PBD -- Mean PARM = 0009 [mgkg]

-100 000 100 200

h-values

10L

4L

46L

26L

12L

44L

Labo

rato

ries

Mandels h statistics(Compost 1 - Sum PBD)

Compost 1-Sum PBD

Unit mgkg

Mandels k statistics(Sludge 1 - Sum PBD)Mandels h statistics(Sludge 1 - Sum PBD)

Sample Sludge 1 Sludge 1 - Sum PBD -- Mean PARM = 0256 [mgkg]

Element Sum PBD

General calcparmT1= 531806E+00T2= 162188E+00T3= 22T4= 84T5= 25223E-02

n= variabelp= 6

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00423 0025 4 -156 044 Fail 00423 00252 4 3 -02146L 01808 0118 4 -049 205 - - 46L - - -0074L 01810 0056 4 -049 097 01810 00558 4 3 -007

38L 02168 0006 4 -022 010 02168 00059 4 3 -00412L 02890 0065 4 034 113 02890 00647 4 3 00364L 03958 0008 4 116 014 Fail 03958 00079 4 3 01426L 04094 0034 2 126 059 Fail 04094 00337 2 1 015

Totgem 0245 0044 mgkg 1-level 198 (179) 6 02557 (46L) 6 5Totstd= 0130 0039 5-level 171 (155) 1

RESULTS Mean = 025570 mgkg

Repeatability variance S2r = 000158Repeatability std Sr = 003970 --gt 1553 r = 01112Between lab variance S2L = 001807Reproducibility var S2R = 001964Reproducibility std SR = 014015 --gt 5481 R = 03924Remarks 1 Lab rejected (46L)

000 050 100 150 200 250

k-values

10L

46L

4L

38L

12L

64L

26L

Mandels k statistics(Sludge 1 - Sum PBD)

-03 -02 -02 -01 -01 00 01 01 02 02

Deviation from Mean

10L

46L

4L

38L

12L

64L

26L

Labo

rato

ries

Sludge 1 - Sum PBD -- Mean PARM = 0256 [mgkg]

-200 -100 000 100 200

h-values

10L

46L

4L

38L

12L

64L

26L

Labo

rato

ries

Mandels h statistics(Sludge 1 - Sum PBD)

Sludge 1-Sum PBD

Unit mgkg

Mandels k statistics(Soil 3 - Sum PBD)Mandels h statistics(Soil 3 - Sum PBD)

Sample Soil 3 Soil 3 - Sum PBD -- Mean PARM = 0227 [mgkg]

Element Sum PBD

General calcparmT1= 610980E+00T2= 200876E+00T3= 26T4= 100T5= 13106E-02

n= variabelp= 7

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00028 0001 4 -037 000 Fail 00028 00005 4 3 -02226L 01179 0021 2 -036 003 Fail 01179 00208 2 1 -0114L 01305 0031 4 -036 004 Fail 01305 00308 4 3 -010

46L 02065 0035 4 -036 005 Fail 02065 00350 4 3 -00244L 02923 0037 4 -035 005 Fail 02923 00365 4 3 00712L 04051 0015 4 -034 002 Fail 04051 00149 4 3 01864L 04314 0022 4 -033 003 Fail 04314 00223 4 3 0203L 305500 2051 2 247 283 Fail - - 3L - - 3032

Totgem 4017 0276 mgkg 1-level 206 (181) 7 02266 (3L) 7 6Totstd= 10722 0717 5-level 175 (156) 1

RESULTS Mean = 022663 mgkg

Repeatability variance S2r = 000069Repeatability std Sr = 002626 --gt 1159 r = 00735Between lab variance S2L = 002568Reproducibility var S2R = 002637Reproducibility std SR = 016238 --gt 7165 R = 04547Remarks 1 Lab rejected (3L)

000 050 100 150 200 250 300

k-values

10L

26L

4L

46L

44L

12L

64L

3L

Mandels k statistics(Soil 3 - Sum PBD)

-50 00 50 100 150 200 250 300 350

Deviation from Mean

10L

26L

4L

46L

44L

12L

64L

3L

Labo

rato

ries

Soil 3 - Sum PBD -- Mean PARM = 0227 [mgkg]

-100 000 100 200 300

h-values

10L

26L

4L

46L

44L

12L

64L

3L

Labo

rato

ries

Mandels h statistics(Soil 3 - Sum PBD)

Soil 3-Sum PBD

19

Annex 4

Raw data submitted

Sample Compost1 Sample Compost 1 Sample Compost 1Element PBD 99 Element PBD 100 Element PBD 153

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]4L 00021 10L 00008 44L 000504L 00024 10L 00008 44L 000604L 00014 10L 00007 44L 000504L 00020 10L 00011 46L 00004

10L 00029 46L 00007 46L 0001210L 00027 46L 00012 46L 0000410L 00032 46L 00009 46L 0000946L 00025 46L 00007 12L 0000446L 00052 12L 00008 12L 0000846L 00029 12L 00012 12L 0000446L 00026 12L 00008 12L 0000712L 00026 12L 00014 26L 0000512L 00043 26L 00007 26L 0000512L 00026 26L 0000612L 0004726L 0002626L 00024

Sample Compost 1 Sample Compost 1 Sample Compost 1Element PBD 154 Element PBD 183 Element PBD 196

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]4L 00010 46L 00002 46L 00011

46L 00003 46L 00024 46L 0000846L 00007 46L 00021 12L 0000246L 00003 46L 00003 12L 0000346L 00004 12L 00003 12L 0000112L 00003 12L 00011 12L 0000212L 00005 12L 0000312L 00031 12L 0000312L 00006

Sample Compost 1 Sample Compost 1 Sample Compost 1Element PBD 197 Element PBD 203 Element PBD 209

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00002 46L 00010 4L 0004146L 00023 12L 00002 4L 0008946L 00022 12L 00003 44L 0041012L 00004 12L 00002 44L 0084012L 00006 12L 00002 44L 0064012L 00003 44L 0040012L 00004 12L 00079

12L 0007312L 0006512L 0009326L 0004926L 00049

Sample Compost 1Element PBD 47

LAB PARM [mgkg]26L 0003826L 00039

Element PBD 99 Element PBD 47 Element PBD 209LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]

4L 00170 10L 00210 4L 010004L 00200 10L 00220 4L 018004L 00170 10L 00210 4L 012004L 00190 46L 00300 4L 0220010L 00280 46L 00280 46L 0210010L 00300 46L 00250 46L 0200010L 00290 46L 00260 64L 0351846L 00340 64L 00059 64L 0363846L 00330 64L 00057 64L 0364546L 00300 64L 00062 64L 0350846L 00310 64L 00060 12L 0220964L 00194 12L 00191 12L 0177164L 00154 12L 00187 12L 0292264L 00185 12L 00190 12L 0164664L 00159 12L 00186 26L 0329712L 00242 26L 00666 26L 0300012L 00223 26L 0033212L 0022112L 0022226L 0024626L 00400

Element PBD 203 Element PBD 197 Element PBD 196LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00022 46L 00027 46L 0002446L 00014 46L 00024 46L 0002264L 00036 12L 00161 64L 0005864L 00058 12L 00060 64L 0006512L 00063 12L 00061 12L 0004812L 00034 12L 00036 12L 0002512L 00038 12L 0003212L 00027 12L 00022

Element PBD 183 Element PBD 154 Element PBD 153LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00049 4L 00020 4L 0002246L 00035 4L 00022 4L 0002446L 00036 4L 00020 4L 0002246L 00034 46L 00025 4L 0002664L 00027 46L 00025 46L 0004064L 00023 46L 00025 46L 0004264L 00024 46L 00023 46L 0003564L 00020 64L 00034 46L 0003812L 00230 64L 00023 64L 0007412L 00032 64L 00017 64L 0004712L 00031 64L 00011 64L 0004612L 00030 12L 00030 64L 0003026L 00007 12L 00021 12L 0006526L 00008 12L 00021 12L 00029

12L 00021 12L 0003226L 00015 12L 0002926L 00019 26L 00039

26L 00040

Element PBD 100LAB PARM [mgkg]

4L 000384L 000414L 000374L 00038

38L 0219038L 0220038L 0208038L 0220010L 0004410L 0005010L 0004310L 0004646L 0005746L 0005946L 0005346L 0005312L 0004312L 0004512L 0004312L 0004326L 0006226L 00057

Sample Soil 3 Sample Soil 3 Sample Soil 3Element PBD 99 Element PBD 47 Element PBD 100

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]10L 00016 10L 00011 10L 0000310L 00019 10L 00010 10L 0000410L 00013 10L 00012 10L 0000410L 00019 46L 00007 10L 0000246L 00025 46L 00022 46L 0000246L 00025 46L 00005 46L 0000646L 00008 46L 00007 46L 0000246L 00011 12L 00010 46L 0000264L 00005 12L 00017 3L 29100064L 00005 12L 00010 3L 32000064L 00006 12L 00009 26L 0000564L 00007 26L 00007 26L 0000512L 00012 26L 0000712L 0001312L 0001312L 0001226L 0000526L 00006

Sample Soil 3 Sample Soil 3 Sample Soil 3Element PBD 153 Element PBD 154 Element PBD 196

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]44L 00050 4L 00010 46L 0000744L 00050 46L 00001 46L 0001146L 00002 46L 00002 46L 0000846L 00003 46L 00001 46L 0001146L 00002 46L 00002 64L 0002646L 00002 64L 00001 64L 0002664L 00001 64L 00001 64L 0002964L 00001 64L 00001 64L 0003464L 00001 64L 00002 12L 0004564L 00002 12L 00003 12L 00032

12L 00002 12L 0002212L 00002 12L 0002112L 00002

Sample Soil 3 Sample Soil 3 Sample Soil 3Element PBD 197 Element PBD 203 Element PBD 209

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00006 46L 00011 4L 0091046L 00013 46L 00017 4L 0150046L 00011 46L 00015 4L 0120046L 00013 46L 00018 4L 0160012L 00090 64L 00013 44L 0337012L 00056 64L 00014 44L 0281012L 00033 64L 00016 44L 0287012L 00032 64L 00015 44L 02540

12L 00055 46L 0230012L 00041 46L 0220012L 00027 46L 0150012L 00026 46L 01900

64L 0438164L 0401664L 0414464L 0449812L 0367112L 0397812L 0409112L 03838

Sample Soil 3 26L 0102Element PBD 183 26L 0131

LAB PARM [mgkg]46L 0000746L 0000846L 0005846L 0000764L 0000264L 0000364L 0000364L 0000312L 0001512L 0001112L 0000712L 00007

European Commission EUR 23003 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on polybrominated diphenylethers Author(s) E Sobiecka H van der Sloot D Barcelo B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 68 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07403-5 Abstract Project HORIZONTAL is interdisciplinary aiming at a harmonisation and horizontal standardisation of test procedures in particular for sludge soils and biowastes In the context of this standardization project a series of draft technical specification were designed upon an extensive desk study fine-tuned after expert consultations and finally validated in international intercomparisons exercise This report summarises the work performed within the validation study of the draft standard for the determination of polybrominated diphenylethers (PBDE) in soils sludge and treated bio-waste using gas-chromatography method with mass selective detection (GC-MS) It further explains the underlying statistical concept for the calculation of reproducibility and repeatability from intercomparisons data In addition all single values results of the statistical evaluation as well as background information on the validation materials used are described and explained

The mission of the JRC is to provide customer-driven scientific and technical support for the conception development implementation and monitoring of EU policies As a service of the European Commission the JRC functions as a reference centre of science and technology for the Union Close to the policy-making process it serves the common interest of the Member States while being independent of special interests whether private or national

LB

-NA

-23003-EN

-C

16

Annex 1

Model questionnaire to be filled by the participating laboratories

Model questionnaire to be filled by the participating laboratories Name of laboratory Contact person Contact details email Phone Fax Mail address of lab Dispatch address of lab for shipment of samples (no PO boxes) Title of measurement method (copy attached) Our laboratory is willing to participate in the precision experiment for this draft standard method

Yes No As participant we understand that

bull All essential apparatus chemicals and other requirements specified in the method must be available in our laboratory when the programme begins

bull Specified timing requirements such as starting and finishing date of the programme must be rigidly met

bull The method must be strictly adhered to bull Samples must be handled in accordance with instructions bull A qualified operator must perform the measurements

Having studied the method and having made a fair appraisal of our capabilities and facilities we feel that we will be adequately prepared for cooperative testing of this method Comments helliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphellip Signature Date

17

Annex 2

Report on the validation materials used

VI

Abstract This report gives an overview on the available analytical information on the following raw materials to be used for the production of validation materials of the so-called Project HORIZONTAL

bull Four sludge materials from Duumlsseldorf Germany

bull An agricultural soil material from Reading United Kingdom

bull A compost material from Vienna Austria

bull A compost material from Korschenbroich Germany

bull A sludge-amended agricultural soil from Pavia Province Italy

bull A sludge-amended soil from Barcelona Spain

bull A sludge-amended soil from Essen Germany

bull A long-term sludge exposed soil from Hohenheim Germany

VII

List of Abbreviations Throughout this report the following abbreviations are used

AOX absorbable organic halogens

Corg organic carbon content

Ctotal total carbon content

CAT cation exchangeable

CDD chlorinated dibenzodioxin

CDF chlorinated dibenzofuran

DEHP di(2-ethylhexyl)phthalate

DM dry matter

EPA Environment Protection Agency

EU European Union

FM fresh matter

Hp hepta

Hx hexa

IES Institute for Environment and Sustainability

IRMM Institute for Reference Materials and Measurements

JRC Joint Research Centre

LAS linear alkylsulfonates

LoD limit of detection

LUA Landesumweltamt

Ntotal total nitrogen content

NH4-N Ammonium nitrogen

NO3-N Nitrate nitrogen

NP nonylphenol

NRW North Rhine Westphalia

O octa

P poly

PAH polycyclic aromatic hydrocarbon

PCB polychlorinated biphenyl

Pe penta

T tetra

TEQ toxicity equivalent

UBA Umweltbundesamt

WHO World Health Organization

WWTP waste water treatment plant

6

1 Introduction This report gives an overview on the available analytical information on the following raw materials to be used for the production of validation materials of the so-called Project HORIZONTAL

bull Four sludge materials from Duumlsseldorf Germany

bull An agricultural soil material from Reading United Kingdom

bull A compost material from Vienna Austria

bull A compost material from Korschenbroich Germany

bull A sludge-amended agricultural soil from Pavia Province Italy

bull A sludge-amended soil from Barcelona Spain

bull A sludge-amended soil from Essen Germany

bull A long-term sludge exposed soil from Hohenheim Germany

The following analytical information was gathered partly before and during the sampling of the raw materials to be used for the production of the HORIZONTAL validation materials The material were sampled by IES and shipped to IRMM in the course of the year 2005 The information gathered was then completed by various analytical screenings for PAHs and PCBs done by the Institute for Reference Materials and Measurements Geel Belgium for phthalates done by UBA Berlin Germany for PBDE done by IIQAB-CSIC Barcelona Spain for trace elements and some selected major and minor elements by the Institute for Environment and Sustainability Ispra Italy

The work compiled hereafter is based on the numerous additional efforts of the scientists working at various members of the consortium Project HORIZONTAL-Org and contributing organisations

This work is gratefully acknowledged

2 Overview on property values

21 Sludge materials from Duumlsseldorf Germany

The various sewage sludge materials originate from various installations in the North Rhine Westphalia and were produced and sampled by staff from the Landesumweltamt (LUA) NRW under the responsibility from Dr K Furtmann

In total four sludge materials (Sludge A and D from a major municipal WWTP Sludge B from a municipal WWTP with industrial input and Sludge C from a municipal WWTP with high PCB-Content) were obtained and will be blended to two final materials Before sampling the following analytical data for a typical sample were received

7

Table 1 ndash Analytical data obtained on an average sludge sample in LUA NRW (with courtesy of K Furtmann LUA Duumlsseldorf)

Parameter Concentration PCB 120 ugkg DEHP 110 mgkg PAH 5 mgkg (EPA) PCDDF 15 ng TEkg PBDE 400 ugkg NP 40 mgkg LAS 3 gkg AOX 300 mgkg

Subsequent screening led to the information displayed hereafter It should be stressed that the data were obtained as SCREENING information on the UNTREATED or partially treated raw materials Therefore the final target values which are relevant for the validation intercomparison can be different

Table 2 ndash Analytical data obtained on a first screening on the sludge samples from LUA NRW

Sewage sludge A

Dusseldorf

sewage sludge D

Dusseldorf PCB (ngg) 28 62 35 52 101 65 101 31 38 118 49 40 153 30 33 105 24 11 138 46 38 156 lt1 lt1 180 34 23 170 23 19 PAH (ngg) Naphtalene 34 381 Acenaphtylene 15 43 Acenaphthene 81 108 Fluorene 94 1167 Phenantrene 3440 Anthracene 22 344 Flouranthene 316 4817 Pyrene 235 3011 Benz(a)anthracene 473 791 Chrysene 691 1078 Benz(b)fluoranthene 538 1688 Benz(k)fluoranthene 228 635 Benz(a)pyrene 383 1114 Indeno(123-cd)pyrene 92 229 Dibenzo(ah)anthracene 71 70 Benzo(ghi)perylene 80 185

8

Table 3 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Sludge D (1) 0135 41474 385 Sludge B (2) 0538 0034 30634 547 Sludge A (3) 0184 0037 31399 146 Sludge C (4) 0354 1528 6678 229

Table 4 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Sludge 2

(B)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

554

959

694

591

772

509

nq

nq

970

2216

2379

Table 5 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena IES Ispra Spain) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Sludge 1 (D) 265 290 533 359 1231 338 784 438 lt 005 232 786 Sludge 2 (B) 119 311 626 202 278 299 722 251 lt 005 118 625 Sludge 3 (A) 168 360 621 332 847 416 119 451 lt 005 116 1237 Sludge 4 (C) 563 198 116 273 726 511 473 618 lt 005 444 2015

Table 6 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Sludge 1 (D) 2154 58 844 099 103 101 4367 lt15 50448 Sludge 2 (B) 1067 366 692 046 1491 077 5217 lt15 57633 Sludge 3 (A) 731 663 684 035 1287 068 3733 lt15 60369 Sludge 4 (C) 4379 965 527 163 522 107 5628 lt15 23945

Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM)Sludge 1 (D) 03 2403 101 1002 350 15 1944 132Sludge 2 (B) 031 315 97 879 172 12 514 180Sludge 3 (A) 031 1281 153 1567 265 16 1440 168Sludge 4 (C) 055 231 628 2625 371 81 1101 244

9

22 Agricultural soil material from Reading United Kingdom

The material was proposed by the University of Reading (S Nortcliff) and was sampled from a site called ldquoFrogmore Farmrdquo which was featured in the ldquoMetalsrdquo Report for HORIZONTAL This site is close to Reading with soils developed on flintyloamy periglacial materials over Chalk has a long and well documented history of sludge application The focus of the work of Nortcliff et al undertook at this site and the monitoring and control at the site (by Thames Water and the subsequent subsidiary bodies dealing with sludge application to soil) was on metals (and metal loads) with no analysis or indeed any form of investigation in to organics in the broadest sense

The analytical information produced in the context of the screening of the raw material is displayed below

Table 7 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 3

(Reading) 0032 0119 669

Table 8 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 3 (Reading) 015 706 279 138 152 901 267 300 lt 005 258 931

Table 9 ndash Analytical data obtained on a first screening on the sludge-amended soil from Reading (courtesy of IRMM)

Parameter Concentration

PCB ngg 28 lt1 52 lt1 101 lt1 118 lt1 153 lt1 105 lt1 138 lt1 156 lt1 180 lt1 170 lt1 PAH ngg Naphtalene lt10 Acenaphtylene 21 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene lt10 Flouranthene 818 Pyrene 776 Benz(a)anthracene 565

10

Parameter Concentration

Chrysene 608 Benz(b)fluoranthene 824 Benz(k)fluoranthene 329 Benz(a)pyrene 799 Indeno(123-cd)pyrene

779

Dibenzo(ah)anthracene 118 Benzo(ghi)perylene 394

Table 10 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 3

(Reading)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

103

003

nq

nq

nq

nd

nd

272

273

Table 11 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 3 (Reading) 015 706 279 138 152 901 267 300 lt 005 258 931

Table 12 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 3 (Reading) 7936 477 112 096 194 017 4107 443 2102 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 3 (Reading) 042 13 45 69 69 69 216 92

Table 13 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 3 (Reading) 012

11

23 Compost from Vienna Austria

The fresh compost material was obtained from the Austrian Federal Environment Agency (UBA Vienna) which had used a sub-batch of the raw material for national intercomparson The remainder of the material was stored at 4degC until shipment to IRMM for further processing The following analytical information was provided by UBA Austria and completed with various screenings

Table 14 ndash Analytical data on compost material received from UBA Austria Inorganic and sum parameters

Parameter Unit Sample fraction used Observed mean B CAT mgl FM Fresh sample lt10mm 61 K CAT mgl FM Fresh sample lt10mm 2624 Mg CAT mgl FM Fresh sample lt10mm 242 P CAT mgl FM Fresh sample lt10mm 49 B CAT DM Fresh sample lt10mm 00017 K CAT DM Fresh sample lt10mm 072 Mg CAT DM Fresh sample lt10mm 007 P CAT DM Fresh sample lt10mm 001 NO3-N mgkg FM Fresh sample lt10mm 35 NH4-N mgkg FM Fresh sample lt10mm 230 Ctotal DM lt45degdry milled 29 Corg DM lt45degdry milled 27 Ntotal DM lt45degdry milled 17 P mgkg DM lt45degdry milled 2596 K mgkg DM lt45degdry milled 11019 K DM lt45degdry milled 110 B mgkg DM lt45degdry milled 60 Cd mgkg DM lt45degdry milled 046 Cr mgkg DM lt45degdry milled 25 Cu mgkg DM lt45degdry milled 46 Hg mgkg DM lt45degdry milled 020 Ni mgkg DM lt45degdry milled 18 Pb mgkg DM lt45degdry milled 45 Zn mgkg DM lt45degdry milled 198 Ca mgkg DM lt45degdry milled 68776 Ca DM lt45degdry milled 69 Mo mgkg DM lt45degdry milled 08 S mgkg DM lt45degdry milled 2137 Fe mgkg DM lt45degdry milled 9959 Mn mgkg DM lt45degdry milled 418 Na mgkg DM lt45degdry milled 742 Co mgkg DM lt45degdry milled 41 AOX mgkg DM lt30deg dry milled 62

Table 15 ndash Analytical data on compost material received from UBA Austria Polycyclic aromatic hydrocarbons

PAH Unit Result Naphthaline microgkg DM 93 Acenaphthylene microgkg DM 86 Acenaphthene microgkg DM 5 Fluorene microgkg DM 80 Phenanthrene microgkg DM 89 Anthracene microgkg DM 27 Fluoranthene microgkg DM 487 Pyrene microgkg DM 380

12

PAH Unit Result Benzo(a)anthracene microgkg DM 278 Chrysene microgkg DM 317 Benzo(b)fluoranthene microgkg DM 365 Benzo(k)fluoranthene microgkg DM 193 Benz(a)pyrene microgkg DM 320 Indeno(123-cd)pyrene microgkg DM 233 Dibenz(ah)anthracene microgkg DM 67 Benzo(ghi)perylene microgkg DM 225 Sum EPA microgkg DM 3013 Sum EPA mgkg DM 30

Table 16 ndash Analytical data on compost material received from UBA Austria Sum PCDDs and PCBs

Parameter

Dioxine TEQ (ITEF) ngkg DM 73 TEQ (WHO) ngkg DM 35 PCB Σ Ballschmiter mgkg DM 005

Table 17 ndash Analytical data on compost material obtained by screening in IRMM

Parameter Result in ngg

PCB 28 2 52 2 101 4 118 3 153 10 105 1 138 8 156 1 180 5 170 lt1 PAH Naphtalene lt10 Acenaphtylene lt10 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene 26 Fluoranthene 611 Pyrene 510 Benz(a)anthracene 888 Chrysene 957 Benz(b)fluoranthene 1531 Benz(k)fluoranthene 547 Benz(a)pyrene 1101 Indeno(123-cd)pyrene 416 Dibenzo(ah)anthracene 81 Benzo(ghi)perylene 295

13

Table 18 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Compost 1

(Vienna)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

402

019

259

nq

023

004

nq

nq

144

174

259

Table 19 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Compost 1

(Vienna) 0058 1426 557

Table 20 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Compost 1 (Vienna) 039 736 319 410 365 127 495 004 079 013 208

Table 21 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Compost 1 (Vienna) 2063 431 617 426 199 249 1602 lt15 10521

Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Compost 1 (Vienna) 035 3496 81 375 79 55 653 60

Table 22 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Compost 1 (Vienna) 017

14

24 Agricultural soil sludge amended soil from Pavia Italy

This sludge-amended soil material was obtained during a monitoring campaign which aimed at a generic description of the over-all soil quality in Pavia Province Italy The material which was collected from the upper horizon originates from a small farm called ldquoCascina Novellordquo During the characterisation of the site the following analytical information was obtained on a pooled sample of a sub-area of the farm of 20 X 20 m2

Table 23 ndash Analytical data on Pavia soil

Parameter Result Al 713 Wgt As 224 mgkg Cd 079 mgkg Cr 59 mgkg Cu 308 mgkg Hg 008 mgkg Ni 344 mgkg Pb 246 mgkg Zn 95 mgkg C 091 Wgt 2378-TCDD 0047 pgg 12378-PeCDD 015 pgg 123478-HxCDD 019 pgg 123678-HxCDD 15 pgg 123789-HxCDD 074 pgg 1234678-HpCDD 26 pgg OCDD 382 pgg 2378-TCDF 068 pgg 12378-PeCDF 053 pgg 23478-PeCDF 071 pgg 123478-HxDF 100 pgg 123678-HxDF 066 pgg 234678-HxDF 16 pgg 123789-HxDF 027 pgg 1234678-HpDF 12 pgg 1234789-HpDF 068 pgg OCDF 33 pgg I-TEQ 20 pgg WHO-TEQ 17 pgg

In addition the screening performed at IRMM did not reveal significant quantities of PCBs and PAHs which were all below the LoDs (1 ngg for PCBs and 10 ngg for PAHs respectively)

Table 24 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 5 (Pavia) 0005 0011 154

15

Table 25 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 5

(Pavia)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

039

nq

nq

008

nq

nd

nd

670

671

Table 26 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 5 (Pavia) 033 184 573 225 426 305 206 200 lt 005 381 878

Table 27 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 5 (Pavia) 6939 129 145 224 425 116 6118 255 1789 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 5 (Pavia) 184 62 38 108 55 66 597 110

Table 28 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 5 (Pavia) 006

16

25 Sludge-amended-soil from Barcelona Spain

The sludge-amended soil material from Barcelona sampled upon indication from the Barcelorsquo- Group in Barcelona

Table 29 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 2 (Lleida T) 0015 0183 1138

Table 30 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 2

(Lleida T)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

159

045

nq

048

160

nq

nq

1000

1004

Table 31 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 2 (Lleida T) 059 141 327 536 405 186 184 224 lt 005 318 111

Table 32 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 2 (Lleida T) 4443 1067 1429 253 344 204 4116 780 3396 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 2 (Lleida T) 064 65 26 125 59 17 547 65

Table 33 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 2 (Lleida T) 010

17

26 Sludge amended soil from Essen Germany

The German sludge-amended soil from Essen which was provided as the three sludge materials by LUA NRW did not feature significant concentrations of the PCB congeners 28 52 101 118 153 105 138 156 180 170 but had detectable amounts of some PAHs

Table 34 ndash Analytical screening data on the German sludge-amended soil

Parameter Concentration(ngg)

Naphtalene lt10 Acenaphtylene lt10 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene lt10 Fluoranthene 28 Pyrene 20 Benz(a)anthracene 24 Chrysene 47 Benz(b)fluoranthene 76 Benz(k)fluoranthene 20 Benz(a)pyrene 35 Indeno(123-cd)pyrene 35 Dibenzo(ah)anthracene 10 Benzo(ghi)perylene 26

Table 35 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 4 (Essen) 0011 0302 055

Table 36 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 4

(Essen)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

nq

nq

nq

nq

nq

nq

128

191

203

18

Table 37 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 4 (Essen) 052 545 261 805 320 403 273 273 lt 005 295 781

Table 38 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 4 (Essen) 7947 442 085 06 086 007 2163 189 2019 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 4 (Essen) 045 19 42 87 683 60 462 61

Table 39 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 4 (Essen) 004

27 Long-term sludge exposed soil from Hohenheim-Stuttgart Germany

Similarly an additional sludge exposed soil was sampled at the University of Hohenheim Stuttgart were a test soil was long-term exposed to elevated concentrations of sewage sludge

Table 40 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 1 (Stuttgart) 0045 0263 1765

Table 41 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 1

(Stuttgart)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

230

006

004

004

nq

nd

nd

498

500

19

Table 42 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 1 (Stuttgart) 069 127 361 262 504 183 252 262 lt 005 266 142

Table 43 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 1 (Stuttgart) 7194 1006 133 186 366 088 7874 275 3571 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 1 (Stuttgart) 123 50 47 212 85 69 991 129

Table 44 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 1 (Stuttgart) 177

18

Annex 3

Statistical calculations

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 47)Mandels h statistics(Sludge 1 - PBD 47)

Sample Sludge 1 NUM

Element PBD 47

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00213 0001 3 -021 005 - - 10L - - NUM46L 00273 0002 4 016 021 - - 46L - - NUM64L 00059 0000 4 -116 002 NUM - 64L - - NUM12L 00188 0000 4 -036 002 - - 12L - - NUM26L 00499 0024 2 157 223 Fail - - 26L - - NUM

Totgem 0025 0005 mgkg 1-level 172 (185) NUM (10L46L64L12L26L) -1Totstd= 0016 0010 5-level 157 (162) 5

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 5 Labs rejected (10L46L64L12L26L)

000 050 100 150 200 250

k-values

10L

46L

64L

12L

26L

Mandels k statistics(Sludge 1 - PBD 47)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

10L

46L

64L

12L

26L

Labo

rato

ries

NUM

-200 -100 000 100 200

h-values

10L

46L

64L

12L

26L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 47)

Sludge 1-PBD 47

Unit mgkg

Mandels k statistics(Soil 3 - PBD 47)Mandels h statistics(Soil 3 - PBD 47)

Sample Soil 3 Soil 3 - PBD 47 -- Mean PARM = 0001 [mgkg]

Element PBD 47

General calcparmT1= 134814E-02T2= 142830E-05T3= 13T4= 45T5= 22767E-06

n= variabelp= 4

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean26L 00007 0000 2 -143 001 00007 00000 2 1 00046L 00010 0001 4 010 181 00010 00008 4 3 00010L 00011 0000 3 049 023 00011 00001 3 2 00012L 00012 0000 4 084 081 00012 00004 4 3 000

Totgem 0001 0000 mgkg 1-level 149 (177) 4 00010 () 4 3Totstd= 0000 0000 5-level 142 (159)

RESULTS Mean = 000100 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000050 --gt 5031 r = 00014Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000050 --gt 5031 R = 00014Remarks none

000 050 100 150 200

k-values

26L

46L

10L

12L

Mandels k statistics(Soil 3 - PBD 47)

00 00 00 00 00 00 00 00 00 00 00

Deviation from Mean

26L

46L

10L

12L

Labo

rato

ries

Soil 3 - PBD 47 -- Mean PARM = 0001 [mgkg]

-200 -100 000 100

h-values

26L

46L

10L

12L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 47)

Soil 3-PBD 47

Unit mgkg

Mandels k statistics(Compost 1 - PBD 99)Mandels h statistics(Compost 1 - PBD 99)

Sample Compost 1 Compost 1 - PBD 99 -- Mean PARM = 0003 [mgkg]

Element PBD 99

General calcparmT1= 492124E-02T2= 148747E-04T3= 17T4= 61T5= 93196E-06

n= variabelp= 5

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00020 0000 4 -137 053 00020 00004 4 3 000

26L 00025 0000 2 -058 024 00025 00002 2 1 00010L 00029 0000 3 012 032 00029 00003 3 2 00046L 00033 0001 4 069 161 00033 00013 4 3 00012L 00036 0001 4 114 140 00036 00011 4 3 000

Totgem 0003 0001 mgkg 1-level 172 (185) 5 00029 () 5 4Totstd= 0001 0001 5-level 157 (162)

RESULTS Mean = 000286 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000088 --gt 3086 r = 00025Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000101 --gt 3525 R = 00028Remarks none

000 050 100 150 200

k-values

4L

26L

10L

46L

12L

Mandels k statistics(Compost 1 - PBD 99)

00 00 00 00 00 00 00 00 00 00

Deviation from Mean

4L

26L

10L

46L

12L

Labo

rato

ries

Compost 1 - PBD 99 -- Mean PARM = 0003 [mgkg]

-200 -100 000 100 200

h-values

4L

26L

10L

46L

12L

Labo

rato

ries

Mandels h statistics(Compost 1 - PBD 99)

Compost 1-PBD 99

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 99)Mandels h statistics(Sludge 1 - PBD 99)

Sample Sludge 1 Sludge 1 - PBD 99 -- Mean PARM = 0024 [mgkg]

Element PBD 99

General calcparmT1= 448050E-01T2= 112113E-02T3= 19T4= 73T5= 32972E-05

n= variabelp= 5

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean64L 00173 0002 4 -118 041 Fail 00173 00019 4 3 -0014L 00183 0002 4 -104 032 00183 00015 4 3 -001

12L 00227 0001 4 -038 022 00227 00010 4 3 00010L 00290 0001 3 055 021 00290 00010 3 2 00146L 00320 0002 4 100 039 00320 00018 4 3 00126L 00323 0011 2 105 234 - - 26L - - 001

Totgem 0025 0003 mgkg 1-level 187 (177) 5 00239 (26L) 5 4Totstd= 0007 0004 5-level 166 (154) 1

RESULTS Mean = 002385 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000153 --gt 643 r = 00043Between lab variance S2L = 000004Reproducibility var S2R = 000004Reproducibility std SR = 000666 --gt 2791 R = 00186Remarks 1 Lab rejected (26L)

000 050 100 150 200 250

k-values

64L

4L

12L

10L

46L

26L

Mandels k statistics(Sludge 1 - PBD 99)

00 00 00 00 00 00 00 00 00 00

Deviation from Mean

64L

4L

12L

10L

46L

26L

Labo

rato

ries

Sludge 1 - PBD 99 -- Mean PARM = 0024 [mgkg]

-200 -100 000 100 200

h-values

64L

4L

12L

10L

46L

26L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 99)

Sludge 1-PBD 99

Unit mgkg

Mandels k statistics(Soil 3 - PBD 99)Mandels h statistics(Soil 3 - PBD 99)

Sample Soil 3 NUM

Element PBD 99

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00017 0000 4 091 068 - - 10L - - NUM46L 00017 0001 4 100 211 - - 46L - - NUM64L 00005 0000 4 -106 023 NUM - 64L - - NUM12L 00012 0000 4 015 014 - - 12L - - NUM26L 00006 0000 2 -101 012 - - 26L - - NUM

Totgem 0001 0000 mgkg 1-level 172 (173) NUM (10L46L64L12L26L) -1Totstd= 0001 0000 5-level 157 (153) 5

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 5 Labs rejected (10L46L64L12L26L)

000 050 100 150 200 250

k-values

10L

46L

64L

12L

26L

Mandels k statistics(Soil 3 - PBD 99)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

10L

46L

64L

12L

26L

Labo

rato

ries

NUM

-200 -100 000 100 200

h-values

10L

46L

64L

12L

26L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 99)

Soil 3-PBD 99

Unit mgkg

Mandels k statistics(Compost 1 - PBD 100)Mandels h statistics(Compost 1 - PBD 100)

Sample Compost 1 Compost 1 - PBD 100 -- Mean PARM = 0001 [mgkg]

Element PBD 100

General calcparmT1= 124272E-02T2= 113129E-05T3= 14T4= 52T5= 46584E-07

n= variabelp= 4

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean26L 00006 0000 2 -131 037 Fail 00006 00001 2 1 00010L 00009 0000 4 003 083 00009 00002 4 3 00046L 00009 0000 4 016 115 00009 00002 4 3 00012L 00011 0000 4 112 136 Fail 00011 00003 4 3 000

Totgem 0001 0000 mgkg 1-level 149 (167) 4 00009 () 4 3Totstd= 0000 0000 5-level 142 (15)

RESULTS Mean = 000085 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000022 --gt 2531 r = 00006Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000025 --gt 2882 R = 00007Remarks none

000 050 100 150

k-values

26L

10L

46L

12L

Mandels k statistics(Compost 1 - PBD 100)

00 00 00 00 00 00 00 00 00 00 00

Deviation from Mean

26L

10L

46L

12L

Labo

rato

ries

Compost 1 - PBD 100 -- Mean PARM = 0001 [mgkg]

-200 -100 000 100 200

h-values

26L

10L

46L

12L

Labo

rato

ries

Mandels h statistics(Compost 1 - PBD 100)

Compost 1-PBD 100

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 100)Mandels h statistics(Sludge 1 - PBD 100)

Sample Sludge 1 Sludge 1 - PBD 100 -- Mean PARM = 0005 [mgkg]

Element PBD 100

General calcparmT1= 852065E-02T2= 412762E-04T3= 18T4= 68T5= 78914E-07

n= variabelp= 5

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00039 0000 4 -042 007 Fail 00039 00002 4 3 000

12L 00044 0000 4 -041 005 Fail 00044 00001 4 3 00010L 00046 0000 4 -041 013 Fail 00046 00003 4 3 00046L 00056 0000 4 -040 012 Fail 00056 00003 4 3 00026L 00059 0000 2 -040 013 Fail 00059 00003 2 1 00038L 02168 0006 4 204 244 Fail - - 38L - - 021

Totgem 0040 0001 mgkg 1-level 187 (177) 5 00049 (38L) 5 4Totstd= 0087 0002 5-level 166 (154) 1

RESULTS Mean = 000486 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000025 --gt 507 r = 00007Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000084 --gt 1731 R = 00024Remarks 1 Lab rejected (38L)

000 050 100 150 200 250

k-values

4L

12L

10L

46L

26L

38L

Mandels k statistics(Sludge 1 - PBD 100)

-01 00 01 01 02 02 03

Deviation from Mean

4L

12L

10L

46L

26L

38L

Labo

rato

ries

Sludge 1 - PBD 100 -- Mean PARM = 0005 [mgkg]

-100 000 100 200 300

h-values

4L

12L

10L

46L

26L

38L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 100)

Sludge 1-PBD 100

Unit mgkg

Mandels k statistics(Soil 3 - PBD 100)Mandels h statistics(Soil 3 - PBD 100)

Sample Soil 3 NUM

Element PBD 100

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00003 0000 4 -050 000 Fail - - 10L - - NUM46L 00003 0000 4 -050 000 Fail NUM - 46L - - NUM3L 305500 2051 2 150 200 Fail - - 3L - - NUM

26L 00005 0000 2 -050 000 Fail - - 26L - - NUM

Totgem 7638 0513 mgkg 1-level 149 (177) NUM (10L46L3L26L) -1Totstd= 15275 1025 5-level 142 (159) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (10L46L3L26L)

000 050 100 150 200

k-values

10L

46L

3L

26L

Mandels k statistics(Soil 3 - PBD 100)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

10L

46L

3L

26L

Labo

rato

ries

NUM

-100 000 100 200

h-values

10L

46L

3L

26L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 100)

Soil 3-PBD 100

Unit mgkg

Mandels k statistics(Compost 1 - PBD 153)Mandels h statistics(Compost 1 - PBD 153)

Sample Compost 1 NUM

Element PBD 153

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean44L 00053 0001 3 150 157 Fail - - 44L - - NUM46L 00007 0000 4 -044 111 Fail - - 46L - - NUM12L 00005 0000 4 -051 055 Fail - - 12L - - NUM26L 00005 0000 2 -054 001 Fail NUM - 26L - - NUM

Totgem 0002 0000 mgkg 1-level 149 (177) NUM (44L46L12L26L) -1Totstd= 0002 0000 5-level 142 (159) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (44L46L12L26L)

000 050 100 150 200

k-values

44L

46L

12L

26L

Mandels k statistics(Compost 1 - PBD 153)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

44L

46L

12L

26L

Labo

rato

ries

NUM

-100 000 100 200

h-values

44L

46L

12L

26L

Labo

rato

ries

Mandels h statistics(Compost 1 - PBD 153)

Compost 1-PBD 153

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 153)Mandels h statistics(Sludge 1 - PBD 153)

Sample Sludge 1 Sludge 1 - PBD 153 -- Mean PARM = 0004 [mgkg]

Element PBD 153

General calcparmT1= 676738E-02T2= 267609E-04T3= 18T4= 68T5= 19626E-05

n= variabelp= 5

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00024 0000 4 -157 017 00024 00002 4 3 000

12L 00038 0002 4 006 154 00038 00018 4 3 00046L 00039 0000 4 011 026 00039 00003 4 3 00026L 00039 0000 2 018 004 00039 00000 2 1 00064L 00049 0002 4 122 159 00049 00018 4 3 000

Totgem 0004 0001 mgkg 1-level 172 (173) 5 00038 () 5 4Totstd= 0001 0001 5-level 157 (153)

RESULTS Mean = 000378 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000123 --gt 3252 r = 00034Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000142 --gt 3754 R = 00040Remarks none

000 050 100 150 200

k-values

4L

12L

46L

26L

64L

Mandels k statistics(Sludge 1 - PBD 153)

00 00 00 00 00 00 00

Deviation from Mean

4L

12L

46L

26L

64L

Labo

rato

ries

Sludge 1 - PBD 153 -- Mean PARM = 0004 [mgkg]

-200 -100 000 100 200

h-values

4L

12L

46L

26L

64L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 153)

Sludge 1-PBD 153

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 154)Mandels h statistics(Sludge 1 - PBD 154)

Sample Sludge 1 NA

Element PBD 154

General calcparmT1= NAT2= NAT3=T4=T5=

n= variabelp=

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00021 0000 3 -100 021 NA - 4L - - NA

46L 00025 0000 4 115 018 NA - 46L - - NA64L 00021 0001 4 -066 179 - - 64L - - NA12L 00023 0000 4 050 085 - - 12L - - NA

Totgem 0002 0000 mgkg 1-level 149 (167) NA (4L46L64L12L) -1Totstd= 0000 0000 5-level 142 (15) 4

RESULTS Mean = NA mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NAReproducibility var S2R = NAReproducibility std SR = NA --gt NA R = NARemarks 4 Labs rejected (4L46L64L12L)

000 050 100 150 200

k-values

4L

46L

64L

12L

Mandels k statistics(Sludge 1 - PBD 154)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

4L

46L

64L

12L

Labo

rato

ries

NA

-100 000 100 200

h-values

4L

46L

64L

12L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 154)

Sludge 1-PBD 154

Unit mgkg

Mandels k statistics(Soil 3 - PBD 154)Mandels h statistics(Soil 3 - PBD 154)

Sample Soil 3 NUM

Element PBD 154

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

4L 00010 - 1 150 Fail - - 4L - - NUM46L 00001 0000 4 -053 096 Fail - - 46L - - NUM64L 00001 0000 4 -056 105 Fail NUM - 64L - - NUM12L 00002 0000 4 -040 099 Fail - - 12L - - NUM

Totgem 000037 0000 mgkg 1-level 149 (164) NUM (4L46L64L12L) -1Totstd= 000042 0000 5-level 142 (153) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (4L46L64L12L)

000 050 100 150

k-values

4L

46L

64L

12L

Mandels k statistics(Soil 3 - PBD 154)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

4L

46L

64L

12L

Labo

rato

ries

NUM

-100 000 100 200

h-values

4L

46L

64L

12L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 154)

Soil 3-PBD 154

Unit mgkg

Mandels k statistics(Compost 1 - PBD 209)Mandels h statistics(Compost 1 - PBD 209)

Sample Compost 1 NUM

Element PBD 209

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00065 0003 2 -049 032 - - 4L - - NUM

44L 00573 0021 4 150 197 Fail - - 44L - - NUM12L 00078 0001 4 -045 011 - - 12L - - NUM26L 00049 0000 2 -056 000 NUM - 26L - - NUM

Totgem 0019 0006 mgkg 1-level 149 (177) NUM (4L44L12L26L) -1Totstd= 0025 0010 5-level 142 (159) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (4L44L12L26L)

000 050 100 150 200

k-values

4L

44L

12L

26L

Mandels k statistics(Compost 1 - PBD 209)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

4L

44L

12L

26L

Labo

rato

ries

NUM

-100 000 100 200

h-values

4L

44L

12L

26L

Labo

rato

ries

Mandels h statistics(Compost 1 - PBD 209)

Compost 1-PBD 209

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 209)Mandels h statistics(Sludge 1 - PBD 209)

Sample Sludge 1 Sludge 1 - PBD 209 -- Mean PARM = 0249 [mgkg]

Element PBD 209

General calcparmT1= 394542E+00T2= 107296E+00T3= 16T4= 56T5= 19723E-02

n= variabelp= 5

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 01550 0055 4 -112 148 Fail 01550 00551 4 3 -009

46L 02050 0007 2 -053 019 02050 00071 2 1 -00412L 02137 0058 4 -042 155 02137 00576 4 3 -00426L 03149 0021 2 078 057 Fail 03149 00210 2 1 00764L 03577 0007 4 129 020 Fail 03577 00074 4 3 011

Totgem 0249 0030 mgkg 1-level 172 (185) 5 02493 () 5 4Totstd= 0084 0025 5-level 157 (162)

RESULTS Mean = 024926 mgkg

Repeatability variance S2r = 000179Repeatability std Sr = 004234 --gt 1699 r = 01186Between lab variance S2L = 000743Reproducibility var S2R = 000922Reproducibility std SR = 009604 --gt 3853 R = 02689Remarks none

000 050 100 150 200

k-values

4L

46L

12L

26L

64L

Mandels k statistics(Sludge 1 - PBD 209)

-01 -01 00 01 01 02

Deviation from Mean

4L

46L

12L

26L

64L

Labo

rato

ries

Sludge 1 - PBD 209 -- Mean PARM = 0249 [mgkg]

-200 -100 000 100 200

h-values

4L

46L

12L

26L

64L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 209)

Sludge 1-PBD 209

Unit mgkg

Mandels k statistics(Soil 3 - PBD 209)Mandels h statistics(Soil 3 - PBD 209)

Sample Soil 3 Soil 3 - PBD 209 -- Mean PARM = 0258 [mgkg]

Element PBD 209

General calcparmT1= 596398E+00T2= 191917E+00T3= 22T4= 84T5= 13249E-02

n= variabelp= 6

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean26L 01162 0021 2 -108 074 Fail 01162 00207 2 1 -0144L 01303 0031 4 -097 111 Fail 01303 00312 4 3 -013

46L 01975 0036 4 -046 128 Fail 01975 00359 4 3 -00644L 02898 0035 4 024 124 Fail 02898 00346 4 3 00312L 03895 0018 4 100 065 Fail 03895 00181 4 3 01364L 04260 0022 4 127 078 Fail 04260 00219 4 3 017

Totgem 0258 0027 mgkg 1-level 187 (177) 6 02582 () 6 5Totstd= 0132 0008 5-level 166 (154)

RESULTS Mean = 025818 mgkg

Repeatability variance S2r = 000083Repeatability std Sr = 002878 --gt 1115 r = 00806Between lab variance S2L = 001640Reproducibility var S2R = 001723Reproducibility std SR = 013127 --gt 5084 R = 03676Remarks none

000 050 100 150

k-values

26L

4L

46L

44L

12L

64L

Mandels k statistics(Soil 3 - PBD 209)

-02 -01 -01 00 01 01 02 02

Deviation from Mean

26L

4L

46L

44L

12L

64L

Labo

rato

ries

Soil 3 - PBD 209 -- Mean PARM = 0258 [mgkg]

-200 -100 000 100 200

h-values

26L

4L

46L

44L

12L

64L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 209)

Soil 3-PBD 209

Unit mgkg

Mandels k statistics(Compost 1 - Sum PBD)Mandels h statistics(Compost 1 - Sum PBD)

Sample Compost 1 Compost 1 - Sum PBD -- Mean PARM = 0009 [mgkg]

Element Sum PBD

General calcparmT1= 154064E-01T2= 169065E-03T3= 18T4= 68T5= 11354E-04

n= variabelp= 5

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00031 0002 4 -067 016 00031 00016 4 3 -0014L 00055 0005 4 -056 048 00055 00047 4 3 000

46L 00085 0003 4 -042 031 00085 00030 4 3 00026L 00123 0000 2 -024 003 00123 00002 2 1 00012L 00154 0002 4 -011 021 00154 00021 4 3 00144L 00613 0023 4 200 237 Fail - - 44L - - 005

Totgem 0018 0006 mgkg 1-level 187 (177) 5 00089 (44L) 5 4Totstd= 0022 0009 5-level 166 (154) 1

RESULTS Mean = 000893 mgkg

Repeatability variance S2r = 000001Repeatability std Sr = 000296 --gt 3308 r = 00083Between lab variance S2L = 000002Reproducibility var S2R = 000003Reproducibility std SR = 000570 --gt 6374 R = 00159Remarks 1 Lab rejected (44L)

000 050 100 150 200 250

k-values

10L

4L

46L

26L

12L

44L

Mandels k statistics(Compost 1 - Sum PBD)

00 00 00 00 00 00 01 01

Deviation from Mean

10L

4L

46L

26L

12L

44L

Labo

rato

ries

Compost 1 - Sum PBD -- Mean PARM = 0009 [mgkg]

-100 000 100 200

h-values

10L

4L

46L

26L

12L

44L

Labo

rato

ries

Mandels h statistics(Compost 1 - Sum PBD)

Compost 1-Sum PBD

Unit mgkg

Mandels k statistics(Sludge 1 - Sum PBD)Mandels h statistics(Sludge 1 - Sum PBD)

Sample Sludge 1 Sludge 1 - Sum PBD -- Mean PARM = 0256 [mgkg]

Element Sum PBD

General calcparmT1= 531806E+00T2= 162188E+00T3= 22T4= 84T5= 25223E-02

n= variabelp= 6

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00423 0025 4 -156 044 Fail 00423 00252 4 3 -02146L 01808 0118 4 -049 205 - - 46L - - -0074L 01810 0056 4 -049 097 01810 00558 4 3 -007

38L 02168 0006 4 -022 010 02168 00059 4 3 -00412L 02890 0065 4 034 113 02890 00647 4 3 00364L 03958 0008 4 116 014 Fail 03958 00079 4 3 01426L 04094 0034 2 126 059 Fail 04094 00337 2 1 015

Totgem 0245 0044 mgkg 1-level 198 (179) 6 02557 (46L) 6 5Totstd= 0130 0039 5-level 171 (155) 1

RESULTS Mean = 025570 mgkg

Repeatability variance S2r = 000158Repeatability std Sr = 003970 --gt 1553 r = 01112Between lab variance S2L = 001807Reproducibility var S2R = 001964Reproducibility std SR = 014015 --gt 5481 R = 03924Remarks 1 Lab rejected (46L)

000 050 100 150 200 250

k-values

10L

46L

4L

38L

12L

64L

26L

Mandels k statistics(Sludge 1 - Sum PBD)

-03 -02 -02 -01 -01 00 01 01 02 02

Deviation from Mean

10L

46L

4L

38L

12L

64L

26L

Labo

rato

ries

Sludge 1 - Sum PBD -- Mean PARM = 0256 [mgkg]

-200 -100 000 100 200

h-values

10L

46L

4L

38L

12L

64L

26L

Labo

rato

ries

Mandels h statistics(Sludge 1 - Sum PBD)

Sludge 1-Sum PBD

Unit mgkg

Mandels k statistics(Soil 3 - Sum PBD)Mandels h statistics(Soil 3 - Sum PBD)

Sample Soil 3 Soil 3 - Sum PBD -- Mean PARM = 0227 [mgkg]

Element Sum PBD

General calcparmT1= 610980E+00T2= 200876E+00T3= 26T4= 100T5= 13106E-02

n= variabelp= 7

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00028 0001 4 -037 000 Fail 00028 00005 4 3 -02226L 01179 0021 2 -036 003 Fail 01179 00208 2 1 -0114L 01305 0031 4 -036 004 Fail 01305 00308 4 3 -010

46L 02065 0035 4 -036 005 Fail 02065 00350 4 3 -00244L 02923 0037 4 -035 005 Fail 02923 00365 4 3 00712L 04051 0015 4 -034 002 Fail 04051 00149 4 3 01864L 04314 0022 4 -033 003 Fail 04314 00223 4 3 0203L 305500 2051 2 247 283 Fail - - 3L - - 3032

Totgem 4017 0276 mgkg 1-level 206 (181) 7 02266 (3L) 7 6Totstd= 10722 0717 5-level 175 (156) 1

RESULTS Mean = 022663 mgkg

Repeatability variance S2r = 000069Repeatability std Sr = 002626 --gt 1159 r = 00735Between lab variance S2L = 002568Reproducibility var S2R = 002637Reproducibility std SR = 016238 --gt 7165 R = 04547Remarks 1 Lab rejected (3L)

000 050 100 150 200 250 300

k-values

10L

26L

4L

46L

44L

12L

64L

3L

Mandels k statistics(Soil 3 - Sum PBD)

-50 00 50 100 150 200 250 300 350

Deviation from Mean

10L

26L

4L

46L

44L

12L

64L

3L

Labo

rato

ries

Soil 3 - Sum PBD -- Mean PARM = 0227 [mgkg]

-100 000 100 200 300

h-values

10L

26L

4L

46L

44L

12L

64L

3L

Labo

rato

ries

Mandels h statistics(Soil 3 - Sum PBD)

Soil 3-Sum PBD

19

Annex 4

Raw data submitted

Sample Compost1 Sample Compost 1 Sample Compost 1Element PBD 99 Element PBD 100 Element PBD 153

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]4L 00021 10L 00008 44L 000504L 00024 10L 00008 44L 000604L 00014 10L 00007 44L 000504L 00020 10L 00011 46L 00004

10L 00029 46L 00007 46L 0001210L 00027 46L 00012 46L 0000410L 00032 46L 00009 46L 0000946L 00025 46L 00007 12L 0000446L 00052 12L 00008 12L 0000846L 00029 12L 00012 12L 0000446L 00026 12L 00008 12L 0000712L 00026 12L 00014 26L 0000512L 00043 26L 00007 26L 0000512L 00026 26L 0000612L 0004726L 0002626L 00024

Sample Compost 1 Sample Compost 1 Sample Compost 1Element PBD 154 Element PBD 183 Element PBD 196

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]4L 00010 46L 00002 46L 00011

46L 00003 46L 00024 46L 0000846L 00007 46L 00021 12L 0000246L 00003 46L 00003 12L 0000346L 00004 12L 00003 12L 0000112L 00003 12L 00011 12L 0000212L 00005 12L 0000312L 00031 12L 0000312L 00006

Sample Compost 1 Sample Compost 1 Sample Compost 1Element PBD 197 Element PBD 203 Element PBD 209

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00002 46L 00010 4L 0004146L 00023 12L 00002 4L 0008946L 00022 12L 00003 44L 0041012L 00004 12L 00002 44L 0084012L 00006 12L 00002 44L 0064012L 00003 44L 0040012L 00004 12L 00079

12L 0007312L 0006512L 0009326L 0004926L 00049

Sample Compost 1Element PBD 47

LAB PARM [mgkg]26L 0003826L 00039

Element PBD 99 Element PBD 47 Element PBD 209LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]

4L 00170 10L 00210 4L 010004L 00200 10L 00220 4L 018004L 00170 10L 00210 4L 012004L 00190 46L 00300 4L 0220010L 00280 46L 00280 46L 0210010L 00300 46L 00250 46L 0200010L 00290 46L 00260 64L 0351846L 00340 64L 00059 64L 0363846L 00330 64L 00057 64L 0364546L 00300 64L 00062 64L 0350846L 00310 64L 00060 12L 0220964L 00194 12L 00191 12L 0177164L 00154 12L 00187 12L 0292264L 00185 12L 00190 12L 0164664L 00159 12L 00186 26L 0329712L 00242 26L 00666 26L 0300012L 00223 26L 0033212L 0022112L 0022226L 0024626L 00400

Element PBD 203 Element PBD 197 Element PBD 196LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00022 46L 00027 46L 0002446L 00014 46L 00024 46L 0002264L 00036 12L 00161 64L 0005864L 00058 12L 00060 64L 0006512L 00063 12L 00061 12L 0004812L 00034 12L 00036 12L 0002512L 00038 12L 0003212L 00027 12L 00022

Element PBD 183 Element PBD 154 Element PBD 153LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00049 4L 00020 4L 0002246L 00035 4L 00022 4L 0002446L 00036 4L 00020 4L 0002246L 00034 46L 00025 4L 0002664L 00027 46L 00025 46L 0004064L 00023 46L 00025 46L 0004264L 00024 46L 00023 46L 0003564L 00020 64L 00034 46L 0003812L 00230 64L 00023 64L 0007412L 00032 64L 00017 64L 0004712L 00031 64L 00011 64L 0004612L 00030 12L 00030 64L 0003026L 00007 12L 00021 12L 0006526L 00008 12L 00021 12L 00029

12L 00021 12L 0003226L 00015 12L 0002926L 00019 26L 00039

26L 00040

Element PBD 100LAB PARM [mgkg]

4L 000384L 000414L 000374L 00038

38L 0219038L 0220038L 0208038L 0220010L 0004410L 0005010L 0004310L 0004646L 0005746L 0005946L 0005346L 0005312L 0004312L 0004512L 0004312L 0004326L 0006226L 00057

Sample Soil 3 Sample Soil 3 Sample Soil 3Element PBD 99 Element PBD 47 Element PBD 100

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]10L 00016 10L 00011 10L 0000310L 00019 10L 00010 10L 0000410L 00013 10L 00012 10L 0000410L 00019 46L 00007 10L 0000246L 00025 46L 00022 46L 0000246L 00025 46L 00005 46L 0000646L 00008 46L 00007 46L 0000246L 00011 12L 00010 46L 0000264L 00005 12L 00017 3L 29100064L 00005 12L 00010 3L 32000064L 00006 12L 00009 26L 0000564L 00007 26L 00007 26L 0000512L 00012 26L 0000712L 0001312L 0001312L 0001226L 0000526L 00006

Sample Soil 3 Sample Soil 3 Sample Soil 3Element PBD 153 Element PBD 154 Element PBD 196

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]44L 00050 4L 00010 46L 0000744L 00050 46L 00001 46L 0001146L 00002 46L 00002 46L 0000846L 00003 46L 00001 46L 0001146L 00002 46L 00002 64L 0002646L 00002 64L 00001 64L 0002664L 00001 64L 00001 64L 0002964L 00001 64L 00001 64L 0003464L 00001 64L 00002 12L 0004564L 00002 12L 00003 12L 00032

12L 00002 12L 0002212L 00002 12L 0002112L 00002

Sample Soil 3 Sample Soil 3 Sample Soil 3Element PBD 197 Element PBD 203 Element PBD 209

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00006 46L 00011 4L 0091046L 00013 46L 00017 4L 0150046L 00011 46L 00015 4L 0120046L 00013 46L 00018 4L 0160012L 00090 64L 00013 44L 0337012L 00056 64L 00014 44L 0281012L 00033 64L 00016 44L 0287012L 00032 64L 00015 44L 02540

12L 00055 46L 0230012L 00041 46L 0220012L 00027 46L 0150012L 00026 46L 01900

64L 0438164L 0401664L 0414464L 0449812L 0367112L 0397812L 0409112L 03838

Sample Soil 3 26L 0102Element PBD 183 26L 0131

LAB PARM [mgkg]46L 0000746L 0000846L 0005846L 0000764L 0000264L 0000364L 0000364L 0000312L 0001512L 0001112L 0000712L 00007

European Commission EUR 23003 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on polybrominated diphenylethers Author(s) E Sobiecka H van der Sloot D Barcelo B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 68 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07403-5 Abstract Project HORIZONTAL is interdisciplinary aiming at a harmonisation and horizontal standardisation of test procedures in particular for sludge soils and biowastes In the context of this standardization project a series of draft technical specification were designed upon an extensive desk study fine-tuned after expert consultations and finally validated in international intercomparisons exercise This report summarises the work performed within the validation study of the draft standard for the determination of polybrominated diphenylethers (PBDE) in soils sludge and treated bio-waste using gas-chromatography method with mass selective detection (GC-MS) It further explains the underlying statistical concept for the calculation of reproducibility and repeatability from intercomparisons data In addition all single values results of the statistical evaluation as well as background information on the validation materials used are described and explained

The mission of the JRC is to provide customer-driven scientific and technical support for the conception development implementation and monitoring of EU policies As a service of the European Commission the JRC functions as a reference centre of science and technology for the Union Close to the policy-making process it serves the common interest of the Member States while being independent of special interests whether private or national

LB

-NA

-23003-EN

-C

Model questionnaire to be filled by the participating laboratories Name of laboratory Contact person Contact details email Phone Fax Mail address of lab Dispatch address of lab for shipment of samples (no PO boxes) Title of measurement method (copy attached) Our laboratory is willing to participate in the precision experiment for this draft standard method

Yes No As participant we understand that

bull All essential apparatus chemicals and other requirements specified in the method must be available in our laboratory when the programme begins

bull Specified timing requirements such as starting and finishing date of the programme must be rigidly met

bull The method must be strictly adhered to bull Samples must be handled in accordance with instructions bull A qualified operator must perform the measurements

Having studied the method and having made a fair appraisal of our capabilities and facilities we feel that we will be adequately prepared for cooperative testing of this method Comments helliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphellip Signature Date

17

Annex 2

Report on the validation materials used

VI

Abstract This report gives an overview on the available analytical information on the following raw materials to be used for the production of validation materials of the so-called Project HORIZONTAL

bull Four sludge materials from Duumlsseldorf Germany

bull An agricultural soil material from Reading United Kingdom

bull A compost material from Vienna Austria

bull A compost material from Korschenbroich Germany

bull A sludge-amended agricultural soil from Pavia Province Italy

bull A sludge-amended soil from Barcelona Spain

bull A sludge-amended soil from Essen Germany

bull A long-term sludge exposed soil from Hohenheim Germany

VII

List of Abbreviations Throughout this report the following abbreviations are used

AOX absorbable organic halogens

Corg organic carbon content

Ctotal total carbon content

CAT cation exchangeable

CDD chlorinated dibenzodioxin

CDF chlorinated dibenzofuran

DEHP di(2-ethylhexyl)phthalate

DM dry matter

EPA Environment Protection Agency

EU European Union

FM fresh matter

Hp hepta

Hx hexa

IES Institute for Environment and Sustainability

IRMM Institute for Reference Materials and Measurements

JRC Joint Research Centre

LAS linear alkylsulfonates

LoD limit of detection

LUA Landesumweltamt

Ntotal total nitrogen content

NH4-N Ammonium nitrogen

NO3-N Nitrate nitrogen

NP nonylphenol

NRW North Rhine Westphalia

O octa

P poly

PAH polycyclic aromatic hydrocarbon

PCB polychlorinated biphenyl

Pe penta

T tetra

TEQ toxicity equivalent

UBA Umweltbundesamt

WHO World Health Organization

WWTP waste water treatment plant

6

1 Introduction This report gives an overview on the available analytical information on the following raw materials to be used for the production of validation materials of the so-called Project HORIZONTAL

bull Four sludge materials from Duumlsseldorf Germany

bull An agricultural soil material from Reading United Kingdom

bull A compost material from Vienna Austria

bull A compost material from Korschenbroich Germany

bull A sludge-amended agricultural soil from Pavia Province Italy

bull A sludge-amended soil from Barcelona Spain

bull A sludge-amended soil from Essen Germany

bull A long-term sludge exposed soil from Hohenheim Germany

The following analytical information was gathered partly before and during the sampling of the raw materials to be used for the production of the HORIZONTAL validation materials The material were sampled by IES and shipped to IRMM in the course of the year 2005 The information gathered was then completed by various analytical screenings for PAHs and PCBs done by the Institute for Reference Materials and Measurements Geel Belgium for phthalates done by UBA Berlin Germany for PBDE done by IIQAB-CSIC Barcelona Spain for trace elements and some selected major and minor elements by the Institute for Environment and Sustainability Ispra Italy

The work compiled hereafter is based on the numerous additional efforts of the scientists working at various members of the consortium Project HORIZONTAL-Org and contributing organisations

This work is gratefully acknowledged

2 Overview on property values

21 Sludge materials from Duumlsseldorf Germany

The various sewage sludge materials originate from various installations in the North Rhine Westphalia and were produced and sampled by staff from the Landesumweltamt (LUA) NRW under the responsibility from Dr K Furtmann

In total four sludge materials (Sludge A and D from a major municipal WWTP Sludge B from a municipal WWTP with industrial input and Sludge C from a municipal WWTP with high PCB-Content) were obtained and will be blended to two final materials Before sampling the following analytical data for a typical sample were received

7

Table 1 ndash Analytical data obtained on an average sludge sample in LUA NRW (with courtesy of K Furtmann LUA Duumlsseldorf)

Parameter Concentration PCB 120 ugkg DEHP 110 mgkg PAH 5 mgkg (EPA) PCDDF 15 ng TEkg PBDE 400 ugkg NP 40 mgkg LAS 3 gkg AOX 300 mgkg

Subsequent screening led to the information displayed hereafter It should be stressed that the data were obtained as SCREENING information on the UNTREATED or partially treated raw materials Therefore the final target values which are relevant for the validation intercomparison can be different

Table 2 ndash Analytical data obtained on a first screening on the sludge samples from LUA NRW

Sewage sludge A

Dusseldorf

sewage sludge D

Dusseldorf PCB (ngg) 28 62 35 52 101 65 101 31 38 118 49 40 153 30 33 105 24 11 138 46 38 156 lt1 lt1 180 34 23 170 23 19 PAH (ngg) Naphtalene 34 381 Acenaphtylene 15 43 Acenaphthene 81 108 Fluorene 94 1167 Phenantrene 3440 Anthracene 22 344 Flouranthene 316 4817 Pyrene 235 3011 Benz(a)anthracene 473 791 Chrysene 691 1078 Benz(b)fluoranthene 538 1688 Benz(k)fluoranthene 228 635 Benz(a)pyrene 383 1114 Indeno(123-cd)pyrene 92 229 Dibenzo(ah)anthracene 71 70 Benzo(ghi)perylene 80 185

8

Table 3 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Sludge D (1) 0135 41474 385 Sludge B (2) 0538 0034 30634 547 Sludge A (3) 0184 0037 31399 146 Sludge C (4) 0354 1528 6678 229

Table 4 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Sludge 2

(B)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

554

959

694

591

772

509

nq

nq

970

2216

2379

Table 5 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena IES Ispra Spain) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Sludge 1 (D) 265 290 533 359 1231 338 784 438 lt 005 232 786 Sludge 2 (B) 119 311 626 202 278 299 722 251 lt 005 118 625 Sludge 3 (A) 168 360 621 332 847 416 119 451 lt 005 116 1237 Sludge 4 (C) 563 198 116 273 726 511 473 618 lt 005 444 2015

Table 6 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Sludge 1 (D) 2154 58 844 099 103 101 4367 lt15 50448 Sludge 2 (B) 1067 366 692 046 1491 077 5217 lt15 57633 Sludge 3 (A) 731 663 684 035 1287 068 3733 lt15 60369 Sludge 4 (C) 4379 965 527 163 522 107 5628 lt15 23945

Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM)Sludge 1 (D) 03 2403 101 1002 350 15 1944 132Sludge 2 (B) 031 315 97 879 172 12 514 180Sludge 3 (A) 031 1281 153 1567 265 16 1440 168Sludge 4 (C) 055 231 628 2625 371 81 1101 244

9

22 Agricultural soil material from Reading United Kingdom

The material was proposed by the University of Reading (S Nortcliff) and was sampled from a site called ldquoFrogmore Farmrdquo which was featured in the ldquoMetalsrdquo Report for HORIZONTAL This site is close to Reading with soils developed on flintyloamy periglacial materials over Chalk has a long and well documented history of sludge application The focus of the work of Nortcliff et al undertook at this site and the monitoring and control at the site (by Thames Water and the subsequent subsidiary bodies dealing with sludge application to soil) was on metals (and metal loads) with no analysis or indeed any form of investigation in to organics in the broadest sense

The analytical information produced in the context of the screening of the raw material is displayed below

Table 7 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 3

(Reading) 0032 0119 669

Table 8 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 3 (Reading) 015 706 279 138 152 901 267 300 lt 005 258 931

Table 9 ndash Analytical data obtained on a first screening on the sludge-amended soil from Reading (courtesy of IRMM)

Parameter Concentration

PCB ngg 28 lt1 52 lt1 101 lt1 118 lt1 153 lt1 105 lt1 138 lt1 156 lt1 180 lt1 170 lt1 PAH ngg Naphtalene lt10 Acenaphtylene 21 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene lt10 Flouranthene 818 Pyrene 776 Benz(a)anthracene 565

10

Parameter Concentration

Chrysene 608 Benz(b)fluoranthene 824 Benz(k)fluoranthene 329 Benz(a)pyrene 799 Indeno(123-cd)pyrene

779

Dibenzo(ah)anthracene 118 Benzo(ghi)perylene 394

Table 10 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 3

(Reading)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

103

003

nq

nq

nq

nd

nd

272

273

Table 11 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 3 (Reading) 015 706 279 138 152 901 267 300 lt 005 258 931

Table 12 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 3 (Reading) 7936 477 112 096 194 017 4107 443 2102 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 3 (Reading) 042 13 45 69 69 69 216 92

Table 13 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 3 (Reading) 012

11

23 Compost from Vienna Austria

The fresh compost material was obtained from the Austrian Federal Environment Agency (UBA Vienna) which had used a sub-batch of the raw material for national intercomparson The remainder of the material was stored at 4degC until shipment to IRMM for further processing The following analytical information was provided by UBA Austria and completed with various screenings

Table 14 ndash Analytical data on compost material received from UBA Austria Inorganic and sum parameters

Parameter Unit Sample fraction used Observed mean B CAT mgl FM Fresh sample lt10mm 61 K CAT mgl FM Fresh sample lt10mm 2624 Mg CAT mgl FM Fresh sample lt10mm 242 P CAT mgl FM Fresh sample lt10mm 49 B CAT DM Fresh sample lt10mm 00017 K CAT DM Fresh sample lt10mm 072 Mg CAT DM Fresh sample lt10mm 007 P CAT DM Fresh sample lt10mm 001 NO3-N mgkg FM Fresh sample lt10mm 35 NH4-N mgkg FM Fresh sample lt10mm 230 Ctotal DM lt45degdry milled 29 Corg DM lt45degdry milled 27 Ntotal DM lt45degdry milled 17 P mgkg DM lt45degdry milled 2596 K mgkg DM lt45degdry milled 11019 K DM lt45degdry milled 110 B mgkg DM lt45degdry milled 60 Cd mgkg DM lt45degdry milled 046 Cr mgkg DM lt45degdry milled 25 Cu mgkg DM lt45degdry milled 46 Hg mgkg DM lt45degdry milled 020 Ni mgkg DM lt45degdry milled 18 Pb mgkg DM lt45degdry milled 45 Zn mgkg DM lt45degdry milled 198 Ca mgkg DM lt45degdry milled 68776 Ca DM lt45degdry milled 69 Mo mgkg DM lt45degdry milled 08 S mgkg DM lt45degdry milled 2137 Fe mgkg DM lt45degdry milled 9959 Mn mgkg DM lt45degdry milled 418 Na mgkg DM lt45degdry milled 742 Co mgkg DM lt45degdry milled 41 AOX mgkg DM lt30deg dry milled 62

Table 15 ndash Analytical data on compost material received from UBA Austria Polycyclic aromatic hydrocarbons

PAH Unit Result Naphthaline microgkg DM 93 Acenaphthylene microgkg DM 86 Acenaphthene microgkg DM 5 Fluorene microgkg DM 80 Phenanthrene microgkg DM 89 Anthracene microgkg DM 27 Fluoranthene microgkg DM 487 Pyrene microgkg DM 380

12

PAH Unit Result Benzo(a)anthracene microgkg DM 278 Chrysene microgkg DM 317 Benzo(b)fluoranthene microgkg DM 365 Benzo(k)fluoranthene microgkg DM 193 Benz(a)pyrene microgkg DM 320 Indeno(123-cd)pyrene microgkg DM 233 Dibenz(ah)anthracene microgkg DM 67 Benzo(ghi)perylene microgkg DM 225 Sum EPA microgkg DM 3013 Sum EPA mgkg DM 30

Table 16 ndash Analytical data on compost material received from UBA Austria Sum PCDDs and PCBs

Parameter

Dioxine TEQ (ITEF) ngkg DM 73 TEQ (WHO) ngkg DM 35 PCB Σ Ballschmiter mgkg DM 005

Table 17 ndash Analytical data on compost material obtained by screening in IRMM

Parameter Result in ngg

PCB 28 2 52 2 101 4 118 3 153 10 105 1 138 8 156 1 180 5 170 lt1 PAH Naphtalene lt10 Acenaphtylene lt10 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene 26 Fluoranthene 611 Pyrene 510 Benz(a)anthracene 888 Chrysene 957 Benz(b)fluoranthene 1531 Benz(k)fluoranthene 547 Benz(a)pyrene 1101 Indeno(123-cd)pyrene 416 Dibenzo(ah)anthracene 81 Benzo(ghi)perylene 295

13

Table 18 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Compost 1

(Vienna)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

402

019

259

nq

023

004

nq

nq

144

174

259

Table 19 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Compost 1

(Vienna) 0058 1426 557

Table 20 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Compost 1 (Vienna) 039 736 319 410 365 127 495 004 079 013 208

Table 21 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Compost 1 (Vienna) 2063 431 617 426 199 249 1602 lt15 10521

Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Compost 1 (Vienna) 035 3496 81 375 79 55 653 60

Table 22 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Compost 1 (Vienna) 017

14

24 Agricultural soil sludge amended soil from Pavia Italy

This sludge-amended soil material was obtained during a monitoring campaign which aimed at a generic description of the over-all soil quality in Pavia Province Italy The material which was collected from the upper horizon originates from a small farm called ldquoCascina Novellordquo During the characterisation of the site the following analytical information was obtained on a pooled sample of a sub-area of the farm of 20 X 20 m2

Table 23 ndash Analytical data on Pavia soil

Parameter Result Al 713 Wgt As 224 mgkg Cd 079 mgkg Cr 59 mgkg Cu 308 mgkg Hg 008 mgkg Ni 344 mgkg Pb 246 mgkg Zn 95 mgkg C 091 Wgt 2378-TCDD 0047 pgg 12378-PeCDD 015 pgg 123478-HxCDD 019 pgg 123678-HxCDD 15 pgg 123789-HxCDD 074 pgg 1234678-HpCDD 26 pgg OCDD 382 pgg 2378-TCDF 068 pgg 12378-PeCDF 053 pgg 23478-PeCDF 071 pgg 123478-HxDF 100 pgg 123678-HxDF 066 pgg 234678-HxDF 16 pgg 123789-HxDF 027 pgg 1234678-HpDF 12 pgg 1234789-HpDF 068 pgg OCDF 33 pgg I-TEQ 20 pgg WHO-TEQ 17 pgg

In addition the screening performed at IRMM did not reveal significant quantities of PCBs and PAHs which were all below the LoDs (1 ngg for PCBs and 10 ngg for PAHs respectively)

Table 24 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 5 (Pavia) 0005 0011 154

15

Table 25 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 5

(Pavia)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

039

nq

nq

008

nq

nd

nd

670

671

Table 26 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 5 (Pavia) 033 184 573 225 426 305 206 200 lt 005 381 878

Table 27 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 5 (Pavia) 6939 129 145 224 425 116 6118 255 1789 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 5 (Pavia) 184 62 38 108 55 66 597 110

Table 28 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 5 (Pavia) 006

16

25 Sludge-amended-soil from Barcelona Spain

The sludge-amended soil material from Barcelona sampled upon indication from the Barcelorsquo- Group in Barcelona

Table 29 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 2 (Lleida T) 0015 0183 1138

Table 30 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 2

(Lleida T)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

159

045

nq

048

160

nq

nq

1000

1004

Table 31 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 2 (Lleida T) 059 141 327 536 405 186 184 224 lt 005 318 111

Table 32 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 2 (Lleida T) 4443 1067 1429 253 344 204 4116 780 3396 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 2 (Lleida T) 064 65 26 125 59 17 547 65

Table 33 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 2 (Lleida T) 010

17

26 Sludge amended soil from Essen Germany

The German sludge-amended soil from Essen which was provided as the three sludge materials by LUA NRW did not feature significant concentrations of the PCB congeners 28 52 101 118 153 105 138 156 180 170 but had detectable amounts of some PAHs

Table 34 ndash Analytical screening data on the German sludge-amended soil

Parameter Concentration(ngg)

Naphtalene lt10 Acenaphtylene lt10 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene lt10 Fluoranthene 28 Pyrene 20 Benz(a)anthracene 24 Chrysene 47 Benz(b)fluoranthene 76 Benz(k)fluoranthene 20 Benz(a)pyrene 35 Indeno(123-cd)pyrene 35 Dibenzo(ah)anthracene 10 Benzo(ghi)perylene 26

Table 35 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 4 (Essen) 0011 0302 055

Table 36 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 4

(Essen)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

nq

nq

nq

nq

nq

nq

128

191

203

18

Table 37 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 4 (Essen) 052 545 261 805 320 403 273 273 lt 005 295 781

Table 38 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 4 (Essen) 7947 442 085 06 086 007 2163 189 2019 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 4 (Essen) 045 19 42 87 683 60 462 61

Table 39 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 4 (Essen) 004

27 Long-term sludge exposed soil from Hohenheim-Stuttgart Germany

Similarly an additional sludge exposed soil was sampled at the University of Hohenheim Stuttgart were a test soil was long-term exposed to elevated concentrations of sewage sludge

Table 40 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 1 (Stuttgart) 0045 0263 1765

Table 41 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 1

(Stuttgart)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

230

006

004

004

nq

nd

nd

498

500

19

Table 42 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 1 (Stuttgart) 069 127 361 262 504 183 252 262 lt 005 266 142

Table 43 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 1 (Stuttgart) 7194 1006 133 186 366 088 7874 275 3571 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 1 (Stuttgart) 123 50 47 212 85 69 991 129

Table 44 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 1 (Stuttgart) 177

18

Annex 3

Statistical calculations

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 47)Mandels h statistics(Sludge 1 - PBD 47)

Sample Sludge 1 NUM

Element PBD 47

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00213 0001 3 -021 005 - - 10L - - NUM46L 00273 0002 4 016 021 - - 46L - - NUM64L 00059 0000 4 -116 002 NUM - 64L - - NUM12L 00188 0000 4 -036 002 - - 12L - - NUM26L 00499 0024 2 157 223 Fail - - 26L - - NUM

Totgem 0025 0005 mgkg 1-level 172 (185) NUM (10L46L64L12L26L) -1Totstd= 0016 0010 5-level 157 (162) 5

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 5 Labs rejected (10L46L64L12L26L)

000 050 100 150 200 250

k-values

10L

46L

64L

12L

26L

Mandels k statistics(Sludge 1 - PBD 47)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

10L

46L

64L

12L

26L

Labo

rato

ries

NUM

-200 -100 000 100 200

h-values

10L

46L

64L

12L

26L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 47)

Sludge 1-PBD 47

Unit mgkg

Mandels k statistics(Soil 3 - PBD 47)Mandels h statistics(Soil 3 - PBD 47)

Sample Soil 3 Soil 3 - PBD 47 -- Mean PARM = 0001 [mgkg]

Element PBD 47

General calcparmT1= 134814E-02T2= 142830E-05T3= 13T4= 45T5= 22767E-06

n= variabelp= 4

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean26L 00007 0000 2 -143 001 00007 00000 2 1 00046L 00010 0001 4 010 181 00010 00008 4 3 00010L 00011 0000 3 049 023 00011 00001 3 2 00012L 00012 0000 4 084 081 00012 00004 4 3 000

Totgem 0001 0000 mgkg 1-level 149 (177) 4 00010 () 4 3Totstd= 0000 0000 5-level 142 (159)

RESULTS Mean = 000100 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000050 --gt 5031 r = 00014Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000050 --gt 5031 R = 00014Remarks none

000 050 100 150 200

k-values

26L

46L

10L

12L

Mandels k statistics(Soil 3 - PBD 47)

00 00 00 00 00 00 00 00 00 00 00

Deviation from Mean

26L

46L

10L

12L

Labo

rato

ries

Soil 3 - PBD 47 -- Mean PARM = 0001 [mgkg]

-200 -100 000 100

h-values

26L

46L

10L

12L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 47)

Soil 3-PBD 47

Unit mgkg

Mandels k statistics(Compost 1 - PBD 99)Mandels h statistics(Compost 1 - PBD 99)

Sample Compost 1 Compost 1 - PBD 99 -- Mean PARM = 0003 [mgkg]

Element PBD 99

General calcparmT1= 492124E-02T2= 148747E-04T3= 17T4= 61T5= 93196E-06

n= variabelp= 5

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00020 0000 4 -137 053 00020 00004 4 3 000

26L 00025 0000 2 -058 024 00025 00002 2 1 00010L 00029 0000 3 012 032 00029 00003 3 2 00046L 00033 0001 4 069 161 00033 00013 4 3 00012L 00036 0001 4 114 140 00036 00011 4 3 000

Totgem 0003 0001 mgkg 1-level 172 (185) 5 00029 () 5 4Totstd= 0001 0001 5-level 157 (162)

RESULTS Mean = 000286 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000088 --gt 3086 r = 00025Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000101 --gt 3525 R = 00028Remarks none

000 050 100 150 200

k-values

4L

26L

10L

46L

12L

Mandels k statistics(Compost 1 - PBD 99)

00 00 00 00 00 00 00 00 00 00

Deviation from Mean

4L

26L

10L

46L

12L

Labo

rato

ries

Compost 1 - PBD 99 -- Mean PARM = 0003 [mgkg]

-200 -100 000 100 200

h-values

4L

26L

10L

46L

12L

Labo

rato

ries

Mandels h statistics(Compost 1 - PBD 99)

Compost 1-PBD 99

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 99)Mandels h statistics(Sludge 1 - PBD 99)

Sample Sludge 1 Sludge 1 - PBD 99 -- Mean PARM = 0024 [mgkg]

Element PBD 99

General calcparmT1= 448050E-01T2= 112113E-02T3= 19T4= 73T5= 32972E-05

n= variabelp= 5

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean64L 00173 0002 4 -118 041 Fail 00173 00019 4 3 -0014L 00183 0002 4 -104 032 00183 00015 4 3 -001

12L 00227 0001 4 -038 022 00227 00010 4 3 00010L 00290 0001 3 055 021 00290 00010 3 2 00146L 00320 0002 4 100 039 00320 00018 4 3 00126L 00323 0011 2 105 234 - - 26L - - 001

Totgem 0025 0003 mgkg 1-level 187 (177) 5 00239 (26L) 5 4Totstd= 0007 0004 5-level 166 (154) 1

RESULTS Mean = 002385 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000153 --gt 643 r = 00043Between lab variance S2L = 000004Reproducibility var S2R = 000004Reproducibility std SR = 000666 --gt 2791 R = 00186Remarks 1 Lab rejected (26L)

000 050 100 150 200 250

k-values

64L

4L

12L

10L

46L

26L

Mandels k statistics(Sludge 1 - PBD 99)

00 00 00 00 00 00 00 00 00 00

Deviation from Mean

64L

4L

12L

10L

46L

26L

Labo

rato

ries

Sludge 1 - PBD 99 -- Mean PARM = 0024 [mgkg]

-200 -100 000 100 200

h-values

64L

4L

12L

10L

46L

26L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 99)

Sludge 1-PBD 99

Unit mgkg

Mandels k statistics(Soil 3 - PBD 99)Mandels h statistics(Soil 3 - PBD 99)

Sample Soil 3 NUM

Element PBD 99

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00017 0000 4 091 068 - - 10L - - NUM46L 00017 0001 4 100 211 - - 46L - - NUM64L 00005 0000 4 -106 023 NUM - 64L - - NUM12L 00012 0000 4 015 014 - - 12L - - NUM26L 00006 0000 2 -101 012 - - 26L - - NUM

Totgem 0001 0000 mgkg 1-level 172 (173) NUM (10L46L64L12L26L) -1Totstd= 0001 0000 5-level 157 (153) 5

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 5 Labs rejected (10L46L64L12L26L)

000 050 100 150 200 250

k-values

10L

46L

64L

12L

26L

Mandels k statistics(Soil 3 - PBD 99)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

10L

46L

64L

12L

26L

Labo

rato

ries

NUM

-200 -100 000 100 200

h-values

10L

46L

64L

12L

26L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 99)

Soil 3-PBD 99

Unit mgkg

Mandels k statistics(Compost 1 - PBD 100)Mandels h statistics(Compost 1 - PBD 100)

Sample Compost 1 Compost 1 - PBD 100 -- Mean PARM = 0001 [mgkg]

Element PBD 100

General calcparmT1= 124272E-02T2= 113129E-05T3= 14T4= 52T5= 46584E-07

n= variabelp= 4

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean26L 00006 0000 2 -131 037 Fail 00006 00001 2 1 00010L 00009 0000 4 003 083 00009 00002 4 3 00046L 00009 0000 4 016 115 00009 00002 4 3 00012L 00011 0000 4 112 136 Fail 00011 00003 4 3 000

Totgem 0001 0000 mgkg 1-level 149 (167) 4 00009 () 4 3Totstd= 0000 0000 5-level 142 (15)

RESULTS Mean = 000085 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000022 --gt 2531 r = 00006Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000025 --gt 2882 R = 00007Remarks none

000 050 100 150

k-values

26L

10L

46L

12L

Mandels k statistics(Compost 1 - PBD 100)

00 00 00 00 00 00 00 00 00 00 00

Deviation from Mean

26L

10L

46L

12L

Labo

rato

ries

Compost 1 - PBD 100 -- Mean PARM = 0001 [mgkg]

-200 -100 000 100 200

h-values

26L

10L

46L

12L

Labo

rato

ries

Mandels h statistics(Compost 1 - PBD 100)

Compost 1-PBD 100

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 100)Mandels h statistics(Sludge 1 - PBD 100)

Sample Sludge 1 Sludge 1 - PBD 100 -- Mean PARM = 0005 [mgkg]

Element PBD 100

General calcparmT1= 852065E-02T2= 412762E-04T3= 18T4= 68T5= 78914E-07

n= variabelp= 5

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00039 0000 4 -042 007 Fail 00039 00002 4 3 000

12L 00044 0000 4 -041 005 Fail 00044 00001 4 3 00010L 00046 0000 4 -041 013 Fail 00046 00003 4 3 00046L 00056 0000 4 -040 012 Fail 00056 00003 4 3 00026L 00059 0000 2 -040 013 Fail 00059 00003 2 1 00038L 02168 0006 4 204 244 Fail - - 38L - - 021

Totgem 0040 0001 mgkg 1-level 187 (177) 5 00049 (38L) 5 4Totstd= 0087 0002 5-level 166 (154) 1

RESULTS Mean = 000486 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000025 --gt 507 r = 00007Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000084 --gt 1731 R = 00024Remarks 1 Lab rejected (38L)

000 050 100 150 200 250

k-values

4L

12L

10L

46L

26L

38L

Mandels k statistics(Sludge 1 - PBD 100)

-01 00 01 01 02 02 03

Deviation from Mean

4L

12L

10L

46L

26L

38L

Labo

rato

ries

Sludge 1 - PBD 100 -- Mean PARM = 0005 [mgkg]

-100 000 100 200 300

h-values

4L

12L

10L

46L

26L

38L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 100)

Sludge 1-PBD 100

Unit mgkg

Mandels k statistics(Soil 3 - PBD 100)Mandels h statistics(Soil 3 - PBD 100)

Sample Soil 3 NUM

Element PBD 100

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00003 0000 4 -050 000 Fail - - 10L - - NUM46L 00003 0000 4 -050 000 Fail NUM - 46L - - NUM3L 305500 2051 2 150 200 Fail - - 3L - - NUM

26L 00005 0000 2 -050 000 Fail - - 26L - - NUM

Totgem 7638 0513 mgkg 1-level 149 (177) NUM (10L46L3L26L) -1Totstd= 15275 1025 5-level 142 (159) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (10L46L3L26L)

000 050 100 150 200

k-values

10L

46L

3L

26L

Mandels k statistics(Soil 3 - PBD 100)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

10L

46L

3L

26L

Labo

rato

ries

NUM

-100 000 100 200

h-values

10L

46L

3L

26L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 100)

Soil 3-PBD 100

Unit mgkg

Mandels k statistics(Compost 1 - PBD 153)Mandels h statistics(Compost 1 - PBD 153)

Sample Compost 1 NUM

Element PBD 153

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean44L 00053 0001 3 150 157 Fail - - 44L - - NUM46L 00007 0000 4 -044 111 Fail - - 46L - - NUM12L 00005 0000 4 -051 055 Fail - - 12L - - NUM26L 00005 0000 2 -054 001 Fail NUM - 26L - - NUM

Totgem 0002 0000 mgkg 1-level 149 (177) NUM (44L46L12L26L) -1Totstd= 0002 0000 5-level 142 (159) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (44L46L12L26L)

000 050 100 150 200

k-values

44L

46L

12L

26L

Mandels k statistics(Compost 1 - PBD 153)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

44L

46L

12L

26L

Labo

rato

ries

NUM

-100 000 100 200

h-values

44L

46L

12L

26L

Labo

rato

ries

Mandels h statistics(Compost 1 - PBD 153)

Compost 1-PBD 153

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 153)Mandels h statistics(Sludge 1 - PBD 153)

Sample Sludge 1 Sludge 1 - PBD 153 -- Mean PARM = 0004 [mgkg]

Element PBD 153

General calcparmT1= 676738E-02T2= 267609E-04T3= 18T4= 68T5= 19626E-05

n= variabelp= 5

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00024 0000 4 -157 017 00024 00002 4 3 000

12L 00038 0002 4 006 154 00038 00018 4 3 00046L 00039 0000 4 011 026 00039 00003 4 3 00026L 00039 0000 2 018 004 00039 00000 2 1 00064L 00049 0002 4 122 159 00049 00018 4 3 000

Totgem 0004 0001 mgkg 1-level 172 (173) 5 00038 () 5 4Totstd= 0001 0001 5-level 157 (153)

RESULTS Mean = 000378 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000123 --gt 3252 r = 00034Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000142 --gt 3754 R = 00040Remarks none

000 050 100 150 200

k-values

4L

12L

46L

26L

64L

Mandels k statistics(Sludge 1 - PBD 153)

00 00 00 00 00 00 00

Deviation from Mean

4L

12L

46L

26L

64L

Labo

rato

ries

Sludge 1 - PBD 153 -- Mean PARM = 0004 [mgkg]

-200 -100 000 100 200

h-values

4L

12L

46L

26L

64L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 153)

Sludge 1-PBD 153

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 154)Mandels h statistics(Sludge 1 - PBD 154)

Sample Sludge 1 NA

Element PBD 154

General calcparmT1= NAT2= NAT3=T4=T5=

n= variabelp=

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00021 0000 3 -100 021 NA - 4L - - NA

46L 00025 0000 4 115 018 NA - 46L - - NA64L 00021 0001 4 -066 179 - - 64L - - NA12L 00023 0000 4 050 085 - - 12L - - NA

Totgem 0002 0000 mgkg 1-level 149 (167) NA (4L46L64L12L) -1Totstd= 0000 0000 5-level 142 (15) 4

RESULTS Mean = NA mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NAReproducibility var S2R = NAReproducibility std SR = NA --gt NA R = NARemarks 4 Labs rejected (4L46L64L12L)

000 050 100 150 200

k-values

4L

46L

64L

12L

Mandels k statistics(Sludge 1 - PBD 154)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

4L

46L

64L

12L

Labo

rato

ries

NA

-100 000 100 200

h-values

4L

46L

64L

12L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 154)

Sludge 1-PBD 154

Unit mgkg

Mandels k statistics(Soil 3 - PBD 154)Mandels h statistics(Soil 3 - PBD 154)

Sample Soil 3 NUM

Element PBD 154

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

4L 00010 - 1 150 Fail - - 4L - - NUM46L 00001 0000 4 -053 096 Fail - - 46L - - NUM64L 00001 0000 4 -056 105 Fail NUM - 64L - - NUM12L 00002 0000 4 -040 099 Fail - - 12L - - NUM

Totgem 000037 0000 mgkg 1-level 149 (164) NUM (4L46L64L12L) -1Totstd= 000042 0000 5-level 142 (153) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (4L46L64L12L)

000 050 100 150

k-values

4L

46L

64L

12L

Mandels k statistics(Soil 3 - PBD 154)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

4L

46L

64L

12L

Labo

rato

ries

NUM

-100 000 100 200

h-values

4L

46L

64L

12L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 154)

Soil 3-PBD 154

Unit mgkg

Mandels k statistics(Compost 1 - PBD 209)Mandels h statistics(Compost 1 - PBD 209)

Sample Compost 1 NUM

Element PBD 209

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00065 0003 2 -049 032 - - 4L - - NUM

44L 00573 0021 4 150 197 Fail - - 44L - - NUM12L 00078 0001 4 -045 011 - - 12L - - NUM26L 00049 0000 2 -056 000 NUM - 26L - - NUM

Totgem 0019 0006 mgkg 1-level 149 (177) NUM (4L44L12L26L) -1Totstd= 0025 0010 5-level 142 (159) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (4L44L12L26L)

000 050 100 150 200

k-values

4L

44L

12L

26L

Mandels k statistics(Compost 1 - PBD 209)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

4L

44L

12L

26L

Labo

rato

ries

NUM

-100 000 100 200

h-values

4L

44L

12L

26L

Labo

rato

ries

Mandels h statistics(Compost 1 - PBD 209)

Compost 1-PBD 209

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 209)Mandels h statistics(Sludge 1 - PBD 209)

Sample Sludge 1 Sludge 1 - PBD 209 -- Mean PARM = 0249 [mgkg]

Element PBD 209

General calcparmT1= 394542E+00T2= 107296E+00T3= 16T4= 56T5= 19723E-02

n= variabelp= 5

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 01550 0055 4 -112 148 Fail 01550 00551 4 3 -009

46L 02050 0007 2 -053 019 02050 00071 2 1 -00412L 02137 0058 4 -042 155 02137 00576 4 3 -00426L 03149 0021 2 078 057 Fail 03149 00210 2 1 00764L 03577 0007 4 129 020 Fail 03577 00074 4 3 011

Totgem 0249 0030 mgkg 1-level 172 (185) 5 02493 () 5 4Totstd= 0084 0025 5-level 157 (162)

RESULTS Mean = 024926 mgkg

Repeatability variance S2r = 000179Repeatability std Sr = 004234 --gt 1699 r = 01186Between lab variance S2L = 000743Reproducibility var S2R = 000922Reproducibility std SR = 009604 --gt 3853 R = 02689Remarks none

000 050 100 150 200

k-values

4L

46L

12L

26L

64L

Mandels k statistics(Sludge 1 - PBD 209)

-01 -01 00 01 01 02

Deviation from Mean

4L

46L

12L

26L

64L

Labo

rato

ries

Sludge 1 - PBD 209 -- Mean PARM = 0249 [mgkg]

-200 -100 000 100 200

h-values

4L

46L

12L

26L

64L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 209)

Sludge 1-PBD 209

Unit mgkg

Mandels k statistics(Soil 3 - PBD 209)Mandels h statistics(Soil 3 - PBD 209)

Sample Soil 3 Soil 3 - PBD 209 -- Mean PARM = 0258 [mgkg]

Element PBD 209

General calcparmT1= 596398E+00T2= 191917E+00T3= 22T4= 84T5= 13249E-02

n= variabelp= 6

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean26L 01162 0021 2 -108 074 Fail 01162 00207 2 1 -0144L 01303 0031 4 -097 111 Fail 01303 00312 4 3 -013

46L 01975 0036 4 -046 128 Fail 01975 00359 4 3 -00644L 02898 0035 4 024 124 Fail 02898 00346 4 3 00312L 03895 0018 4 100 065 Fail 03895 00181 4 3 01364L 04260 0022 4 127 078 Fail 04260 00219 4 3 017

Totgem 0258 0027 mgkg 1-level 187 (177) 6 02582 () 6 5Totstd= 0132 0008 5-level 166 (154)

RESULTS Mean = 025818 mgkg

Repeatability variance S2r = 000083Repeatability std Sr = 002878 --gt 1115 r = 00806Between lab variance S2L = 001640Reproducibility var S2R = 001723Reproducibility std SR = 013127 --gt 5084 R = 03676Remarks none

000 050 100 150

k-values

26L

4L

46L

44L

12L

64L

Mandels k statistics(Soil 3 - PBD 209)

-02 -01 -01 00 01 01 02 02

Deviation from Mean

26L

4L

46L

44L

12L

64L

Labo

rato

ries

Soil 3 - PBD 209 -- Mean PARM = 0258 [mgkg]

-200 -100 000 100 200

h-values

26L

4L

46L

44L

12L

64L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 209)

Soil 3-PBD 209

Unit mgkg

Mandels k statistics(Compost 1 - Sum PBD)Mandels h statistics(Compost 1 - Sum PBD)

Sample Compost 1 Compost 1 - Sum PBD -- Mean PARM = 0009 [mgkg]

Element Sum PBD

General calcparmT1= 154064E-01T2= 169065E-03T3= 18T4= 68T5= 11354E-04

n= variabelp= 5

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00031 0002 4 -067 016 00031 00016 4 3 -0014L 00055 0005 4 -056 048 00055 00047 4 3 000

46L 00085 0003 4 -042 031 00085 00030 4 3 00026L 00123 0000 2 -024 003 00123 00002 2 1 00012L 00154 0002 4 -011 021 00154 00021 4 3 00144L 00613 0023 4 200 237 Fail - - 44L - - 005

Totgem 0018 0006 mgkg 1-level 187 (177) 5 00089 (44L) 5 4Totstd= 0022 0009 5-level 166 (154) 1

RESULTS Mean = 000893 mgkg

Repeatability variance S2r = 000001Repeatability std Sr = 000296 --gt 3308 r = 00083Between lab variance S2L = 000002Reproducibility var S2R = 000003Reproducibility std SR = 000570 --gt 6374 R = 00159Remarks 1 Lab rejected (44L)

000 050 100 150 200 250

k-values

10L

4L

46L

26L

12L

44L

Mandels k statistics(Compost 1 - Sum PBD)

00 00 00 00 00 00 01 01

Deviation from Mean

10L

4L

46L

26L

12L

44L

Labo

rato

ries

Compost 1 - Sum PBD -- Mean PARM = 0009 [mgkg]

-100 000 100 200

h-values

10L

4L

46L

26L

12L

44L

Labo

rato

ries

Mandels h statistics(Compost 1 - Sum PBD)

Compost 1-Sum PBD

Unit mgkg

Mandels k statistics(Sludge 1 - Sum PBD)Mandels h statistics(Sludge 1 - Sum PBD)

Sample Sludge 1 Sludge 1 - Sum PBD -- Mean PARM = 0256 [mgkg]

Element Sum PBD

General calcparmT1= 531806E+00T2= 162188E+00T3= 22T4= 84T5= 25223E-02

n= variabelp= 6

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00423 0025 4 -156 044 Fail 00423 00252 4 3 -02146L 01808 0118 4 -049 205 - - 46L - - -0074L 01810 0056 4 -049 097 01810 00558 4 3 -007

38L 02168 0006 4 -022 010 02168 00059 4 3 -00412L 02890 0065 4 034 113 02890 00647 4 3 00364L 03958 0008 4 116 014 Fail 03958 00079 4 3 01426L 04094 0034 2 126 059 Fail 04094 00337 2 1 015

Totgem 0245 0044 mgkg 1-level 198 (179) 6 02557 (46L) 6 5Totstd= 0130 0039 5-level 171 (155) 1

RESULTS Mean = 025570 mgkg

Repeatability variance S2r = 000158Repeatability std Sr = 003970 --gt 1553 r = 01112Between lab variance S2L = 001807Reproducibility var S2R = 001964Reproducibility std SR = 014015 --gt 5481 R = 03924Remarks 1 Lab rejected (46L)

000 050 100 150 200 250

k-values

10L

46L

4L

38L

12L

64L

26L

Mandels k statistics(Sludge 1 - Sum PBD)

-03 -02 -02 -01 -01 00 01 01 02 02

Deviation from Mean

10L

46L

4L

38L

12L

64L

26L

Labo

rato

ries

Sludge 1 - Sum PBD -- Mean PARM = 0256 [mgkg]

-200 -100 000 100 200

h-values

10L

46L

4L

38L

12L

64L

26L

Labo

rato

ries

Mandels h statistics(Sludge 1 - Sum PBD)

Sludge 1-Sum PBD

Unit mgkg

Mandels k statistics(Soil 3 - Sum PBD)Mandels h statistics(Soil 3 - Sum PBD)

Sample Soil 3 Soil 3 - Sum PBD -- Mean PARM = 0227 [mgkg]

Element Sum PBD

General calcparmT1= 610980E+00T2= 200876E+00T3= 26T4= 100T5= 13106E-02

n= variabelp= 7

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00028 0001 4 -037 000 Fail 00028 00005 4 3 -02226L 01179 0021 2 -036 003 Fail 01179 00208 2 1 -0114L 01305 0031 4 -036 004 Fail 01305 00308 4 3 -010

46L 02065 0035 4 -036 005 Fail 02065 00350 4 3 -00244L 02923 0037 4 -035 005 Fail 02923 00365 4 3 00712L 04051 0015 4 -034 002 Fail 04051 00149 4 3 01864L 04314 0022 4 -033 003 Fail 04314 00223 4 3 0203L 305500 2051 2 247 283 Fail - - 3L - - 3032

Totgem 4017 0276 mgkg 1-level 206 (181) 7 02266 (3L) 7 6Totstd= 10722 0717 5-level 175 (156) 1

RESULTS Mean = 022663 mgkg

Repeatability variance S2r = 000069Repeatability std Sr = 002626 --gt 1159 r = 00735Between lab variance S2L = 002568Reproducibility var S2R = 002637Reproducibility std SR = 016238 --gt 7165 R = 04547Remarks 1 Lab rejected (3L)

000 050 100 150 200 250 300

k-values

10L

26L

4L

46L

44L

12L

64L

3L

Mandels k statistics(Soil 3 - Sum PBD)

-50 00 50 100 150 200 250 300 350

Deviation from Mean

10L

26L

4L

46L

44L

12L

64L

3L

Labo

rato

ries

Soil 3 - Sum PBD -- Mean PARM = 0227 [mgkg]

-100 000 100 200 300

h-values

10L

26L

4L

46L

44L

12L

64L

3L

Labo

rato

ries

Mandels h statistics(Soil 3 - Sum PBD)

Soil 3-Sum PBD

19

Annex 4

Raw data submitted

Sample Compost1 Sample Compost 1 Sample Compost 1Element PBD 99 Element PBD 100 Element PBD 153

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]4L 00021 10L 00008 44L 000504L 00024 10L 00008 44L 000604L 00014 10L 00007 44L 000504L 00020 10L 00011 46L 00004

10L 00029 46L 00007 46L 0001210L 00027 46L 00012 46L 0000410L 00032 46L 00009 46L 0000946L 00025 46L 00007 12L 0000446L 00052 12L 00008 12L 0000846L 00029 12L 00012 12L 0000446L 00026 12L 00008 12L 0000712L 00026 12L 00014 26L 0000512L 00043 26L 00007 26L 0000512L 00026 26L 0000612L 0004726L 0002626L 00024

Sample Compost 1 Sample Compost 1 Sample Compost 1Element PBD 154 Element PBD 183 Element PBD 196

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]4L 00010 46L 00002 46L 00011

46L 00003 46L 00024 46L 0000846L 00007 46L 00021 12L 0000246L 00003 46L 00003 12L 0000346L 00004 12L 00003 12L 0000112L 00003 12L 00011 12L 0000212L 00005 12L 0000312L 00031 12L 0000312L 00006

Sample Compost 1 Sample Compost 1 Sample Compost 1Element PBD 197 Element PBD 203 Element PBD 209

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00002 46L 00010 4L 0004146L 00023 12L 00002 4L 0008946L 00022 12L 00003 44L 0041012L 00004 12L 00002 44L 0084012L 00006 12L 00002 44L 0064012L 00003 44L 0040012L 00004 12L 00079

12L 0007312L 0006512L 0009326L 0004926L 00049

Sample Compost 1Element PBD 47

LAB PARM [mgkg]26L 0003826L 00039

Element PBD 99 Element PBD 47 Element PBD 209LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]

4L 00170 10L 00210 4L 010004L 00200 10L 00220 4L 018004L 00170 10L 00210 4L 012004L 00190 46L 00300 4L 0220010L 00280 46L 00280 46L 0210010L 00300 46L 00250 46L 0200010L 00290 46L 00260 64L 0351846L 00340 64L 00059 64L 0363846L 00330 64L 00057 64L 0364546L 00300 64L 00062 64L 0350846L 00310 64L 00060 12L 0220964L 00194 12L 00191 12L 0177164L 00154 12L 00187 12L 0292264L 00185 12L 00190 12L 0164664L 00159 12L 00186 26L 0329712L 00242 26L 00666 26L 0300012L 00223 26L 0033212L 0022112L 0022226L 0024626L 00400

Element PBD 203 Element PBD 197 Element PBD 196LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00022 46L 00027 46L 0002446L 00014 46L 00024 46L 0002264L 00036 12L 00161 64L 0005864L 00058 12L 00060 64L 0006512L 00063 12L 00061 12L 0004812L 00034 12L 00036 12L 0002512L 00038 12L 0003212L 00027 12L 00022

Element PBD 183 Element PBD 154 Element PBD 153LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00049 4L 00020 4L 0002246L 00035 4L 00022 4L 0002446L 00036 4L 00020 4L 0002246L 00034 46L 00025 4L 0002664L 00027 46L 00025 46L 0004064L 00023 46L 00025 46L 0004264L 00024 46L 00023 46L 0003564L 00020 64L 00034 46L 0003812L 00230 64L 00023 64L 0007412L 00032 64L 00017 64L 0004712L 00031 64L 00011 64L 0004612L 00030 12L 00030 64L 0003026L 00007 12L 00021 12L 0006526L 00008 12L 00021 12L 00029

12L 00021 12L 0003226L 00015 12L 0002926L 00019 26L 00039

26L 00040

Element PBD 100LAB PARM [mgkg]

4L 000384L 000414L 000374L 00038

38L 0219038L 0220038L 0208038L 0220010L 0004410L 0005010L 0004310L 0004646L 0005746L 0005946L 0005346L 0005312L 0004312L 0004512L 0004312L 0004326L 0006226L 00057

Sample Soil 3 Sample Soil 3 Sample Soil 3Element PBD 99 Element PBD 47 Element PBD 100

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]10L 00016 10L 00011 10L 0000310L 00019 10L 00010 10L 0000410L 00013 10L 00012 10L 0000410L 00019 46L 00007 10L 0000246L 00025 46L 00022 46L 0000246L 00025 46L 00005 46L 0000646L 00008 46L 00007 46L 0000246L 00011 12L 00010 46L 0000264L 00005 12L 00017 3L 29100064L 00005 12L 00010 3L 32000064L 00006 12L 00009 26L 0000564L 00007 26L 00007 26L 0000512L 00012 26L 0000712L 0001312L 0001312L 0001226L 0000526L 00006

Sample Soil 3 Sample Soil 3 Sample Soil 3Element PBD 153 Element PBD 154 Element PBD 196

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]44L 00050 4L 00010 46L 0000744L 00050 46L 00001 46L 0001146L 00002 46L 00002 46L 0000846L 00003 46L 00001 46L 0001146L 00002 46L 00002 64L 0002646L 00002 64L 00001 64L 0002664L 00001 64L 00001 64L 0002964L 00001 64L 00001 64L 0003464L 00001 64L 00002 12L 0004564L 00002 12L 00003 12L 00032

12L 00002 12L 0002212L 00002 12L 0002112L 00002

Sample Soil 3 Sample Soil 3 Sample Soil 3Element PBD 197 Element PBD 203 Element PBD 209

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00006 46L 00011 4L 0091046L 00013 46L 00017 4L 0150046L 00011 46L 00015 4L 0120046L 00013 46L 00018 4L 0160012L 00090 64L 00013 44L 0337012L 00056 64L 00014 44L 0281012L 00033 64L 00016 44L 0287012L 00032 64L 00015 44L 02540

12L 00055 46L 0230012L 00041 46L 0220012L 00027 46L 0150012L 00026 46L 01900

64L 0438164L 0401664L 0414464L 0449812L 0367112L 0397812L 0409112L 03838

Sample Soil 3 26L 0102Element PBD 183 26L 0131

LAB PARM [mgkg]46L 0000746L 0000846L 0005846L 0000764L 0000264L 0000364L 0000364L 0000312L 0001512L 0001112L 0000712L 00007

European Commission EUR 23003 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on polybrominated diphenylethers Author(s) E Sobiecka H van der Sloot D Barcelo B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 68 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07403-5 Abstract Project HORIZONTAL is interdisciplinary aiming at a harmonisation and horizontal standardisation of test procedures in particular for sludge soils and biowastes In the context of this standardization project a series of draft technical specification were designed upon an extensive desk study fine-tuned after expert consultations and finally validated in international intercomparisons exercise This report summarises the work performed within the validation study of the draft standard for the determination of polybrominated diphenylethers (PBDE) in soils sludge and treated bio-waste using gas-chromatography method with mass selective detection (GC-MS) It further explains the underlying statistical concept for the calculation of reproducibility and repeatability from intercomparisons data In addition all single values results of the statistical evaluation as well as background information on the validation materials used are described and explained

The mission of the JRC is to provide customer-driven scientific and technical support for the conception development implementation and monitoring of EU policies As a service of the European Commission the JRC functions as a reference centre of science and technology for the Union Close to the policy-making process it serves the common interest of the Member States while being independent of special interests whether private or national

LB

-NA

-23003-EN

-C

17

Annex 2

Report on the validation materials used

VI

Abstract This report gives an overview on the available analytical information on the following raw materials to be used for the production of validation materials of the so-called Project HORIZONTAL

bull Four sludge materials from Duumlsseldorf Germany

bull An agricultural soil material from Reading United Kingdom

bull A compost material from Vienna Austria

bull A compost material from Korschenbroich Germany

bull A sludge-amended agricultural soil from Pavia Province Italy

bull A sludge-amended soil from Barcelona Spain

bull A sludge-amended soil from Essen Germany

bull A long-term sludge exposed soil from Hohenheim Germany

VII

List of Abbreviations Throughout this report the following abbreviations are used

AOX absorbable organic halogens

Corg organic carbon content

Ctotal total carbon content

CAT cation exchangeable

CDD chlorinated dibenzodioxin

CDF chlorinated dibenzofuran

DEHP di(2-ethylhexyl)phthalate

DM dry matter

EPA Environment Protection Agency

EU European Union

FM fresh matter

Hp hepta

Hx hexa

IES Institute for Environment and Sustainability

IRMM Institute for Reference Materials and Measurements

JRC Joint Research Centre

LAS linear alkylsulfonates

LoD limit of detection

LUA Landesumweltamt

Ntotal total nitrogen content

NH4-N Ammonium nitrogen

NO3-N Nitrate nitrogen

NP nonylphenol

NRW North Rhine Westphalia

O octa

P poly

PAH polycyclic aromatic hydrocarbon

PCB polychlorinated biphenyl

Pe penta

T tetra

TEQ toxicity equivalent

UBA Umweltbundesamt

WHO World Health Organization

WWTP waste water treatment plant

6

1 Introduction This report gives an overview on the available analytical information on the following raw materials to be used for the production of validation materials of the so-called Project HORIZONTAL

bull Four sludge materials from Duumlsseldorf Germany

bull An agricultural soil material from Reading United Kingdom

bull A compost material from Vienna Austria

bull A compost material from Korschenbroich Germany

bull A sludge-amended agricultural soil from Pavia Province Italy

bull A sludge-amended soil from Barcelona Spain

bull A sludge-amended soil from Essen Germany

bull A long-term sludge exposed soil from Hohenheim Germany

The following analytical information was gathered partly before and during the sampling of the raw materials to be used for the production of the HORIZONTAL validation materials The material were sampled by IES and shipped to IRMM in the course of the year 2005 The information gathered was then completed by various analytical screenings for PAHs and PCBs done by the Institute for Reference Materials and Measurements Geel Belgium for phthalates done by UBA Berlin Germany for PBDE done by IIQAB-CSIC Barcelona Spain for trace elements and some selected major and minor elements by the Institute for Environment and Sustainability Ispra Italy

The work compiled hereafter is based on the numerous additional efforts of the scientists working at various members of the consortium Project HORIZONTAL-Org and contributing organisations

This work is gratefully acknowledged

2 Overview on property values

21 Sludge materials from Duumlsseldorf Germany

The various sewage sludge materials originate from various installations in the North Rhine Westphalia and were produced and sampled by staff from the Landesumweltamt (LUA) NRW under the responsibility from Dr K Furtmann

In total four sludge materials (Sludge A and D from a major municipal WWTP Sludge B from a municipal WWTP with industrial input and Sludge C from a municipal WWTP with high PCB-Content) were obtained and will be blended to two final materials Before sampling the following analytical data for a typical sample were received

7

Table 1 ndash Analytical data obtained on an average sludge sample in LUA NRW (with courtesy of K Furtmann LUA Duumlsseldorf)

Parameter Concentration PCB 120 ugkg DEHP 110 mgkg PAH 5 mgkg (EPA) PCDDF 15 ng TEkg PBDE 400 ugkg NP 40 mgkg LAS 3 gkg AOX 300 mgkg

Subsequent screening led to the information displayed hereafter It should be stressed that the data were obtained as SCREENING information on the UNTREATED or partially treated raw materials Therefore the final target values which are relevant for the validation intercomparison can be different

Table 2 ndash Analytical data obtained on a first screening on the sludge samples from LUA NRW

Sewage sludge A

Dusseldorf

sewage sludge D

Dusseldorf PCB (ngg) 28 62 35 52 101 65 101 31 38 118 49 40 153 30 33 105 24 11 138 46 38 156 lt1 lt1 180 34 23 170 23 19 PAH (ngg) Naphtalene 34 381 Acenaphtylene 15 43 Acenaphthene 81 108 Fluorene 94 1167 Phenantrene 3440 Anthracene 22 344 Flouranthene 316 4817 Pyrene 235 3011 Benz(a)anthracene 473 791 Chrysene 691 1078 Benz(b)fluoranthene 538 1688 Benz(k)fluoranthene 228 635 Benz(a)pyrene 383 1114 Indeno(123-cd)pyrene 92 229 Dibenzo(ah)anthracene 71 70 Benzo(ghi)perylene 80 185

8

Table 3 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Sludge D (1) 0135 41474 385 Sludge B (2) 0538 0034 30634 547 Sludge A (3) 0184 0037 31399 146 Sludge C (4) 0354 1528 6678 229

Table 4 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Sludge 2

(B)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

554

959

694

591

772

509

nq

nq

970

2216

2379

Table 5 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena IES Ispra Spain) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Sludge 1 (D) 265 290 533 359 1231 338 784 438 lt 005 232 786 Sludge 2 (B) 119 311 626 202 278 299 722 251 lt 005 118 625 Sludge 3 (A) 168 360 621 332 847 416 119 451 lt 005 116 1237 Sludge 4 (C) 563 198 116 273 726 511 473 618 lt 005 444 2015

Table 6 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Sludge 1 (D) 2154 58 844 099 103 101 4367 lt15 50448 Sludge 2 (B) 1067 366 692 046 1491 077 5217 lt15 57633 Sludge 3 (A) 731 663 684 035 1287 068 3733 lt15 60369 Sludge 4 (C) 4379 965 527 163 522 107 5628 lt15 23945

Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM)Sludge 1 (D) 03 2403 101 1002 350 15 1944 132Sludge 2 (B) 031 315 97 879 172 12 514 180Sludge 3 (A) 031 1281 153 1567 265 16 1440 168Sludge 4 (C) 055 231 628 2625 371 81 1101 244

9

22 Agricultural soil material from Reading United Kingdom

The material was proposed by the University of Reading (S Nortcliff) and was sampled from a site called ldquoFrogmore Farmrdquo which was featured in the ldquoMetalsrdquo Report for HORIZONTAL This site is close to Reading with soils developed on flintyloamy periglacial materials over Chalk has a long and well documented history of sludge application The focus of the work of Nortcliff et al undertook at this site and the monitoring and control at the site (by Thames Water and the subsequent subsidiary bodies dealing with sludge application to soil) was on metals (and metal loads) with no analysis or indeed any form of investigation in to organics in the broadest sense

The analytical information produced in the context of the screening of the raw material is displayed below

Table 7 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 3

(Reading) 0032 0119 669

Table 8 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 3 (Reading) 015 706 279 138 152 901 267 300 lt 005 258 931

Table 9 ndash Analytical data obtained on a first screening on the sludge-amended soil from Reading (courtesy of IRMM)

Parameter Concentration

PCB ngg 28 lt1 52 lt1 101 lt1 118 lt1 153 lt1 105 lt1 138 lt1 156 lt1 180 lt1 170 lt1 PAH ngg Naphtalene lt10 Acenaphtylene 21 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene lt10 Flouranthene 818 Pyrene 776 Benz(a)anthracene 565

10

Parameter Concentration

Chrysene 608 Benz(b)fluoranthene 824 Benz(k)fluoranthene 329 Benz(a)pyrene 799 Indeno(123-cd)pyrene

779

Dibenzo(ah)anthracene 118 Benzo(ghi)perylene 394

Table 10 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 3

(Reading)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

103

003

nq

nq

nq

nd

nd

272

273

Table 11 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 3 (Reading) 015 706 279 138 152 901 267 300 lt 005 258 931

Table 12 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 3 (Reading) 7936 477 112 096 194 017 4107 443 2102 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 3 (Reading) 042 13 45 69 69 69 216 92

Table 13 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 3 (Reading) 012

11

23 Compost from Vienna Austria

The fresh compost material was obtained from the Austrian Federal Environment Agency (UBA Vienna) which had used a sub-batch of the raw material for national intercomparson The remainder of the material was stored at 4degC until shipment to IRMM for further processing The following analytical information was provided by UBA Austria and completed with various screenings

Table 14 ndash Analytical data on compost material received from UBA Austria Inorganic and sum parameters

Parameter Unit Sample fraction used Observed mean B CAT mgl FM Fresh sample lt10mm 61 K CAT mgl FM Fresh sample lt10mm 2624 Mg CAT mgl FM Fresh sample lt10mm 242 P CAT mgl FM Fresh sample lt10mm 49 B CAT DM Fresh sample lt10mm 00017 K CAT DM Fresh sample lt10mm 072 Mg CAT DM Fresh sample lt10mm 007 P CAT DM Fresh sample lt10mm 001 NO3-N mgkg FM Fresh sample lt10mm 35 NH4-N mgkg FM Fresh sample lt10mm 230 Ctotal DM lt45degdry milled 29 Corg DM lt45degdry milled 27 Ntotal DM lt45degdry milled 17 P mgkg DM lt45degdry milled 2596 K mgkg DM lt45degdry milled 11019 K DM lt45degdry milled 110 B mgkg DM lt45degdry milled 60 Cd mgkg DM lt45degdry milled 046 Cr mgkg DM lt45degdry milled 25 Cu mgkg DM lt45degdry milled 46 Hg mgkg DM lt45degdry milled 020 Ni mgkg DM lt45degdry milled 18 Pb mgkg DM lt45degdry milled 45 Zn mgkg DM lt45degdry milled 198 Ca mgkg DM lt45degdry milled 68776 Ca DM lt45degdry milled 69 Mo mgkg DM lt45degdry milled 08 S mgkg DM lt45degdry milled 2137 Fe mgkg DM lt45degdry milled 9959 Mn mgkg DM lt45degdry milled 418 Na mgkg DM lt45degdry milled 742 Co mgkg DM lt45degdry milled 41 AOX mgkg DM lt30deg dry milled 62

Table 15 ndash Analytical data on compost material received from UBA Austria Polycyclic aromatic hydrocarbons

PAH Unit Result Naphthaline microgkg DM 93 Acenaphthylene microgkg DM 86 Acenaphthene microgkg DM 5 Fluorene microgkg DM 80 Phenanthrene microgkg DM 89 Anthracene microgkg DM 27 Fluoranthene microgkg DM 487 Pyrene microgkg DM 380

12

PAH Unit Result Benzo(a)anthracene microgkg DM 278 Chrysene microgkg DM 317 Benzo(b)fluoranthene microgkg DM 365 Benzo(k)fluoranthene microgkg DM 193 Benz(a)pyrene microgkg DM 320 Indeno(123-cd)pyrene microgkg DM 233 Dibenz(ah)anthracene microgkg DM 67 Benzo(ghi)perylene microgkg DM 225 Sum EPA microgkg DM 3013 Sum EPA mgkg DM 30

Table 16 ndash Analytical data on compost material received from UBA Austria Sum PCDDs and PCBs

Parameter

Dioxine TEQ (ITEF) ngkg DM 73 TEQ (WHO) ngkg DM 35 PCB Σ Ballschmiter mgkg DM 005

Table 17 ndash Analytical data on compost material obtained by screening in IRMM

Parameter Result in ngg

PCB 28 2 52 2 101 4 118 3 153 10 105 1 138 8 156 1 180 5 170 lt1 PAH Naphtalene lt10 Acenaphtylene lt10 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene 26 Fluoranthene 611 Pyrene 510 Benz(a)anthracene 888 Chrysene 957 Benz(b)fluoranthene 1531 Benz(k)fluoranthene 547 Benz(a)pyrene 1101 Indeno(123-cd)pyrene 416 Dibenzo(ah)anthracene 81 Benzo(ghi)perylene 295

13

Table 18 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Compost 1

(Vienna)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

402

019

259

nq

023

004

nq

nq

144

174

259

Table 19 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Compost 1

(Vienna) 0058 1426 557

Table 20 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Compost 1 (Vienna) 039 736 319 410 365 127 495 004 079 013 208

Table 21 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Compost 1 (Vienna) 2063 431 617 426 199 249 1602 lt15 10521

Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Compost 1 (Vienna) 035 3496 81 375 79 55 653 60

Table 22 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Compost 1 (Vienna) 017

14

24 Agricultural soil sludge amended soil from Pavia Italy

This sludge-amended soil material was obtained during a monitoring campaign which aimed at a generic description of the over-all soil quality in Pavia Province Italy The material which was collected from the upper horizon originates from a small farm called ldquoCascina Novellordquo During the characterisation of the site the following analytical information was obtained on a pooled sample of a sub-area of the farm of 20 X 20 m2

Table 23 ndash Analytical data on Pavia soil

Parameter Result Al 713 Wgt As 224 mgkg Cd 079 mgkg Cr 59 mgkg Cu 308 mgkg Hg 008 mgkg Ni 344 mgkg Pb 246 mgkg Zn 95 mgkg C 091 Wgt 2378-TCDD 0047 pgg 12378-PeCDD 015 pgg 123478-HxCDD 019 pgg 123678-HxCDD 15 pgg 123789-HxCDD 074 pgg 1234678-HpCDD 26 pgg OCDD 382 pgg 2378-TCDF 068 pgg 12378-PeCDF 053 pgg 23478-PeCDF 071 pgg 123478-HxDF 100 pgg 123678-HxDF 066 pgg 234678-HxDF 16 pgg 123789-HxDF 027 pgg 1234678-HpDF 12 pgg 1234789-HpDF 068 pgg OCDF 33 pgg I-TEQ 20 pgg WHO-TEQ 17 pgg

In addition the screening performed at IRMM did not reveal significant quantities of PCBs and PAHs which were all below the LoDs (1 ngg for PCBs and 10 ngg for PAHs respectively)

Table 24 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 5 (Pavia) 0005 0011 154

15

Table 25 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 5

(Pavia)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

039

nq

nq

008

nq

nd

nd

670

671

Table 26 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 5 (Pavia) 033 184 573 225 426 305 206 200 lt 005 381 878

Table 27 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 5 (Pavia) 6939 129 145 224 425 116 6118 255 1789 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 5 (Pavia) 184 62 38 108 55 66 597 110

Table 28 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 5 (Pavia) 006

16

25 Sludge-amended-soil from Barcelona Spain

The sludge-amended soil material from Barcelona sampled upon indication from the Barcelorsquo- Group in Barcelona

Table 29 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 2 (Lleida T) 0015 0183 1138

Table 30 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 2

(Lleida T)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

159

045

nq

048

160

nq

nq

1000

1004

Table 31 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 2 (Lleida T) 059 141 327 536 405 186 184 224 lt 005 318 111

Table 32 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 2 (Lleida T) 4443 1067 1429 253 344 204 4116 780 3396 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 2 (Lleida T) 064 65 26 125 59 17 547 65

Table 33 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 2 (Lleida T) 010

17

26 Sludge amended soil from Essen Germany

The German sludge-amended soil from Essen which was provided as the three sludge materials by LUA NRW did not feature significant concentrations of the PCB congeners 28 52 101 118 153 105 138 156 180 170 but had detectable amounts of some PAHs

Table 34 ndash Analytical screening data on the German sludge-amended soil

Parameter Concentration(ngg)

Naphtalene lt10 Acenaphtylene lt10 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene lt10 Fluoranthene 28 Pyrene 20 Benz(a)anthracene 24 Chrysene 47 Benz(b)fluoranthene 76 Benz(k)fluoranthene 20 Benz(a)pyrene 35 Indeno(123-cd)pyrene 35 Dibenzo(ah)anthracene 10 Benzo(ghi)perylene 26

Table 35 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 4 (Essen) 0011 0302 055

Table 36 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 4

(Essen)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

nq

nq

nq

nq

nq

nq

128

191

203

18

Table 37 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 4 (Essen) 052 545 261 805 320 403 273 273 lt 005 295 781

Table 38 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 4 (Essen) 7947 442 085 06 086 007 2163 189 2019 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 4 (Essen) 045 19 42 87 683 60 462 61

Table 39 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 4 (Essen) 004

27 Long-term sludge exposed soil from Hohenheim-Stuttgart Germany

Similarly an additional sludge exposed soil was sampled at the University of Hohenheim Stuttgart were a test soil was long-term exposed to elevated concentrations of sewage sludge

Table 40 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 1 (Stuttgart) 0045 0263 1765

Table 41 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 1

(Stuttgart)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

230

006

004

004

nq

nd

nd

498

500

19

Table 42 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 1 (Stuttgart) 069 127 361 262 504 183 252 262 lt 005 266 142

Table 43 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 1 (Stuttgart) 7194 1006 133 186 366 088 7874 275 3571 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 1 (Stuttgart) 123 50 47 212 85 69 991 129

Table 44 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 1 (Stuttgart) 177

18

Annex 3

Statistical calculations

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 47)Mandels h statistics(Sludge 1 - PBD 47)

Sample Sludge 1 NUM

Element PBD 47

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00213 0001 3 -021 005 - - 10L - - NUM46L 00273 0002 4 016 021 - - 46L - - NUM64L 00059 0000 4 -116 002 NUM - 64L - - NUM12L 00188 0000 4 -036 002 - - 12L - - NUM26L 00499 0024 2 157 223 Fail - - 26L - - NUM

Totgem 0025 0005 mgkg 1-level 172 (185) NUM (10L46L64L12L26L) -1Totstd= 0016 0010 5-level 157 (162) 5

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 5 Labs rejected (10L46L64L12L26L)

000 050 100 150 200 250

k-values

10L

46L

64L

12L

26L

Mandels k statistics(Sludge 1 - PBD 47)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

10L

46L

64L

12L

26L

Labo

rato

ries

NUM

-200 -100 000 100 200

h-values

10L

46L

64L

12L

26L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 47)

Sludge 1-PBD 47

Unit mgkg

Mandels k statistics(Soil 3 - PBD 47)Mandels h statistics(Soil 3 - PBD 47)

Sample Soil 3 Soil 3 - PBD 47 -- Mean PARM = 0001 [mgkg]

Element PBD 47

General calcparmT1= 134814E-02T2= 142830E-05T3= 13T4= 45T5= 22767E-06

n= variabelp= 4

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean26L 00007 0000 2 -143 001 00007 00000 2 1 00046L 00010 0001 4 010 181 00010 00008 4 3 00010L 00011 0000 3 049 023 00011 00001 3 2 00012L 00012 0000 4 084 081 00012 00004 4 3 000

Totgem 0001 0000 mgkg 1-level 149 (177) 4 00010 () 4 3Totstd= 0000 0000 5-level 142 (159)

RESULTS Mean = 000100 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000050 --gt 5031 r = 00014Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000050 --gt 5031 R = 00014Remarks none

000 050 100 150 200

k-values

26L

46L

10L

12L

Mandels k statistics(Soil 3 - PBD 47)

00 00 00 00 00 00 00 00 00 00 00

Deviation from Mean

26L

46L

10L

12L

Labo

rato

ries

Soil 3 - PBD 47 -- Mean PARM = 0001 [mgkg]

-200 -100 000 100

h-values

26L

46L

10L

12L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 47)

Soil 3-PBD 47

Unit mgkg

Mandels k statistics(Compost 1 - PBD 99)Mandels h statistics(Compost 1 - PBD 99)

Sample Compost 1 Compost 1 - PBD 99 -- Mean PARM = 0003 [mgkg]

Element PBD 99

General calcparmT1= 492124E-02T2= 148747E-04T3= 17T4= 61T5= 93196E-06

n= variabelp= 5

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00020 0000 4 -137 053 00020 00004 4 3 000

26L 00025 0000 2 -058 024 00025 00002 2 1 00010L 00029 0000 3 012 032 00029 00003 3 2 00046L 00033 0001 4 069 161 00033 00013 4 3 00012L 00036 0001 4 114 140 00036 00011 4 3 000

Totgem 0003 0001 mgkg 1-level 172 (185) 5 00029 () 5 4Totstd= 0001 0001 5-level 157 (162)

RESULTS Mean = 000286 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000088 --gt 3086 r = 00025Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000101 --gt 3525 R = 00028Remarks none

000 050 100 150 200

k-values

4L

26L

10L

46L

12L

Mandels k statistics(Compost 1 - PBD 99)

00 00 00 00 00 00 00 00 00 00

Deviation from Mean

4L

26L

10L

46L

12L

Labo

rato

ries

Compost 1 - PBD 99 -- Mean PARM = 0003 [mgkg]

-200 -100 000 100 200

h-values

4L

26L

10L

46L

12L

Labo

rato

ries

Mandels h statistics(Compost 1 - PBD 99)

Compost 1-PBD 99

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 99)Mandels h statistics(Sludge 1 - PBD 99)

Sample Sludge 1 Sludge 1 - PBD 99 -- Mean PARM = 0024 [mgkg]

Element PBD 99

General calcparmT1= 448050E-01T2= 112113E-02T3= 19T4= 73T5= 32972E-05

n= variabelp= 5

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean64L 00173 0002 4 -118 041 Fail 00173 00019 4 3 -0014L 00183 0002 4 -104 032 00183 00015 4 3 -001

12L 00227 0001 4 -038 022 00227 00010 4 3 00010L 00290 0001 3 055 021 00290 00010 3 2 00146L 00320 0002 4 100 039 00320 00018 4 3 00126L 00323 0011 2 105 234 - - 26L - - 001

Totgem 0025 0003 mgkg 1-level 187 (177) 5 00239 (26L) 5 4Totstd= 0007 0004 5-level 166 (154) 1

RESULTS Mean = 002385 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000153 --gt 643 r = 00043Between lab variance S2L = 000004Reproducibility var S2R = 000004Reproducibility std SR = 000666 --gt 2791 R = 00186Remarks 1 Lab rejected (26L)

000 050 100 150 200 250

k-values

64L

4L

12L

10L

46L

26L

Mandels k statistics(Sludge 1 - PBD 99)

00 00 00 00 00 00 00 00 00 00

Deviation from Mean

64L

4L

12L

10L

46L

26L

Labo

rato

ries

Sludge 1 - PBD 99 -- Mean PARM = 0024 [mgkg]

-200 -100 000 100 200

h-values

64L

4L

12L

10L

46L

26L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 99)

Sludge 1-PBD 99

Unit mgkg

Mandels k statistics(Soil 3 - PBD 99)Mandels h statistics(Soil 3 - PBD 99)

Sample Soil 3 NUM

Element PBD 99

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00017 0000 4 091 068 - - 10L - - NUM46L 00017 0001 4 100 211 - - 46L - - NUM64L 00005 0000 4 -106 023 NUM - 64L - - NUM12L 00012 0000 4 015 014 - - 12L - - NUM26L 00006 0000 2 -101 012 - - 26L - - NUM

Totgem 0001 0000 mgkg 1-level 172 (173) NUM (10L46L64L12L26L) -1Totstd= 0001 0000 5-level 157 (153) 5

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 5 Labs rejected (10L46L64L12L26L)

000 050 100 150 200 250

k-values

10L

46L

64L

12L

26L

Mandels k statistics(Soil 3 - PBD 99)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

10L

46L

64L

12L

26L

Labo

rato

ries

NUM

-200 -100 000 100 200

h-values

10L

46L

64L

12L

26L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 99)

Soil 3-PBD 99

Unit mgkg

Mandels k statistics(Compost 1 - PBD 100)Mandels h statistics(Compost 1 - PBD 100)

Sample Compost 1 Compost 1 - PBD 100 -- Mean PARM = 0001 [mgkg]

Element PBD 100

General calcparmT1= 124272E-02T2= 113129E-05T3= 14T4= 52T5= 46584E-07

n= variabelp= 4

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean26L 00006 0000 2 -131 037 Fail 00006 00001 2 1 00010L 00009 0000 4 003 083 00009 00002 4 3 00046L 00009 0000 4 016 115 00009 00002 4 3 00012L 00011 0000 4 112 136 Fail 00011 00003 4 3 000

Totgem 0001 0000 mgkg 1-level 149 (167) 4 00009 () 4 3Totstd= 0000 0000 5-level 142 (15)

RESULTS Mean = 000085 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000022 --gt 2531 r = 00006Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000025 --gt 2882 R = 00007Remarks none

000 050 100 150

k-values

26L

10L

46L

12L

Mandels k statistics(Compost 1 - PBD 100)

00 00 00 00 00 00 00 00 00 00 00

Deviation from Mean

26L

10L

46L

12L

Labo

rato

ries

Compost 1 - PBD 100 -- Mean PARM = 0001 [mgkg]

-200 -100 000 100 200

h-values

26L

10L

46L

12L

Labo

rato

ries

Mandels h statistics(Compost 1 - PBD 100)

Compost 1-PBD 100

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 100)Mandels h statistics(Sludge 1 - PBD 100)

Sample Sludge 1 Sludge 1 - PBD 100 -- Mean PARM = 0005 [mgkg]

Element PBD 100

General calcparmT1= 852065E-02T2= 412762E-04T3= 18T4= 68T5= 78914E-07

n= variabelp= 5

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00039 0000 4 -042 007 Fail 00039 00002 4 3 000

12L 00044 0000 4 -041 005 Fail 00044 00001 4 3 00010L 00046 0000 4 -041 013 Fail 00046 00003 4 3 00046L 00056 0000 4 -040 012 Fail 00056 00003 4 3 00026L 00059 0000 2 -040 013 Fail 00059 00003 2 1 00038L 02168 0006 4 204 244 Fail - - 38L - - 021

Totgem 0040 0001 mgkg 1-level 187 (177) 5 00049 (38L) 5 4Totstd= 0087 0002 5-level 166 (154) 1

RESULTS Mean = 000486 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000025 --gt 507 r = 00007Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000084 --gt 1731 R = 00024Remarks 1 Lab rejected (38L)

000 050 100 150 200 250

k-values

4L

12L

10L

46L

26L

38L

Mandels k statistics(Sludge 1 - PBD 100)

-01 00 01 01 02 02 03

Deviation from Mean

4L

12L

10L

46L

26L

38L

Labo

rato

ries

Sludge 1 - PBD 100 -- Mean PARM = 0005 [mgkg]

-100 000 100 200 300

h-values

4L

12L

10L

46L

26L

38L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 100)

Sludge 1-PBD 100

Unit mgkg

Mandels k statistics(Soil 3 - PBD 100)Mandels h statistics(Soil 3 - PBD 100)

Sample Soil 3 NUM

Element PBD 100

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00003 0000 4 -050 000 Fail - - 10L - - NUM46L 00003 0000 4 -050 000 Fail NUM - 46L - - NUM3L 305500 2051 2 150 200 Fail - - 3L - - NUM

26L 00005 0000 2 -050 000 Fail - - 26L - - NUM

Totgem 7638 0513 mgkg 1-level 149 (177) NUM (10L46L3L26L) -1Totstd= 15275 1025 5-level 142 (159) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (10L46L3L26L)

000 050 100 150 200

k-values

10L

46L

3L

26L

Mandels k statistics(Soil 3 - PBD 100)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

10L

46L

3L

26L

Labo

rato

ries

NUM

-100 000 100 200

h-values

10L

46L

3L

26L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 100)

Soil 3-PBD 100

Unit mgkg

Mandels k statistics(Compost 1 - PBD 153)Mandels h statistics(Compost 1 - PBD 153)

Sample Compost 1 NUM

Element PBD 153

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean44L 00053 0001 3 150 157 Fail - - 44L - - NUM46L 00007 0000 4 -044 111 Fail - - 46L - - NUM12L 00005 0000 4 -051 055 Fail - - 12L - - NUM26L 00005 0000 2 -054 001 Fail NUM - 26L - - NUM

Totgem 0002 0000 mgkg 1-level 149 (177) NUM (44L46L12L26L) -1Totstd= 0002 0000 5-level 142 (159) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (44L46L12L26L)

000 050 100 150 200

k-values

44L

46L

12L

26L

Mandels k statistics(Compost 1 - PBD 153)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

44L

46L

12L

26L

Labo

rato

ries

NUM

-100 000 100 200

h-values

44L

46L

12L

26L

Labo

rato

ries

Mandels h statistics(Compost 1 - PBD 153)

Compost 1-PBD 153

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 153)Mandels h statistics(Sludge 1 - PBD 153)

Sample Sludge 1 Sludge 1 - PBD 153 -- Mean PARM = 0004 [mgkg]

Element PBD 153

General calcparmT1= 676738E-02T2= 267609E-04T3= 18T4= 68T5= 19626E-05

n= variabelp= 5

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00024 0000 4 -157 017 00024 00002 4 3 000

12L 00038 0002 4 006 154 00038 00018 4 3 00046L 00039 0000 4 011 026 00039 00003 4 3 00026L 00039 0000 2 018 004 00039 00000 2 1 00064L 00049 0002 4 122 159 00049 00018 4 3 000

Totgem 0004 0001 mgkg 1-level 172 (173) 5 00038 () 5 4Totstd= 0001 0001 5-level 157 (153)

RESULTS Mean = 000378 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000123 --gt 3252 r = 00034Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000142 --gt 3754 R = 00040Remarks none

000 050 100 150 200

k-values

4L

12L

46L

26L

64L

Mandels k statistics(Sludge 1 - PBD 153)

00 00 00 00 00 00 00

Deviation from Mean

4L

12L

46L

26L

64L

Labo

rato

ries

Sludge 1 - PBD 153 -- Mean PARM = 0004 [mgkg]

-200 -100 000 100 200

h-values

4L

12L

46L

26L

64L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 153)

Sludge 1-PBD 153

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 154)Mandels h statistics(Sludge 1 - PBD 154)

Sample Sludge 1 NA

Element PBD 154

General calcparmT1= NAT2= NAT3=T4=T5=

n= variabelp=

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00021 0000 3 -100 021 NA - 4L - - NA

46L 00025 0000 4 115 018 NA - 46L - - NA64L 00021 0001 4 -066 179 - - 64L - - NA12L 00023 0000 4 050 085 - - 12L - - NA

Totgem 0002 0000 mgkg 1-level 149 (167) NA (4L46L64L12L) -1Totstd= 0000 0000 5-level 142 (15) 4

RESULTS Mean = NA mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NAReproducibility var S2R = NAReproducibility std SR = NA --gt NA R = NARemarks 4 Labs rejected (4L46L64L12L)

000 050 100 150 200

k-values

4L

46L

64L

12L

Mandels k statistics(Sludge 1 - PBD 154)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

4L

46L

64L

12L

Labo

rato

ries

NA

-100 000 100 200

h-values

4L

46L

64L

12L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 154)

Sludge 1-PBD 154

Unit mgkg

Mandels k statistics(Soil 3 - PBD 154)Mandels h statistics(Soil 3 - PBD 154)

Sample Soil 3 NUM

Element PBD 154

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

4L 00010 - 1 150 Fail - - 4L - - NUM46L 00001 0000 4 -053 096 Fail - - 46L - - NUM64L 00001 0000 4 -056 105 Fail NUM - 64L - - NUM12L 00002 0000 4 -040 099 Fail - - 12L - - NUM

Totgem 000037 0000 mgkg 1-level 149 (164) NUM (4L46L64L12L) -1Totstd= 000042 0000 5-level 142 (153) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (4L46L64L12L)

000 050 100 150

k-values

4L

46L

64L

12L

Mandels k statistics(Soil 3 - PBD 154)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

4L

46L

64L

12L

Labo

rato

ries

NUM

-100 000 100 200

h-values

4L

46L

64L

12L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 154)

Soil 3-PBD 154

Unit mgkg

Mandels k statistics(Compost 1 - PBD 209)Mandels h statistics(Compost 1 - PBD 209)

Sample Compost 1 NUM

Element PBD 209

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00065 0003 2 -049 032 - - 4L - - NUM

44L 00573 0021 4 150 197 Fail - - 44L - - NUM12L 00078 0001 4 -045 011 - - 12L - - NUM26L 00049 0000 2 -056 000 NUM - 26L - - NUM

Totgem 0019 0006 mgkg 1-level 149 (177) NUM (4L44L12L26L) -1Totstd= 0025 0010 5-level 142 (159) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (4L44L12L26L)

000 050 100 150 200

k-values

4L

44L

12L

26L

Mandels k statistics(Compost 1 - PBD 209)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

4L

44L

12L

26L

Labo

rato

ries

NUM

-100 000 100 200

h-values

4L

44L

12L

26L

Labo

rato

ries

Mandels h statistics(Compost 1 - PBD 209)

Compost 1-PBD 209

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 209)Mandels h statistics(Sludge 1 - PBD 209)

Sample Sludge 1 Sludge 1 - PBD 209 -- Mean PARM = 0249 [mgkg]

Element PBD 209

General calcparmT1= 394542E+00T2= 107296E+00T3= 16T4= 56T5= 19723E-02

n= variabelp= 5

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 01550 0055 4 -112 148 Fail 01550 00551 4 3 -009

46L 02050 0007 2 -053 019 02050 00071 2 1 -00412L 02137 0058 4 -042 155 02137 00576 4 3 -00426L 03149 0021 2 078 057 Fail 03149 00210 2 1 00764L 03577 0007 4 129 020 Fail 03577 00074 4 3 011

Totgem 0249 0030 mgkg 1-level 172 (185) 5 02493 () 5 4Totstd= 0084 0025 5-level 157 (162)

RESULTS Mean = 024926 mgkg

Repeatability variance S2r = 000179Repeatability std Sr = 004234 --gt 1699 r = 01186Between lab variance S2L = 000743Reproducibility var S2R = 000922Reproducibility std SR = 009604 --gt 3853 R = 02689Remarks none

000 050 100 150 200

k-values

4L

46L

12L

26L

64L

Mandels k statistics(Sludge 1 - PBD 209)

-01 -01 00 01 01 02

Deviation from Mean

4L

46L

12L

26L

64L

Labo

rato

ries

Sludge 1 - PBD 209 -- Mean PARM = 0249 [mgkg]

-200 -100 000 100 200

h-values

4L

46L

12L

26L

64L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 209)

Sludge 1-PBD 209

Unit mgkg

Mandels k statistics(Soil 3 - PBD 209)Mandels h statistics(Soil 3 - PBD 209)

Sample Soil 3 Soil 3 - PBD 209 -- Mean PARM = 0258 [mgkg]

Element PBD 209

General calcparmT1= 596398E+00T2= 191917E+00T3= 22T4= 84T5= 13249E-02

n= variabelp= 6

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean26L 01162 0021 2 -108 074 Fail 01162 00207 2 1 -0144L 01303 0031 4 -097 111 Fail 01303 00312 4 3 -013

46L 01975 0036 4 -046 128 Fail 01975 00359 4 3 -00644L 02898 0035 4 024 124 Fail 02898 00346 4 3 00312L 03895 0018 4 100 065 Fail 03895 00181 4 3 01364L 04260 0022 4 127 078 Fail 04260 00219 4 3 017

Totgem 0258 0027 mgkg 1-level 187 (177) 6 02582 () 6 5Totstd= 0132 0008 5-level 166 (154)

RESULTS Mean = 025818 mgkg

Repeatability variance S2r = 000083Repeatability std Sr = 002878 --gt 1115 r = 00806Between lab variance S2L = 001640Reproducibility var S2R = 001723Reproducibility std SR = 013127 --gt 5084 R = 03676Remarks none

000 050 100 150

k-values

26L

4L

46L

44L

12L

64L

Mandels k statistics(Soil 3 - PBD 209)

-02 -01 -01 00 01 01 02 02

Deviation from Mean

26L

4L

46L

44L

12L

64L

Labo

rato

ries

Soil 3 - PBD 209 -- Mean PARM = 0258 [mgkg]

-200 -100 000 100 200

h-values

26L

4L

46L

44L

12L

64L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 209)

Soil 3-PBD 209

Unit mgkg

Mandels k statistics(Compost 1 - Sum PBD)Mandels h statistics(Compost 1 - Sum PBD)

Sample Compost 1 Compost 1 - Sum PBD -- Mean PARM = 0009 [mgkg]

Element Sum PBD

General calcparmT1= 154064E-01T2= 169065E-03T3= 18T4= 68T5= 11354E-04

n= variabelp= 5

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00031 0002 4 -067 016 00031 00016 4 3 -0014L 00055 0005 4 -056 048 00055 00047 4 3 000

46L 00085 0003 4 -042 031 00085 00030 4 3 00026L 00123 0000 2 -024 003 00123 00002 2 1 00012L 00154 0002 4 -011 021 00154 00021 4 3 00144L 00613 0023 4 200 237 Fail - - 44L - - 005

Totgem 0018 0006 mgkg 1-level 187 (177) 5 00089 (44L) 5 4Totstd= 0022 0009 5-level 166 (154) 1

RESULTS Mean = 000893 mgkg

Repeatability variance S2r = 000001Repeatability std Sr = 000296 --gt 3308 r = 00083Between lab variance S2L = 000002Reproducibility var S2R = 000003Reproducibility std SR = 000570 --gt 6374 R = 00159Remarks 1 Lab rejected (44L)

000 050 100 150 200 250

k-values

10L

4L

46L

26L

12L

44L

Mandels k statistics(Compost 1 - Sum PBD)

00 00 00 00 00 00 01 01

Deviation from Mean

10L

4L

46L

26L

12L

44L

Labo

rato

ries

Compost 1 - Sum PBD -- Mean PARM = 0009 [mgkg]

-100 000 100 200

h-values

10L

4L

46L

26L

12L

44L

Labo

rato

ries

Mandels h statistics(Compost 1 - Sum PBD)

Compost 1-Sum PBD

Unit mgkg

Mandels k statistics(Sludge 1 - Sum PBD)Mandels h statistics(Sludge 1 - Sum PBD)

Sample Sludge 1 Sludge 1 - Sum PBD -- Mean PARM = 0256 [mgkg]

Element Sum PBD

General calcparmT1= 531806E+00T2= 162188E+00T3= 22T4= 84T5= 25223E-02

n= variabelp= 6

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00423 0025 4 -156 044 Fail 00423 00252 4 3 -02146L 01808 0118 4 -049 205 - - 46L - - -0074L 01810 0056 4 -049 097 01810 00558 4 3 -007

38L 02168 0006 4 -022 010 02168 00059 4 3 -00412L 02890 0065 4 034 113 02890 00647 4 3 00364L 03958 0008 4 116 014 Fail 03958 00079 4 3 01426L 04094 0034 2 126 059 Fail 04094 00337 2 1 015

Totgem 0245 0044 mgkg 1-level 198 (179) 6 02557 (46L) 6 5Totstd= 0130 0039 5-level 171 (155) 1

RESULTS Mean = 025570 mgkg

Repeatability variance S2r = 000158Repeatability std Sr = 003970 --gt 1553 r = 01112Between lab variance S2L = 001807Reproducibility var S2R = 001964Reproducibility std SR = 014015 --gt 5481 R = 03924Remarks 1 Lab rejected (46L)

000 050 100 150 200 250

k-values

10L

46L

4L

38L

12L

64L

26L

Mandels k statistics(Sludge 1 - Sum PBD)

-03 -02 -02 -01 -01 00 01 01 02 02

Deviation from Mean

10L

46L

4L

38L

12L

64L

26L

Labo

rato

ries

Sludge 1 - Sum PBD -- Mean PARM = 0256 [mgkg]

-200 -100 000 100 200

h-values

10L

46L

4L

38L

12L

64L

26L

Labo

rato

ries

Mandels h statistics(Sludge 1 - Sum PBD)

Sludge 1-Sum PBD

Unit mgkg

Mandels k statistics(Soil 3 - Sum PBD)Mandels h statistics(Soil 3 - Sum PBD)

Sample Soil 3 Soil 3 - Sum PBD -- Mean PARM = 0227 [mgkg]

Element Sum PBD

General calcparmT1= 610980E+00T2= 200876E+00T3= 26T4= 100T5= 13106E-02

n= variabelp= 7

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00028 0001 4 -037 000 Fail 00028 00005 4 3 -02226L 01179 0021 2 -036 003 Fail 01179 00208 2 1 -0114L 01305 0031 4 -036 004 Fail 01305 00308 4 3 -010

46L 02065 0035 4 -036 005 Fail 02065 00350 4 3 -00244L 02923 0037 4 -035 005 Fail 02923 00365 4 3 00712L 04051 0015 4 -034 002 Fail 04051 00149 4 3 01864L 04314 0022 4 -033 003 Fail 04314 00223 4 3 0203L 305500 2051 2 247 283 Fail - - 3L - - 3032

Totgem 4017 0276 mgkg 1-level 206 (181) 7 02266 (3L) 7 6Totstd= 10722 0717 5-level 175 (156) 1

RESULTS Mean = 022663 mgkg

Repeatability variance S2r = 000069Repeatability std Sr = 002626 --gt 1159 r = 00735Between lab variance S2L = 002568Reproducibility var S2R = 002637Reproducibility std SR = 016238 --gt 7165 R = 04547Remarks 1 Lab rejected (3L)

000 050 100 150 200 250 300

k-values

10L

26L

4L

46L

44L

12L

64L

3L

Mandels k statistics(Soil 3 - Sum PBD)

-50 00 50 100 150 200 250 300 350

Deviation from Mean

10L

26L

4L

46L

44L

12L

64L

3L

Labo

rato

ries

Soil 3 - Sum PBD -- Mean PARM = 0227 [mgkg]

-100 000 100 200 300

h-values

10L

26L

4L

46L

44L

12L

64L

3L

Labo

rato

ries

Mandels h statistics(Soil 3 - Sum PBD)

Soil 3-Sum PBD

19

Annex 4

Raw data submitted

Sample Compost1 Sample Compost 1 Sample Compost 1Element PBD 99 Element PBD 100 Element PBD 153

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]4L 00021 10L 00008 44L 000504L 00024 10L 00008 44L 000604L 00014 10L 00007 44L 000504L 00020 10L 00011 46L 00004

10L 00029 46L 00007 46L 0001210L 00027 46L 00012 46L 0000410L 00032 46L 00009 46L 0000946L 00025 46L 00007 12L 0000446L 00052 12L 00008 12L 0000846L 00029 12L 00012 12L 0000446L 00026 12L 00008 12L 0000712L 00026 12L 00014 26L 0000512L 00043 26L 00007 26L 0000512L 00026 26L 0000612L 0004726L 0002626L 00024

Sample Compost 1 Sample Compost 1 Sample Compost 1Element PBD 154 Element PBD 183 Element PBD 196

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]4L 00010 46L 00002 46L 00011

46L 00003 46L 00024 46L 0000846L 00007 46L 00021 12L 0000246L 00003 46L 00003 12L 0000346L 00004 12L 00003 12L 0000112L 00003 12L 00011 12L 0000212L 00005 12L 0000312L 00031 12L 0000312L 00006

Sample Compost 1 Sample Compost 1 Sample Compost 1Element PBD 197 Element PBD 203 Element PBD 209

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00002 46L 00010 4L 0004146L 00023 12L 00002 4L 0008946L 00022 12L 00003 44L 0041012L 00004 12L 00002 44L 0084012L 00006 12L 00002 44L 0064012L 00003 44L 0040012L 00004 12L 00079

12L 0007312L 0006512L 0009326L 0004926L 00049

Sample Compost 1Element PBD 47

LAB PARM [mgkg]26L 0003826L 00039

Element PBD 99 Element PBD 47 Element PBD 209LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]

4L 00170 10L 00210 4L 010004L 00200 10L 00220 4L 018004L 00170 10L 00210 4L 012004L 00190 46L 00300 4L 0220010L 00280 46L 00280 46L 0210010L 00300 46L 00250 46L 0200010L 00290 46L 00260 64L 0351846L 00340 64L 00059 64L 0363846L 00330 64L 00057 64L 0364546L 00300 64L 00062 64L 0350846L 00310 64L 00060 12L 0220964L 00194 12L 00191 12L 0177164L 00154 12L 00187 12L 0292264L 00185 12L 00190 12L 0164664L 00159 12L 00186 26L 0329712L 00242 26L 00666 26L 0300012L 00223 26L 0033212L 0022112L 0022226L 0024626L 00400

Element PBD 203 Element PBD 197 Element PBD 196LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00022 46L 00027 46L 0002446L 00014 46L 00024 46L 0002264L 00036 12L 00161 64L 0005864L 00058 12L 00060 64L 0006512L 00063 12L 00061 12L 0004812L 00034 12L 00036 12L 0002512L 00038 12L 0003212L 00027 12L 00022

Element PBD 183 Element PBD 154 Element PBD 153LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00049 4L 00020 4L 0002246L 00035 4L 00022 4L 0002446L 00036 4L 00020 4L 0002246L 00034 46L 00025 4L 0002664L 00027 46L 00025 46L 0004064L 00023 46L 00025 46L 0004264L 00024 46L 00023 46L 0003564L 00020 64L 00034 46L 0003812L 00230 64L 00023 64L 0007412L 00032 64L 00017 64L 0004712L 00031 64L 00011 64L 0004612L 00030 12L 00030 64L 0003026L 00007 12L 00021 12L 0006526L 00008 12L 00021 12L 00029

12L 00021 12L 0003226L 00015 12L 0002926L 00019 26L 00039

26L 00040

Element PBD 100LAB PARM [mgkg]

4L 000384L 000414L 000374L 00038

38L 0219038L 0220038L 0208038L 0220010L 0004410L 0005010L 0004310L 0004646L 0005746L 0005946L 0005346L 0005312L 0004312L 0004512L 0004312L 0004326L 0006226L 00057

Sample Soil 3 Sample Soil 3 Sample Soil 3Element PBD 99 Element PBD 47 Element PBD 100

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]10L 00016 10L 00011 10L 0000310L 00019 10L 00010 10L 0000410L 00013 10L 00012 10L 0000410L 00019 46L 00007 10L 0000246L 00025 46L 00022 46L 0000246L 00025 46L 00005 46L 0000646L 00008 46L 00007 46L 0000246L 00011 12L 00010 46L 0000264L 00005 12L 00017 3L 29100064L 00005 12L 00010 3L 32000064L 00006 12L 00009 26L 0000564L 00007 26L 00007 26L 0000512L 00012 26L 0000712L 0001312L 0001312L 0001226L 0000526L 00006

Sample Soil 3 Sample Soil 3 Sample Soil 3Element PBD 153 Element PBD 154 Element PBD 196

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]44L 00050 4L 00010 46L 0000744L 00050 46L 00001 46L 0001146L 00002 46L 00002 46L 0000846L 00003 46L 00001 46L 0001146L 00002 46L 00002 64L 0002646L 00002 64L 00001 64L 0002664L 00001 64L 00001 64L 0002964L 00001 64L 00001 64L 0003464L 00001 64L 00002 12L 0004564L 00002 12L 00003 12L 00032

12L 00002 12L 0002212L 00002 12L 0002112L 00002

Sample Soil 3 Sample Soil 3 Sample Soil 3Element PBD 197 Element PBD 203 Element PBD 209

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00006 46L 00011 4L 0091046L 00013 46L 00017 4L 0150046L 00011 46L 00015 4L 0120046L 00013 46L 00018 4L 0160012L 00090 64L 00013 44L 0337012L 00056 64L 00014 44L 0281012L 00033 64L 00016 44L 0287012L 00032 64L 00015 44L 02540

12L 00055 46L 0230012L 00041 46L 0220012L 00027 46L 0150012L 00026 46L 01900

64L 0438164L 0401664L 0414464L 0449812L 0367112L 0397812L 0409112L 03838

Sample Soil 3 26L 0102Element PBD 183 26L 0131

LAB PARM [mgkg]46L 0000746L 0000846L 0005846L 0000764L 0000264L 0000364L 0000364L 0000312L 0001512L 0001112L 0000712L 00007

European Commission EUR 23003 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on polybrominated diphenylethers Author(s) E Sobiecka H van der Sloot D Barcelo B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 68 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07403-5 Abstract Project HORIZONTAL is interdisciplinary aiming at a harmonisation and horizontal standardisation of test procedures in particular for sludge soils and biowastes In the context of this standardization project a series of draft technical specification were designed upon an extensive desk study fine-tuned after expert consultations and finally validated in international intercomparisons exercise This report summarises the work performed within the validation study of the draft standard for the determination of polybrominated diphenylethers (PBDE) in soils sludge and treated bio-waste using gas-chromatography method with mass selective detection (GC-MS) It further explains the underlying statistical concept for the calculation of reproducibility and repeatability from intercomparisons data In addition all single values results of the statistical evaluation as well as background information on the validation materials used are described and explained

The mission of the JRC is to provide customer-driven scientific and technical support for the conception development implementation and monitoring of EU policies As a service of the European Commission the JRC functions as a reference centre of science and technology for the Union Close to the policy-making process it serves the common interest of the Member States while being independent of special interests whether private or national

LB

-NA

-23003-EN

-C

VI

Abstract This report gives an overview on the available analytical information on the following raw materials to be used for the production of validation materials of the so-called Project HORIZONTAL

bull Four sludge materials from Duumlsseldorf Germany

bull An agricultural soil material from Reading United Kingdom

bull A compost material from Vienna Austria

bull A compost material from Korschenbroich Germany

bull A sludge-amended agricultural soil from Pavia Province Italy

bull A sludge-amended soil from Barcelona Spain

bull A sludge-amended soil from Essen Germany

bull A long-term sludge exposed soil from Hohenheim Germany

VII

List of Abbreviations Throughout this report the following abbreviations are used

AOX absorbable organic halogens

Corg organic carbon content

Ctotal total carbon content

CAT cation exchangeable

CDD chlorinated dibenzodioxin

CDF chlorinated dibenzofuran

DEHP di(2-ethylhexyl)phthalate

DM dry matter

EPA Environment Protection Agency

EU European Union

FM fresh matter

Hp hepta

Hx hexa

IES Institute for Environment and Sustainability

IRMM Institute for Reference Materials and Measurements

JRC Joint Research Centre

LAS linear alkylsulfonates

LoD limit of detection

LUA Landesumweltamt

Ntotal total nitrogen content

NH4-N Ammonium nitrogen

NO3-N Nitrate nitrogen

NP nonylphenol

NRW North Rhine Westphalia

O octa

P poly

PAH polycyclic aromatic hydrocarbon

PCB polychlorinated biphenyl

Pe penta

T tetra

TEQ toxicity equivalent

UBA Umweltbundesamt

WHO World Health Organization

WWTP waste water treatment plant

6

1 Introduction This report gives an overview on the available analytical information on the following raw materials to be used for the production of validation materials of the so-called Project HORIZONTAL

bull Four sludge materials from Duumlsseldorf Germany

bull An agricultural soil material from Reading United Kingdom

bull A compost material from Vienna Austria

bull A compost material from Korschenbroich Germany

bull A sludge-amended agricultural soil from Pavia Province Italy

bull A sludge-amended soil from Barcelona Spain

bull A sludge-amended soil from Essen Germany

bull A long-term sludge exposed soil from Hohenheim Germany

The following analytical information was gathered partly before and during the sampling of the raw materials to be used for the production of the HORIZONTAL validation materials The material were sampled by IES and shipped to IRMM in the course of the year 2005 The information gathered was then completed by various analytical screenings for PAHs and PCBs done by the Institute for Reference Materials and Measurements Geel Belgium for phthalates done by UBA Berlin Germany for PBDE done by IIQAB-CSIC Barcelona Spain for trace elements and some selected major and minor elements by the Institute for Environment and Sustainability Ispra Italy

The work compiled hereafter is based on the numerous additional efforts of the scientists working at various members of the consortium Project HORIZONTAL-Org and contributing organisations

This work is gratefully acknowledged

2 Overview on property values

21 Sludge materials from Duumlsseldorf Germany

The various sewage sludge materials originate from various installations in the North Rhine Westphalia and were produced and sampled by staff from the Landesumweltamt (LUA) NRW under the responsibility from Dr K Furtmann

In total four sludge materials (Sludge A and D from a major municipal WWTP Sludge B from a municipal WWTP with industrial input and Sludge C from a municipal WWTP with high PCB-Content) were obtained and will be blended to two final materials Before sampling the following analytical data for a typical sample were received

7

Table 1 ndash Analytical data obtained on an average sludge sample in LUA NRW (with courtesy of K Furtmann LUA Duumlsseldorf)

Parameter Concentration PCB 120 ugkg DEHP 110 mgkg PAH 5 mgkg (EPA) PCDDF 15 ng TEkg PBDE 400 ugkg NP 40 mgkg LAS 3 gkg AOX 300 mgkg

Subsequent screening led to the information displayed hereafter It should be stressed that the data were obtained as SCREENING information on the UNTREATED or partially treated raw materials Therefore the final target values which are relevant for the validation intercomparison can be different

Table 2 ndash Analytical data obtained on a first screening on the sludge samples from LUA NRW

Sewage sludge A

Dusseldorf

sewage sludge D

Dusseldorf PCB (ngg) 28 62 35 52 101 65 101 31 38 118 49 40 153 30 33 105 24 11 138 46 38 156 lt1 lt1 180 34 23 170 23 19 PAH (ngg) Naphtalene 34 381 Acenaphtylene 15 43 Acenaphthene 81 108 Fluorene 94 1167 Phenantrene 3440 Anthracene 22 344 Flouranthene 316 4817 Pyrene 235 3011 Benz(a)anthracene 473 791 Chrysene 691 1078 Benz(b)fluoranthene 538 1688 Benz(k)fluoranthene 228 635 Benz(a)pyrene 383 1114 Indeno(123-cd)pyrene 92 229 Dibenzo(ah)anthracene 71 70 Benzo(ghi)perylene 80 185

8

Table 3 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Sludge D (1) 0135 41474 385 Sludge B (2) 0538 0034 30634 547 Sludge A (3) 0184 0037 31399 146 Sludge C (4) 0354 1528 6678 229

Table 4 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Sludge 2

(B)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

554

959

694

591

772

509

nq

nq

970

2216

2379

Table 5 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena IES Ispra Spain) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Sludge 1 (D) 265 290 533 359 1231 338 784 438 lt 005 232 786 Sludge 2 (B) 119 311 626 202 278 299 722 251 lt 005 118 625 Sludge 3 (A) 168 360 621 332 847 416 119 451 lt 005 116 1237 Sludge 4 (C) 563 198 116 273 726 511 473 618 lt 005 444 2015

Table 6 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Sludge 1 (D) 2154 58 844 099 103 101 4367 lt15 50448 Sludge 2 (B) 1067 366 692 046 1491 077 5217 lt15 57633 Sludge 3 (A) 731 663 684 035 1287 068 3733 lt15 60369 Sludge 4 (C) 4379 965 527 163 522 107 5628 lt15 23945

Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM)Sludge 1 (D) 03 2403 101 1002 350 15 1944 132Sludge 2 (B) 031 315 97 879 172 12 514 180Sludge 3 (A) 031 1281 153 1567 265 16 1440 168Sludge 4 (C) 055 231 628 2625 371 81 1101 244

9

22 Agricultural soil material from Reading United Kingdom

The material was proposed by the University of Reading (S Nortcliff) and was sampled from a site called ldquoFrogmore Farmrdquo which was featured in the ldquoMetalsrdquo Report for HORIZONTAL This site is close to Reading with soils developed on flintyloamy periglacial materials over Chalk has a long and well documented history of sludge application The focus of the work of Nortcliff et al undertook at this site and the monitoring and control at the site (by Thames Water and the subsequent subsidiary bodies dealing with sludge application to soil) was on metals (and metal loads) with no analysis or indeed any form of investigation in to organics in the broadest sense

The analytical information produced in the context of the screening of the raw material is displayed below

Table 7 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 3

(Reading) 0032 0119 669

Table 8 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 3 (Reading) 015 706 279 138 152 901 267 300 lt 005 258 931

Table 9 ndash Analytical data obtained on a first screening on the sludge-amended soil from Reading (courtesy of IRMM)

Parameter Concentration

PCB ngg 28 lt1 52 lt1 101 lt1 118 lt1 153 lt1 105 lt1 138 lt1 156 lt1 180 lt1 170 lt1 PAH ngg Naphtalene lt10 Acenaphtylene 21 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene lt10 Flouranthene 818 Pyrene 776 Benz(a)anthracene 565

10

Parameter Concentration

Chrysene 608 Benz(b)fluoranthene 824 Benz(k)fluoranthene 329 Benz(a)pyrene 799 Indeno(123-cd)pyrene

779

Dibenzo(ah)anthracene 118 Benzo(ghi)perylene 394

Table 10 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 3

(Reading)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

103

003

nq

nq

nq

nd

nd

272

273

Table 11 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 3 (Reading) 015 706 279 138 152 901 267 300 lt 005 258 931

Table 12 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 3 (Reading) 7936 477 112 096 194 017 4107 443 2102 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 3 (Reading) 042 13 45 69 69 69 216 92

Table 13 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 3 (Reading) 012

11

23 Compost from Vienna Austria

The fresh compost material was obtained from the Austrian Federal Environment Agency (UBA Vienna) which had used a sub-batch of the raw material for national intercomparson The remainder of the material was stored at 4degC until shipment to IRMM for further processing The following analytical information was provided by UBA Austria and completed with various screenings

Table 14 ndash Analytical data on compost material received from UBA Austria Inorganic and sum parameters

Parameter Unit Sample fraction used Observed mean B CAT mgl FM Fresh sample lt10mm 61 K CAT mgl FM Fresh sample lt10mm 2624 Mg CAT mgl FM Fresh sample lt10mm 242 P CAT mgl FM Fresh sample lt10mm 49 B CAT DM Fresh sample lt10mm 00017 K CAT DM Fresh sample lt10mm 072 Mg CAT DM Fresh sample lt10mm 007 P CAT DM Fresh sample lt10mm 001 NO3-N mgkg FM Fresh sample lt10mm 35 NH4-N mgkg FM Fresh sample lt10mm 230 Ctotal DM lt45degdry milled 29 Corg DM lt45degdry milled 27 Ntotal DM lt45degdry milled 17 P mgkg DM lt45degdry milled 2596 K mgkg DM lt45degdry milled 11019 K DM lt45degdry milled 110 B mgkg DM lt45degdry milled 60 Cd mgkg DM lt45degdry milled 046 Cr mgkg DM lt45degdry milled 25 Cu mgkg DM lt45degdry milled 46 Hg mgkg DM lt45degdry milled 020 Ni mgkg DM lt45degdry milled 18 Pb mgkg DM lt45degdry milled 45 Zn mgkg DM lt45degdry milled 198 Ca mgkg DM lt45degdry milled 68776 Ca DM lt45degdry milled 69 Mo mgkg DM lt45degdry milled 08 S mgkg DM lt45degdry milled 2137 Fe mgkg DM lt45degdry milled 9959 Mn mgkg DM lt45degdry milled 418 Na mgkg DM lt45degdry milled 742 Co mgkg DM lt45degdry milled 41 AOX mgkg DM lt30deg dry milled 62

Table 15 ndash Analytical data on compost material received from UBA Austria Polycyclic aromatic hydrocarbons

PAH Unit Result Naphthaline microgkg DM 93 Acenaphthylene microgkg DM 86 Acenaphthene microgkg DM 5 Fluorene microgkg DM 80 Phenanthrene microgkg DM 89 Anthracene microgkg DM 27 Fluoranthene microgkg DM 487 Pyrene microgkg DM 380

12

PAH Unit Result Benzo(a)anthracene microgkg DM 278 Chrysene microgkg DM 317 Benzo(b)fluoranthene microgkg DM 365 Benzo(k)fluoranthene microgkg DM 193 Benz(a)pyrene microgkg DM 320 Indeno(123-cd)pyrene microgkg DM 233 Dibenz(ah)anthracene microgkg DM 67 Benzo(ghi)perylene microgkg DM 225 Sum EPA microgkg DM 3013 Sum EPA mgkg DM 30

Table 16 ndash Analytical data on compost material received from UBA Austria Sum PCDDs and PCBs

Parameter

Dioxine TEQ (ITEF) ngkg DM 73 TEQ (WHO) ngkg DM 35 PCB Σ Ballschmiter mgkg DM 005

Table 17 ndash Analytical data on compost material obtained by screening in IRMM

Parameter Result in ngg

PCB 28 2 52 2 101 4 118 3 153 10 105 1 138 8 156 1 180 5 170 lt1 PAH Naphtalene lt10 Acenaphtylene lt10 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene 26 Fluoranthene 611 Pyrene 510 Benz(a)anthracene 888 Chrysene 957 Benz(b)fluoranthene 1531 Benz(k)fluoranthene 547 Benz(a)pyrene 1101 Indeno(123-cd)pyrene 416 Dibenzo(ah)anthracene 81 Benzo(ghi)perylene 295

13

Table 18 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Compost 1

(Vienna)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

402

019

259

nq

023

004

nq

nq

144

174

259

Table 19 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Compost 1

(Vienna) 0058 1426 557

Table 20 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Compost 1 (Vienna) 039 736 319 410 365 127 495 004 079 013 208

Table 21 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Compost 1 (Vienna) 2063 431 617 426 199 249 1602 lt15 10521

Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Compost 1 (Vienna) 035 3496 81 375 79 55 653 60

Table 22 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Compost 1 (Vienna) 017

14

24 Agricultural soil sludge amended soil from Pavia Italy

This sludge-amended soil material was obtained during a monitoring campaign which aimed at a generic description of the over-all soil quality in Pavia Province Italy The material which was collected from the upper horizon originates from a small farm called ldquoCascina Novellordquo During the characterisation of the site the following analytical information was obtained on a pooled sample of a sub-area of the farm of 20 X 20 m2

Table 23 ndash Analytical data on Pavia soil

Parameter Result Al 713 Wgt As 224 mgkg Cd 079 mgkg Cr 59 mgkg Cu 308 mgkg Hg 008 mgkg Ni 344 mgkg Pb 246 mgkg Zn 95 mgkg C 091 Wgt 2378-TCDD 0047 pgg 12378-PeCDD 015 pgg 123478-HxCDD 019 pgg 123678-HxCDD 15 pgg 123789-HxCDD 074 pgg 1234678-HpCDD 26 pgg OCDD 382 pgg 2378-TCDF 068 pgg 12378-PeCDF 053 pgg 23478-PeCDF 071 pgg 123478-HxDF 100 pgg 123678-HxDF 066 pgg 234678-HxDF 16 pgg 123789-HxDF 027 pgg 1234678-HpDF 12 pgg 1234789-HpDF 068 pgg OCDF 33 pgg I-TEQ 20 pgg WHO-TEQ 17 pgg

In addition the screening performed at IRMM did not reveal significant quantities of PCBs and PAHs which were all below the LoDs (1 ngg for PCBs and 10 ngg for PAHs respectively)

Table 24 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 5 (Pavia) 0005 0011 154

15

Table 25 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 5

(Pavia)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

039

nq

nq

008

nq

nd

nd

670

671

Table 26 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 5 (Pavia) 033 184 573 225 426 305 206 200 lt 005 381 878

Table 27 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 5 (Pavia) 6939 129 145 224 425 116 6118 255 1789 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 5 (Pavia) 184 62 38 108 55 66 597 110

Table 28 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 5 (Pavia) 006

16

25 Sludge-amended-soil from Barcelona Spain

The sludge-amended soil material from Barcelona sampled upon indication from the Barcelorsquo- Group in Barcelona

Table 29 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 2 (Lleida T) 0015 0183 1138

Table 30 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 2

(Lleida T)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

159

045

nq

048

160

nq

nq

1000

1004

Table 31 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 2 (Lleida T) 059 141 327 536 405 186 184 224 lt 005 318 111

Table 32 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 2 (Lleida T) 4443 1067 1429 253 344 204 4116 780 3396 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 2 (Lleida T) 064 65 26 125 59 17 547 65

Table 33 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 2 (Lleida T) 010

17

26 Sludge amended soil from Essen Germany

The German sludge-amended soil from Essen which was provided as the three sludge materials by LUA NRW did not feature significant concentrations of the PCB congeners 28 52 101 118 153 105 138 156 180 170 but had detectable amounts of some PAHs

Table 34 ndash Analytical screening data on the German sludge-amended soil

Parameter Concentration(ngg)

Naphtalene lt10 Acenaphtylene lt10 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene lt10 Fluoranthene 28 Pyrene 20 Benz(a)anthracene 24 Chrysene 47 Benz(b)fluoranthene 76 Benz(k)fluoranthene 20 Benz(a)pyrene 35 Indeno(123-cd)pyrene 35 Dibenzo(ah)anthracene 10 Benzo(ghi)perylene 26

Table 35 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 4 (Essen) 0011 0302 055

Table 36 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 4

(Essen)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

nq

nq

nq

nq

nq

nq

128

191

203

18

Table 37 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 4 (Essen) 052 545 261 805 320 403 273 273 lt 005 295 781

Table 38 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 4 (Essen) 7947 442 085 06 086 007 2163 189 2019 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 4 (Essen) 045 19 42 87 683 60 462 61

Table 39 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 4 (Essen) 004

27 Long-term sludge exposed soil from Hohenheim-Stuttgart Germany

Similarly an additional sludge exposed soil was sampled at the University of Hohenheim Stuttgart were a test soil was long-term exposed to elevated concentrations of sewage sludge

Table 40 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 1 (Stuttgart) 0045 0263 1765

Table 41 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 1

(Stuttgart)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

230

006

004

004

nq

nd

nd

498

500

19

Table 42 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 1 (Stuttgart) 069 127 361 262 504 183 252 262 lt 005 266 142

Table 43 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 1 (Stuttgart) 7194 1006 133 186 366 088 7874 275 3571 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 1 (Stuttgart) 123 50 47 212 85 69 991 129

Table 44 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 1 (Stuttgart) 177

18

Annex 3

Statistical calculations

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 47)Mandels h statistics(Sludge 1 - PBD 47)

Sample Sludge 1 NUM

Element PBD 47

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00213 0001 3 -021 005 - - 10L - - NUM46L 00273 0002 4 016 021 - - 46L - - NUM64L 00059 0000 4 -116 002 NUM - 64L - - NUM12L 00188 0000 4 -036 002 - - 12L - - NUM26L 00499 0024 2 157 223 Fail - - 26L - - NUM

Totgem 0025 0005 mgkg 1-level 172 (185) NUM (10L46L64L12L26L) -1Totstd= 0016 0010 5-level 157 (162) 5

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 5 Labs rejected (10L46L64L12L26L)

000 050 100 150 200 250

k-values

10L

46L

64L

12L

26L

Mandels k statistics(Sludge 1 - PBD 47)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

10L

46L

64L

12L

26L

Labo

rato

ries

NUM

-200 -100 000 100 200

h-values

10L

46L

64L

12L

26L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 47)

Sludge 1-PBD 47

Unit mgkg

Mandels k statistics(Soil 3 - PBD 47)Mandels h statistics(Soil 3 - PBD 47)

Sample Soil 3 Soil 3 - PBD 47 -- Mean PARM = 0001 [mgkg]

Element PBD 47

General calcparmT1= 134814E-02T2= 142830E-05T3= 13T4= 45T5= 22767E-06

n= variabelp= 4

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean26L 00007 0000 2 -143 001 00007 00000 2 1 00046L 00010 0001 4 010 181 00010 00008 4 3 00010L 00011 0000 3 049 023 00011 00001 3 2 00012L 00012 0000 4 084 081 00012 00004 4 3 000

Totgem 0001 0000 mgkg 1-level 149 (177) 4 00010 () 4 3Totstd= 0000 0000 5-level 142 (159)

RESULTS Mean = 000100 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000050 --gt 5031 r = 00014Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000050 --gt 5031 R = 00014Remarks none

000 050 100 150 200

k-values

26L

46L

10L

12L

Mandels k statistics(Soil 3 - PBD 47)

00 00 00 00 00 00 00 00 00 00 00

Deviation from Mean

26L

46L

10L

12L

Labo

rato

ries

Soil 3 - PBD 47 -- Mean PARM = 0001 [mgkg]

-200 -100 000 100

h-values

26L

46L

10L

12L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 47)

Soil 3-PBD 47

Unit mgkg

Mandels k statistics(Compost 1 - PBD 99)Mandels h statistics(Compost 1 - PBD 99)

Sample Compost 1 Compost 1 - PBD 99 -- Mean PARM = 0003 [mgkg]

Element PBD 99

General calcparmT1= 492124E-02T2= 148747E-04T3= 17T4= 61T5= 93196E-06

n= variabelp= 5

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00020 0000 4 -137 053 00020 00004 4 3 000

26L 00025 0000 2 -058 024 00025 00002 2 1 00010L 00029 0000 3 012 032 00029 00003 3 2 00046L 00033 0001 4 069 161 00033 00013 4 3 00012L 00036 0001 4 114 140 00036 00011 4 3 000

Totgem 0003 0001 mgkg 1-level 172 (185) 5 00029 () 5 4Totstd= 0001 0001 5-level 157 (162)

RESULTS Mean = 000286 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000088 --gt 3086 r = 00025Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000101 --gt 3525 R = 00028Remarks none

000 050 100 150 200

k-values

4L

26L

10L

46L

12L

Mandels k statistics(Compost 1 - PBD 99)

00 00 00 00 00 00 00 00 00 00

Deviation from Mean

4L

26L

10L

46L

12L

Labo

rato

ries

Compost 1 - PBD 99 -- Mean PARM = 0003 [mgkg]

-200 -100 000 100 200

h-values

4L

26L

10L

46L

12L

Labo

rato

ries

Mandels h statistics(Compost 1 - PBD 99)

Compost 1-PBD 99

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 99)Mandels h statistics(Sludge 1 - PBD 99)

Sample Sludge 1 Sludge 1 - PBD 99 -- Mean PARM = 0024 [mgkg]

Element PBD 99

General calcparmT1= 448050E-01T2= 112113E-02T3= 19T4= 73T5= 32972E-05

n= variabelp= 5

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean64L 00173 0002 4 -118 041 Fail 00173 00019 4 3 -0014L 00183 0002 4 -104 032 00183 00015 4 3 -001

12L 00227 0001 4 -038 022 00227 00010 4 3 00010L 00290 0001 3 055 021 00290 00010 3 2 00146L 00320 0002 4 100 039 00320 00018 4 3 00126L 00323 0011 2 105 234 - - 26L - - 001

Totgem 0025 0003 mgkg 1-level 187 (177) 5 00239 (26L) 5 4Totstd= 0007 0004 5-level 166 (154) 1

RESULTS Mean = 002385 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000153 --gt 643 r = 00043Between lab variance S2L = 000004Reproducibility var S2R = 000004Reproducibility std SR = 000666 --gt 2791 R = 00186Remarks 1 Lab rejected (26L)

000 050 100 150 200 250

k-values

64L

4L

12L

10L

46L

26L

Mandels k statistics(Sludge 1 - PBD 99)

00 00 00 00 00 00 00 00 00 00

Deviation from Mean

64L

4L

12L

10L

46L

26L

Labo

rato

ries

Sludge 1 - PBD 99 -- Mean PARM = 0024 [mgkg]

-200 -100 000 100 200

h-values

64L

4L

12L

10L

46L

26L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 99)

Sludge 1-PBD 99

Unit mgkg

Mandels k statistics(Soil 3 - PBD 99)Mandels h statistics(Soil 3 - PBD 99)

Sample Soil 3 NUM

Element PBD 99

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00017 0000 4 091 068 - - 10L - - NUM46L 00017 0001 4 100 211 - - 46L - - NUM64L 00005 0000 4 -106 023 NUM - 64L - - NUM12L 00012 0000 4 015 014 - - 12L - - NUM26L 00006 0000 2 -101 012 - - 26L - - NUM

Totgem 0001 0000 mgkg 1-level 172 (173) NUM (10L46L64L12L26L) -1Totstd= 0001 0000 5-level 157 (153) 5

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 5 Labs rejected (10L46L64L12L26L)

000 050 100 150 200 250

k-values

10L

46L

64L

12L

26L

Mandels k statistics(Soil 3 - PBD 99)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

10L

46L

64L

12L

26L

Labo

rato

ries

NUM

-200 -100 000 100 200

h-values

10L

46L

64L

12L

26L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 99)

Soil 3-PBD 99

Unit mgkg

Mandels k statistics(Compost 1 - PBD 100)Mandels h statistics(Compost 1 - PBD 100)

Sample Compost 1 Compost 1 - PBD 100 -- Mean PARM = 0001 [mgkg]

Element PBD 100

General calcparmT1= 124272E-02T2= 113129E-05T3= 14T4= 52T5= 46584E-07

n= variabelp= 4

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean26L 00006 0000 2 -131 037 Fail 00006 00001 2 1 00010L 00009 0000 4 003 083 00009 00002 4 3 00046L 00009 0000 4 016 115 00009 00002 4 3 00012L 00011 0000 4 112 136 Fail 00011 00003 4 3 000

Totgem 0001 0000 mgkg 1-level 149 (167) 4 00009 () 4 3Totstd= 0000 0000 5-level 142 (15)

RESULTS Mean = 000085 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000022 --gt 2531 r = 00006Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000025 --gt 2882 R = 00007Remarks none

000 050 100 150

k-values

26L

10L

46L

12L

Mandels k statistics(Compost 1 - PBD 100)

00 00 00 00 00 00 00 00 00 00 00

Deviation from Mean

26L

10L

46L

12L

Labo

rato

ries

Compost 1 - PBD 100 -- Mean PARM = 0001 [mgkg]

-200 -100 000 100 200

h-values

26L

10L

46L

12L

Labo

rato

ries

Mandels h statistics(Compost 1 - PBD 100)

Compost 1-PBD 100

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 100)Mandels h statistics(Sludge 1 - PBD 100)

Sample Sludge 1 Sludge 1 - PBD 100 -- Mean PARM = 0005 [mgkg]

Element PBD 100

General calcparmT1= 852065E-02T2= 412762E-04T3= 18T4= 68T5= 78914E-07

n= variabelp= 5

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00039 0000 4 -042 007 Fail 00039 00002 4 3 000

12L 00044 0000 4 -041 005 Fail 00044 00001 4 3 00010L 00046 0000 4 -041 013 Fail 00046 00003 4 3 00046L 00056 0000 4 -040 012 Fail 00056 00003 4 3 00026L 00059 0000 2 -040 013 Fail 00059 00003 2 1 00038L 02168 0006 4 204 244 Fail - - 38L - - 021

Totgem 0040 0001 mgkg 1-level 187 (177) 5 00049 (38L) 5 4Totstd= 0087 0002 5-level 166 (154) 1

RESULTS Mean = 000486 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000025 --gt 507 r = 00007Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000084 --gt 1731 R = 00024Remarks 1 Lab rejected (38L)

000 050 100 150 200 250

k-values

4L

12L

10L

46L

26L

38L

Mandels k statistics(Sludge 1 - PBD 100)

-01 00 01 01 02 02 03

Deviation from Mean

4L

12L

10L

46L

26L

38L

Labo

rato

ries

Sludge 1 - PBD 100 -- Mean PARM = 0005 [mgkg]

-100 000 100 200 300

h-values

4L

12L

10L

46L

26L

38L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 100)

Sludge 1-PBD 100

Unit mgkg

Mandels k statistics(Soil 3 - PBD 100)Mandels h statistics(Soil 3 - PBD 100)

Sample Soil 3 NUM

Element PBD 100

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00003 0000 4 -050 000 Fail - - 10L - - NUM46L 00003 0000 4 -050 000 Fail NUM - 46L - - NUM3L 305500 2051 2 150 200 Fail - - 3L - - NUM

26L 00005 0000 2 -050 000 Fail - - 26L - - NUM

Totgem 7638 0513 mgkg 1-level 149 (177) NUM (10L46L3L26L) -1Totstd= 15275 1025 5-level 142 (159) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (10L46L3L26L)

000 050 100 150 200

k-values

10L

46L

3L

26L

Mandels k statistics(Soil 3 - PBD 100)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

10L

46L

3L

26L

Labo

rato

ries

NUM

-100 000 100 200

h-values

10L

46L

3L

26L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 100)

Soil 3-PBD 100

Unit mgkg

Mandels k statistics(Compost 1 - PBD 153)Mandels h statistics(Compost 1 - PBD 153)

Sample Compost 1 NUM

Element PBD 153

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean44L 00053 0001 3 150 157 Fail - - 44L - - NUM46L 00007 0000 4 -044 111 Fail - - 46L - - NUM12L 00005 0000 4 -051 055 Fail - - 12L - - NUM26L 00005 0000 2 -054 001 Fail NUM - 26L - - NUM

Totgem 0002 0000 mgkg 1-level 149 (177) NUM (44L46L12L26L) -1Totstd= 0002 0000 5-level 142 (159) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (44L46L12L26L)

000 050 100 150 200

k-values

44L

46L

12L

26L

Mandels k statistics(Compost 1 - PBD 153)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

44L

46L

12L

26L

Labo

rato

ries

NUM

-100 000 100 200

h-values

44L

46L

12L

26L

Labo

rato

ries

Mandels h statistics(Compost 1 - PBD 153)

Compost 1-PBD 153

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 153)Mandels h statistics(Sludge 1 - PBD 153)

Sample Sludge 1 Sludge 1 - PBD 153 -- Mean PARM = 0004 [mgkg]

Element PBD 153

General calcparmT1= 676738E-02T2= 267609E-04T3= 18T4= 68T5= 19626E-05

n= variabelp= 5

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00024 0000 4 -157 017 00024 00002 4 3 000

12L 00038 0002 4 006 154 00038 00018 4 3 00046L 00039 0000 4 011 026 00039 00003 4 3 00026L 00039 0000 2 018 004 00039 00000 2 1 00064L 00049 0002 4 122 159 00049 00018 4 3 000

Totgem 0004 0001 mgkg 1-level 172 (173) 5 00038 () 5 4Totstd= 0001 0001 5-level 157 (153)

RESULTS Mean = 000378 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000123 --gt 3252 r = 00034Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000142 --gt 3754 R = 00040Remarks none

000 050 100 150 200

k-values

4L

12L

46L

26L

64L

Mandels k statistics(Sludge 1 - PBD 153)

00 00 00 00 00 00 00

Deviation from Mean

4L

12L

46L

26L

64L

Labo

rato

ries

Sludge 1 - PBD 153 -- Mean PARM = 0004 [mgkg]

-200 -100 000 100 200

h-values

4L

12L

46L

26L

64L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 153)

Sludge 1-PBD 153

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 154)Mandels h statistics(Sludge 1 - PBD 154)

Sample Sludge 1 NA

Element PBD 154

General calcparmT1= NAT2= NAT3=T4=T5=

n= variabelp=

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00021 0000 3 -100 021 NA - 4L - - NA

46L 00025 0000 4 115 018 NA - 46L - - NA64L 00021 0001 4 -066 179 - - 64L - - NA12L 00023 0000 4 050 085 - - 12L - - NA

Totgem 0002 0000 mgkg 1-level 149 (167) NA (4L46L64L12L) -1Totstd= 0000 0000 5-level 142 (15) 4

RESULTS Mean = NA mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NAReproducibility var S2R = NAReproducibility std SR = NA --gt NA R = NARemarks 4 Labs rejected (4L46L64L12L)

000 050 100 150 200

k-values

4L

46L

64L

12L

Mandels k statistics(Sludge 1 - PBD 154)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

4L

46L

64L

12L

Labo

rato

ries

NA

-100 000 100 200

h-values

4L

46L

64L

12L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 154)

Sludge 1-PBD 154

Unit mgkg

Mandels k statistics(Soil 3 - PBD 154)Mandels h statistics(Soil 3 - PBD 154)

Sample Soil 3 NUM

Element PBD 154

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

4L 00010 - 1 150 Fail - - 4L - - NUM46L 00001 0000 4 -053 096 Fail - - 46L - - NUM64L 00001 0000 4 -056 105 Fail NUM - 64L - - NUM12L 00002 0000 4 -040 099 Fail - - 12L - - NUM

Totgem 000037 0000 mgkg 1-level 149 (164) NUM (4L46L64L12L) -1Totstd= 000042 0000 5-level 142 (153) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (4L46L64L12L)

000 050 100 150

k-values

4L

46L

64L

12L

Mandels k statistics(Soil 3 - PBD 154)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

4L

46L

64L

12L

Labo

rato

ries

NUM

-100 000 100 200

h-values

4L

46L

64L

12L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 154)

Soil 3-PBD 154

Unit mgkg

Mandels k statistics(Compost 1 - PBD 209)Mandels h statistics(Compost 1 - PBD 209)

Sample Compost 1 NUM

Element PBD 209

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00065 0003 2 -049 032 - - 4L - - NUM

44L 00573 0021 4 150 197 Fail - - 44L - - NUM12L 00078 0001 4 -045 011 - - 12L - - NUM26L 00049 0000 2 -056 000 NUM - 26L - - NUM

Totgem 0019 0006 mgkg 1-level 149 (177) NUM (4L44L12L26L) -1Totstd= 0025 0010 5-level 142 (159) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (4L44L12L26L)

000 050 100 150 200

k-values

4L

44L

12L

26L

Mandels k statistics(Compost 1 - PBD 209)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

4L

44L

12L

26L

Labo

rato

ries

NUM

-100 000 100 200

h-values

4L

44L

12L

26L

Labo

rato

ries

Mandels h statistics(Compost 1 - PBD 209)

Compost 1-PBD 209

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 209)Mandels h statistics(Sludge 1 - PBD 209)

Sample Sludge 1 Sludge 1 - PBD 209 -- Mean PARM = 0249 [mgkg]

Element PBD 209

General calcparmT1= 394542E+00T2= 107296E+00T3= 16T4= 56T5= 19723E-02

n= variabelp= 5

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 01550 0055 4 -112 148 Fail 01550 00551 4 3 -009

46L 02050 0007 2 -053 019 02050 00071 2 1 -00412L 02137 0058 4 -042 155 02137 00576 4 3 -00426L 03149 0021 2 078 057 Fail 03149 00210 2 1 00764L 03577 0007 4 129 020 Fail 03577 00074 4 3 011

Totgem 0249 0030 mgkg 1-level 172 (185) 5 02493 () 5 4Totstd= 0084 0025 5-level 157 (162)

RESULTS Mean = 024926 mgkg

Repeatability variance S2r = 000179Repeatability std Sr = 004234 --gt 1699 r = 01186Between lab variance S2L = 000743Reproducibility var S2R = 000922Reproducibility std SR = 009604 --gt 3853 R = 02689Remarks none

000 050 100 150 200

k-values

4L

46L

12L

26L

64L

Mandels k statistics(Sludge 1 - PBD 209)

-01 -01 00 01 01 02

Deviation from Mean

4L

46L

12L

26L

64L

Labo

rato

ries

Sludge 1 - PBD 209 -- Mean PARM = 0249 [mgkg]

-200 -100 000 100 200

h-values

4L

46L

12L

26L

64L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 209)

Sludge 1-PBD 209

Unit mgkg

Mandels k statistics(Soil 3 - PBD 209)Mandels h statistics(Soil 3 - PBD 209)

Sample Soil 3 Soil 3 - PBD 209 -- Mean PARM = 0258 [mgkg]

Element PBD 209

General calcparmT1= 596398E+00T2= 191917E+00T3= 22T4= 84T5= 13249E-02

n= variabelp= 6

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean26L 01162 0021 2 -108 074 Fail 01162 00207 2 1 -0144L 01303 0031 4 -097 111 Fail 01303 00312 4 3 -013

46L 01975 0036 4 -046 128 Fail 01975 00359 4 3 -00644L 02898 0035 4 024 124 Fail 02898 00346 4 3 00312L 03895 0018 4 100 065 Fail 03895 00181 4 3 01364L 04260 0022 4 127 078 Fail 04260 00219 4 3 017

Totgem 0258 0027 mgkg 1-level 187 (177) 6 02582 () 6 5Totstd= 0132 0008 5-level 166 (154)

RESULTS Mean = 025818 mgkg

Repeatability variance S2r = 000083Repeatability std Sr = 002878 --gt 1115 r = 00806Between lab variance S2L = 001640Reproducibility var S2R = 001723Reproducibility std SR = 013127 --gt 5084 R = 03676Remarks none

000 050 100 150

k-values

26L

4L

46L

44L

12L

64L

Mandels k statistics(Soil 3 - PBD 209)

-02 -01 -01 00 01 01 02 02

Deviation from Mean

26L

4L

46L

44L

12L

64L

Labo

rato

ries

Soil 3 - PBD 209 -- Mean PARM = 0258 [mgkg]

-200 -100 000 100 200

h-values

26L

4L

46L

44L

12L

64L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 209)

Soil 3-PBD 209

Unit mgkg

Mandels k statistics(Compost 1 - Sum PBD)Mandels h statistics(Compost 1 - Sum PBD)

Sample Compost 1 Compost 1 - Sum PBD -- Mean PARM = 0009 [mgkg]

Element Sum PBD

General calcparmT1= 154064E-01T2= 169065E-03T3= 18T4= 68T5= 11354E-04

n= variabelp= 5

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00031 0002 4 -067 016 00031 00016 4 3 -0014L 00055 0005 4 -056 048 00055 00047 4 3 000

46L 00085 0003 4 -042 031 00085 00030 4 3 00026L 00123 0000 2 -024 003 00123 00002 2 1 00012L 00154 0002 4 -011 021 00154 00021 4 3 00144L 00613 0023 4 200 237 Fail - - 44L - - 005

Totgem 0018 0006 mgkg 1-level 187 (177) 5 00089 (44L) 5 4Totstd= 0022 0009 5-level 166 (154) 1

RESULTS Mean = 000893 mgkg

Repeatability variance S2r = 000001Repeatability std Sr = 000296 --gt 3308 r = 00083Between lab variance S2L = 000002Reproducibility var S2R = 000003Reproducibility std SR = 000570 --gt 6374 R = 00159Remarks 1 Lab rejected (44L)

000 050 100 150 200 250

k-values

10L

4L

46L

26L

12L

44L

Mandels k statistics(Compost 1 - Sum PBD)

00 00 00 00 00 00 01 01

Deviation from Mean

10L

4L

46L

26L

12L

44L

Labo

rato

ries

Compost 1 - Sum PBD -- Mean PARM = 0009 [mgkg]

-100 000 100 200

h-values

10L

4L

46L

26L

12L

44L

Labo

rato

ries

Mandels h statistics(Compost 1 - Sum PBD)

Compost 1-Sum PBD

Unit mgkg

Mandels k statistics(Sludge 1 - Sum PBD)Mandels h statistics(Sludge 1 - Sum PBD)

Sample Sludge 1 Sludge 1 - Sum PBD -- Mean PARM = 0256 [mgkg]

Element Sum PBD

General calcparmT1= 531806E+00T2= 162188E+00T3= 22T4= 84T5= 25223E-02

n= variabelp= 6

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00423 0025 4 -156 044 Fail 00423 00252 4 3 -02146L 01808 0118 4 -049 205 - - 46L - - -0074L 01810 0056 4 -049 097 01810 00558 4 3 -007

38L 02168 0006 4 -022 010 02168 00059 4 3 -00412L 02890 0065 4 034 113 02890 00647 4 3 00364L 03958 0008 4 116 014 Fail 03958 00079 4 3 01426L 04094 0034 2 126 059 Fail 04094 00337 2 1 015

Totgem 0245 0044 mgkg 1-level 198 (179) 6 02557 (46L) 6 5Totstd= 0130 0039 5-level 171 (155) 1

RESULTS Mean = 025570 mgkg

Repeatability variance S2r = 000158Repeatability std Sr = 003970 --gt 1553 r = 01112Between lab variance S2L = 001807Reproducibility var S2R = 001964Reproducibility std SR = 014015 --gt 5481 R = 03924Remarks 1 Lab rejected (46L)

000 050 100 150 200 250

k-values

10L

46L

4L

38L

12L

64L

26L

Mandels k statistics(Sludge 1 - Sum PBD)

-03 -02 -02 -01 -01 00 01 01 02 02

Deviation from Mean

10L

46L

4L

38L

12L

64L

26L

Labo

rato

ries

Sludge 1 - Sum PBD -- Mean PARM = 0256 [mgkg]

-200 -100 000 100 200

h-values

10L

46L

4L

38L

12L

64L

26L

Labo

rato

ries

Mandels h statistics(Sludge 1 - Sum PBD)

Sludge 1-Sum PBD

Unit mgkg

Mandels k statistics(Soil 3 - Sum PBD)Mandels h statistics(Soil 3 - Sum PBD)

Sample Soil 3 Soil 3 - Sum PBD -- Mean PARM = 0227 [mgkg]

Element Sum PBD

General calcparmT1= 610980E+00T2= 200876E+00T3= 26T4= 100T5= 13106E-02

n= variabelp= 7

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00028 0001 4 -037 000 Fail 00028 00005 4 3 -02226L 01179 0021 2 -036 003 Fail 01179 00208 2 1 -0114L 01305 0031 4 -036 004 Fail 01305 00308 4 3 -010

46L 02065 0035 4 -036 005 Fail 02065 00350 4 3 -00244L 02923 0037 4 -035 005 Fail 02923 00365 4 3 00712L 04051 0015 4 -034 002 Fail 04051 00149 4 3 01864L 04314 0022 4 -033 003 Fail 04314 00223 4 3 0203L 305500 2051 2 247 283 Fail - - 3L - - 3032

Totgem 4017 0276 mgkg 1-level 206 (181) 7 02266 (3L) 7 6Totstd= 10722 0717 5-level 175 (156) 1

RESULTS Mean = 022663 mgkg

Repeatability variance S2r = 000069Repeatability std Sr = 002626 --gt 1159 r = 00735Between lab variance S2L = 002568Reproducibility var S2R = 002637Reproducibility std SR = 016238 --gt 7165 R = 04547Remarks 1 Lab rejected (3L)

000 050 100 150 200 250 300

k-values

10L

26L

4L

46L

44L

12L

64L

3L

Mandels k statistics(Soil 3 - Sum PBD)

-50 00 50 100 150 200 250 300 350

Deviation from Mean

10L

26L

4L

46L

44L

12L

64L

3L

Labo

rato

ries

Soil 3 - Sum PBD -- Mean PARM = 0227 [mgkg]

-100 000 100 200 300

h-values

10L

26L

4L

46L

44L

12L

64L

3L

Labo

rato

ries

Mandels h statistics(Soil 3 - Sum PBD)

Soil 3-Sum PBD

19

Annex 4

Raw data submitted

Sample Compost1 Sample Compost 1 Sample Compost 1Element PBD 99 Element PBD 100 Element PBD 153

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]4L 00021 10L 00008 44L 000504L 00024 10L 00008 44L 000604L 00014 10L 00007 44L 000504L 00020 10L 00011 46L 00004

10L 00029 46L 00007 46L 0001210L 00027 46L 00012 46L 0000410L 00032 46L 00009 46L 0000946L 00025 46L 00007 12L 0000446L 00052 12L 00008 12L 0000846L 00029 12L 00012 12L 0000446L 00026 12L 00008 12L 0000712L 00026 12L 00014 26L 0000512L 00043 26L 00007 26L 0000512L 00026 26L 0000612L 0004726L 0002626L 00024

Sample Compost 1 Sample Compost 1 Sample Compost 1Element PBD 154 Element PBD 183 Element PBD 196

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]4L 00010 46L 00002 46L 00011

46L 00003 46L 00024 46L 0000846L 00007 46L 00021 12L 0000246L 00003 46L 00003 12L 0000346L 00004 12L 00003 12L 0000112L 00003 12L 00011 12L 0000212L 00005 12L 0000312L 00031 12L 0000312L 00006

Sample Compost 1 Sample Compost 1 Sample Compost 1Element PBD 197 Element PBD 203 Element PBD 209

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00002 46L 00010 4L 0004146L 00023 12L 00002 4L 0008946L 00022 12L 00003 44L 0041012L 00004 12L 00002 44L 0084012L 00006 12L 00002 44L 0064012L 00003 44L 0040012L 00004 12L 00079

12L 0007312L 0006512L 0009326L 0004926L 00049

Sample Compost 1Element PBD 47

LAB PARM [mgkg]26L 0003826L 00039

Element PBD 99 Element PBD 47 Element PBD 209LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]

4L 00170 10L 00210 4L 010004L 00200 10L 00220 4L 018004L 00170 10L 00210 4L 012004L 00190 46L 00300 4L 0220010L 00280 46L 00280 46L 0210010L 00300 46L 00250 46L 0200010L 00290 46L 00260 64L 0351846L 00340 64L 00059 64L 0363846L 00330 64L 00057 64L 0364546L 00300 64L 00062 64L 0350846L 00310 64L 00060 12L 0220964L 00194 12L 00191 12L 0177164L 00154 12L 00187 12L 0292264L 00185 12L 00190 12L 0164664L 00159 12L 00186 26L 0329712L 00242 26L 00666 26L 0300012L 00223 26L 0033212L 0022112L 0022226L 0024626L 00400

Element PBD 203 Element PBD 197 Element PBD 196LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00022 46L 00027 46L 0002446L 00014 46L 00024 46L 0002264L 00036 12L 00161 64L 0005864L 00058 12L 00060 64L 0006512L 00063 12L 00061 12L 0004812L 00034 12L 00036 12L 0002512L 00038 12L 0003212L 00027 12L 00022

Element PBD 183 Element PBD 154 Element PBD 153LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00049 4L 00020 4L 0002246L 00035 4L 00022 4L 0002446L 00036 4L 00020 4L 0002246L 00034 46L 00025 4L 0002664L 00027 46L 00025 46L 0004064L 00023 46L 00025 46L 0004264L 00024 46L 00023 46L 0003564L 00020 64L 00034 46L 0003812L 00230 64L 00023 64L 0007412L 00032 64L 00017 64L 0004712L 00031 64L 00011 64L 0004612L 00030 12L 00030 64L 0003026L 00007 12L 00021 12L 0006526L 00008 12L 00021 12L 00029

12L 00021 12L 0003226L 00015 12L 0002926L 00019 26L 00039

26L 00040

Element PBD 100LAB PARM [mgkg]

4L 000384L 000414L 000374L 00038

38L 0219038L 0220038L 0208038L 0220010L 0004410L 0005010L 0004310L 0004646L 0005746L 0005946L 0005346L 0005312L 0004312L 0004512L 0004312L 0004326L 0006226L 00057

Sample Soil 3 Sample Soil 3 Sample Soil 3Element PBD 99 Element PBD 47 Element PBD 100

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]10L 00016 10L 00011 10L 0000310L 00019 10L 00010 10L 0000410L 00013 10L 00012 10L 0000410L 00019 46L 00007 10L 0000246L 00025 46L 00022 46L 0000246L 00025 46L 00005 46L 0000646L 00008 46L 00007 46L 0000246L 00011 12L 00010 46L 0000264L 00005 12L 00017 3L 29100064L 00005 12L 00010 3L 32000064L 00006 12L 00009 26L 0000564L 00007 26L 00007 26L 0000512L 00012 26L 0000712L 0001312L 0001312L 0001226L 0000526L 00006

Sample Soil 3 Sample Soil 3 Sample Soil 3Element PBD 153 Element PBD 154 Element PBD 196

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]44L 00050 4L 00010 46L 0000744L 00050 46L 00001 46L 0001146L 00002 46L 00002 46L 0000846L 00003 46L 00001 46L 0001146L 00002 46L 00002 64L 0002646L 00002 64L 00001 64L 0002664L 00001 64L 00001 64L 0002964L 00001 64L 00001 64L 0003464L 00001 64L 00002 12L 0004564L 00002 12L 00003 12L 00032

12L 00002 12L 0002212L 00002 12L 0002112L 00002

Sample Soil 3 Sample Soil 3 Sample Soil 3Element PBD 197 Element PBD 203 Element PBD 209

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00006 46L 00011 4L 0091046L 00013 46L 00017 4L 0150046L 00011 46L 00015 4L 0120046L 00013 46L 00018 4L 0160012L 00090 64L 00013 44L 0337012L 00056 64L 00014 44L 0281012L 00033 64L 00016 44L 0287012L 00032 64L 00015 44L 02540

12L 00055 46L 0230012L 00041 46L 0220012L 00027 46L 0150012L 00026 46L 01900

64L 0438164L 0401664L 0414464L 0449812L 0367112L 0397812L 0409112L 03838

Sample Soil 3 26L 0102Element PBD 183 26L 0131

LAB PARM [mgkg]46L 0000746L 0000846L 0005846L 0000764L 0000264L 0000364L 0000364L 0000312L 0001512L 0001112L 0000712L 00007

European Commission EUR 23003 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on polybrominated diphenylethers Author(s) E Sobiecka H van der Sloot D Barcelo B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 68 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07403-5 Abstract Project HORIZONTAL is interdisciplinary aiming at a harmonisation and horizontal standardisation of test procedures in particular for sludge soils and biowastes In the context of this standardization project a series of draft technical specification were designed upon an extensive desk study fine-tuned after expert consultations and finally validated in international intercomparisons exercise This report summarises the work performed within the validation study of the draft standard for the determination of polybrominated diphenylethers (PBDE) in soils sludge and treated bio-waste using gas-chromatography method with mass selective detection (GC-MS) It further explains the underlying statistical concept for the calculation of reproducibility and repeatability from intercomparisons data In addition all single values results of the statistical evaluation as well as background information on the validation materials used are described and explained

The mission of the JRC is to provide customer-driven scientific and technical support for the conception development implementation and monitoring of EU policies As a service of the European Commission the JRC functions as a reference centre of science and technology for the Union Close to the policy-making process it serves the common interest of the Member States while being independent of special interests whether private or national

LB

-NA

-23003-EN

-C

VII

List of Abbreviations Throughout this report the following abbreviations are used

AOX absorbable organic halogens

Corg organic carbon content

Ctotal total carbon content

CAT cation exchangeable

CDD chlorinated dibenzodioxin

CDF chlorinated dibenzofuran

DEHP di(2-ethylhexyl)phthalate

DM dry matter

EPA Environment Protection Agency

EU European Union

FM fresh matter

Hp hepta

Hx hexa

IES Institute for Environment and Sustainability

IRMM Institute for Reference Materials and Measurements

JRC Joint Research Centre

LAS linear alkylsulfonates

LoD limit of detection

LUA Landesumweltamt

Ntotal total nitrogen content

NH4-N Ammonium nitrogen

NO3-N Nitrate nitrogen

NP nonylphenol

NRW North Rhine Westphalia

O octa

P poly

PAH polycyclic aromatic hydrocarbon

PCB polychlorinated biphenyl

Pe penta

T tetra

TEQ toxicity equivalent

UBA Umweltbundesamt

WHO World Health Organization

WWTP waste water treatment plant

6

1 Introduction This report gives an overview on the available analytical information on the following raw materials to be used for the production of validation materials of the so-called Project HORIZONTAL

bull Four sludge materials from Duumlsseldorf Germany

bull An agricultural soil material from Reading United Kingdom

bull A compost material from Vienna Austria

bull A compost material from Korschenbroich Germany

bull A sludge-amended agricultural soil from Pavia Province Italy

bull A sludge-amended soil from Barcelona Spain

bull A sludge-amended soil from Essen Germany

bull A long-term sludge exposed soil from Hohenheim Germany

The following analytical information was gathered partly before and during the sampling of the raw materials to be used for the production of the HORIZONTAL validation materials The material were sampled by IES and shipped to IRMM in the course of the year 2005 The information gathered was then completed by various analytical screenings for PAHs and PCBs done by the Institute for Reference Materials and Measurements Geel Belgium for phthalates done by UBA Berlin Germany for PBDE done by IIQAB-CSIC Barcelona Spain for trace elements and some selected major and minor elements by the Institute for Environment and Sustainability Ispra Italy

The work compiled hereafter is based on the numerous additional efforts of the scientists working at various members of the consortium Project HORIZONTAL-Org and contributing organisations

This work is gratefully acknowledged

2 Overview on property values

21 Sludge materials from Duumlsseldorf Germany

The various sewage sludge materials originate from various installations in the North Rhine Westphalia and were produced and sampled by staff from the Landesumweltamt (LUA) NRW under the responsibility from Dr K Furtmann

In total four sludge materials (Sludge A and D from a major municipal WWTP Sludge B from a municipal WWTP with industrial input and Sludge C from a municipal WWTP with high PCB-Content) were obtained and will be blended to two final materials Before sampling the following analytical data for a typical sample were received

7

Table 1 ndash Analytical data obtained on an average sludge sample in LUA NRW (with courtesy of K Furtmann LUA Duumlsseldorf)

Parameter Concentration PCB 120 ugkg DEHP 110 mgkg PAH 5 mgkg (EPA) PCDDF 15 ng TEkg PBDE 400 ugkg NP 40 mgkg LAS 3 gkg AOX 300 mgkg

Subsequent screening led to the information displayed hereafter It should be stressed that the data were obtained as SCREENING information on the UNTREATED or partially treated raw materials Therefore the final target values which are relevant for the validation intercomparison can be different

Table 2 ndash Analytical data obtained on a first screening on the sludge samples from LUA NRW

Sewage sludge A

Dusseldorf

sewage sludge D

Dusseldorf PCB (ngg) 28 62 35 52 101 65 101 31 38 118 49 40 153 30 33 105 24 11 138 46 38 156 lt1 lt1 180 34 23 170 23 19 PAH (ngg) Naphtalene 34 381 Acenaphtylene 15 43 Acenaphthene 81 108 Fluorene 94 1167 Phenantrene 3440 Anthracene 22 344 Flouranthene 316 4817 Pyrene 235 3011 Benz(a)anthracene 473 791 Chrysene 691 1078 Benz(b)fluoranthene 538 1688 Benz(k)fluoranthene 228 635 Benz(a)pyrene 383 1114 Indeno(123-cd)pyrene 92 229 Dibenzo(ah)anthracene 71 70 Benzo(ghi)perylene 80 185

8

Table 3 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Sludge D (1) 0135 41474 385 Sludge B (2) 0538 0034 30634 547 Sludge A (3) 0184 0037 31399 146 Sludge C (4) 0354 1528 6678 229

Table 4 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Sludge 2

(B)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

554

959

694

591

772

509

nq

nq

970

2216

2379

Table 5 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena IES Ispra Spain) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Sludge 1 (D) 265 290 533 359 1231 338 784 438 lt 005 232 786 Sludge 2 (B) 119 311 626 202 278 299 722 251 lt 005 118 625 Sludge 3 (A) 168 360 621 332 847 416 119 451 lt 005 116 1237 Sludge 4 (C) 563 198 116 273 726 511 473 618 lt 005 444 2015

Table 6 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Sludge 1 (D) 2154 58 844 099 103 101 4367 lt15 50448 Sludge 2 (B) 1067 366 692 046 1491 077 5217 lt15 57633 Sludge 3 (A) 731 663 684 035 1287 068 3733 lt15 60369 Sludge 4 (C) 4379 965 527 163 522 107 5628 lt15 23945

Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM)Sludge 1 (D) 03 2403 101 1002 350 15 1944 132Sludge 2 (B) 031 315 97 879 172 12 514 180Sludge 3 (A) 031 1281 153 1567 265 16 1440 168Sludge 4 (C) 055 231 628 2625 371 81 1101 244

9

22 Agricultural soil material from Reading United Kingdom

The material was proposed by the University of Reading (S Nortcliff) and was sampled from a site called ldquoFrogmore Farmrdquo which was featured in the ldquoMetalsrdquo Report for HORIZONTAL This site is close to Reading with soils developed on flintyloamy periglacial materials over Chalk has a long and well documented history of sludge application The focus of the work of Nortcliff et al undertook at this site and the monitoring and control at the site (by Thames Water and the subsequent subsidiary bodies dealing with sludge application to soil) was on metals (and metal loads) with no analysis or indeed any form of investigation in to organics in the broadest sense

The analytical information produced in the context of the screening of the raw material is displayed below

Table 7 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 3

(Reading) 0032 0119 669

Table 8 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 3 (Reading) 015 706 279 138 152 901 267 300 lt 005 258 931

Table 9 ndash Analytical data obtained on a first screening on the sludge-amended soil from Reading (courtesy of IRMM)

Parameter Concentration

PCB ngg 28 lt1 52 lt1 101 lt1 118 lt1 153 lt1 105 lt1 138 lt1 156 lt1 180 lt1 170 lt1 PAH ngg Naphtalene lt10 Acenaphtylene 21 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene lt10 Flouranthene 818 Pyrene 776 Benz(a)anthracene 565

10

Parameter Concentration

Chrysene 608 Benz(b)fluoranthene 824 Benz(k)fluoranthene 329 Benz(a)pyrene 799 Indeno(123-cd)pyrene

779

Dibenzo(ah)anthracene 118 Benzo(ghi)perylene 394

Table 10 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 3

(Reading)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

103

003

nq

nq

nq

nd

nd

272

273

Table 11 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 3 (Reading) 015 706 279 138 152 901 267 300 lt 005 258 931

Table 12 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 3 (Reading) 7936 477 112 096 194 017 4107 443 2102 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 3 (Reading) 042 13 45 69 69 69 216 92

Table 13 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 3 (Reading) 012

11

23 Compost from Vienna Austria

The fresh compost material was obtained from the Austrian Federal Environment Agency (UBA Vienna) which had used a sub-batch of the raw material for national intercomparson The remainder of the material was stored at 4degC until shipment to IRMM for further processing The following analytical information was provided by UBA Austria and completed with various screenings

Table 14 ndash Analytical data on compost material received from UBA Austria Inorganic and sum parameters

Parameter Unit Sample fraction used Observed mean B CAT mgl FM Fresh sample lt10mm 61 K CAT mgl FM Fresh sample lt10mm 2624 Mg CAT mgl FM Fresh sample lt10mm 242 P CAT mgl FM Fresh sample lt10mm 49 B CAT DM Fresh sample lt10mm 00017 K CAT DM Fresh sample lt10mm 072 Mg CAT DM Fresh sample lt10mm 007 P CAT DM Fresh sample lt10mm 001 NO3-N mgkg FM Fresh sample lt10mm 35 NH4-N mgkg FM Fresh sample lt10mm 230 Ctotal DM lt45degdry milled 29 Corg DM lt45degdry milled 27 Ntotal DM lt45degdry milled 17 P mgkg DM lt45degdry milled 2596 K mgkg DM lt45degdry milled 11019 K DM lt45degdry milled 110 B mgkg DM lt45degdry milled 60 Cd mgkg DM lt45degdry milled 046 Cr mgkg DM lt45degdry milled 25 Cu mgkg DM lt45degdry milled 46 Hg mgkg DM lt45degdry milled 020 Ni mgkg DM lt45degdry milled 18 Pb mgkg DM lt45degdry milled 45 Zn mgkg DM lt45degdry milled 198 Ca mgkg DM lt45degdry milled 68776 Ca DM lt45degdry milled 69 Mo mgkg DM lt45degdry milled 08 S mgkg DM lt45degdry milled 2137 Fe mgkg DM lt45degdry milled 9959 Mn mgkg DM lt45degdry milled 418 Na mgkg DM lt45degdry milled 742 Co mgkg DM lt45degdry milled 41 AOX mgkg DM lt30deg dry milled 62

Table 15 ndash Analytical data on compost material received from UBA Austria Polycyclic aromatic hydrocarbons

PAH Unit Result Naphthaline microgkg DM 93 Acenaphthylene microgkg DM 86 Acenaphthene microgkg DM 5 Fluorene microgkg DM 80 Phenanthrene microgkg DM 89 Anthracene microgkg DM 27 Fluoranthene microgkg DM 487 Pyrene microgkg DM 380

12

PAH Unit Result Benzo(a)anthracene microgkg DM 278 Chrysene microgkg DM 317 Benzo(b)fluoranthene microgkg DM 365 Benzo(k)fluoranthene microgkg DM 193 Benz(a)pyrene microgkg DM 320 Indeno(123-cd)pyrene microgkg DM 233 Dibenz(ah)anthracene microgkg DM 67 Benzo(ghi)perylene microgkg DM 225 Sum EPA microgkg DM 3013 Sum EPA mgkg DM 30

Table 16 ndash Analytical data on compost material received from UBA Austria Sum PCDDs and PCBs

Parameter

Dioxine TEQ (ITEF) ngkg DM 73 TEQ (WHO) ngkg DM 35 PCB Σ Ballschmiter mgkg DM 005

Table 17 ndash Analytical data on compost material obtained by screening in IRMM

Parameter Result in ngg

PCB 28 2 52 2 101 4 118 3 153 10 105 1 138 8 156 1 180 5 170 lt1 PAH Naphtalene lt10 Acenaphtylene lt10 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene 26 Fluoranthene 611 Pyrene 510 Benz(a)anthracene 888 Chrysene 957 Benz(b)fluoranthene 1531 Benz(k)fluoranthene 547 Benz(a)pyrene 1101 Indeno(123-cd)pyrene 416 Dibenzo(ah)anthracene 81 Benzo(ghi)perylene 295

13

Table 18 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Compost 1

(Vienna)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

402

019

259

nq

023

004

nq

nq

144

174

259

Table 19 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Compost 1

(Vienna) 0058 1426 557

Table 20 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Compost 1 (Vienna) 039 736 319 410 365 127 495 004 079 013 208

Table 21 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Compost 1 (Vienna) 2063 431 617 426 199 249 1602 lt15 10521

Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Compost 1 (Vienna) 035 3496 81 375 79 55 653 60

Table 22 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Compost 1 (Vienna) 017

14

24 Agricultural soil sludge amended soil from Pavia Italy

This sludge-amended soil material was obtained during a monitoring campaign which aimed at a generic description of the over-all soil quality in Pavia Province Italy The material which was collected from the upper horizon originates from a small farm called ldquoCascina Novellordquo During the characterisation of the site the following analytical information was obtained on a pooled sample of a sub-area of the farm of 20 X 20 m2

Table 23 ndash Analytical data on Pavia soil

Parameter Result Al 713 Wgt As 224 mgkg Cd 079 mgkg Cr 59 mgkg Cu 308 mgkg Hg 008 mgkg Ni 344 mgkg Pb 246 mgkg Zn 95 mgkg C 091 Wgt 2378-TCDD 0047 pgg 12378-PeCDD 015 pgg 123478-HxCDD 019 pgg 123678-HxCDD 15 pgg 123789-HxCDD 074 pgg 1234678-HpCDD 26 pgg OCDD 382 pgg 2378-TCDF 068 pgg 12378-PeCDF 053 pgg 23478-PeCDF 071 pgg 123478-HxDF 100 pgg 123678-HxDF 066 pgg 234678-HxDF 16 pgg 123789-HxDF 027 pgg 1234678-HpDF 12 pgg 1234789-HpDF 068 pgg OCDF 33 pgg I-TEQ 20 pgg WHO-TEQ 17 pgg

In addition the screening performed at IRMM did not reveal significant quantities of PCBs and PAHs which were all below the LoDs (1 ngg for PCBs and 10 ngg for PAHs respectively)

Table 24 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 5 (Pavia) 0005 0011 154

15

Table 25 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 5

(Pavia)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

039

nq

nq

008

nq

nd

nd

670

671

Table 26 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 5 (Pavia) 033 184 573 225 426 305 206 200 lt 005 381 878

Table 27 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 5 (Pavia) 6939 129 145 224 425 116 6118 255 1789 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 5 (Pavia) 184 62 38 108 55 66 597 110

Table 28 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 5 (Pavia) 006

16

25 Sludge-amended-soil from Barcelona Spain

The sludge-amended soil material from Barcelona sampled upon indication from the Barcelorsquo- Group in Barcelona

Table 29 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 2 (Lleida T) 0015 0183 1138

Table 30 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 2

(Lleida T)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

159

045

nq

048

160

nq

nq

1000

1004

Table 31 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 2 (Lleida T) 059 141 327 536 405 186 184 224 lt 005 318 111

Table 32 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 2 (Lleida T) 4443 1067 1429 253 344 204 4116 780 3396 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 2 (Lleida T) 064 65 26 125 59 17 547 65

Table 33 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 2 (Lleida T) 010

17

26 Sludge amended soil from Essen Germany

The German sludge-amended soil from Essen which was provided as the three sludge materials by LUA NRW did not feature significant concentrations of the PCB congeners 28 52 101 118 153 105 138 156 180 170 but had detectable amounts of some PAHs

Table 34 ndash Analytical screening data on the German sludge-amended soil

Parameter Concentration(ngg)

Naphtalene lt10 Acenaphtylene lt10 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene lt10 Fluoranthene 28 Pyrene 20 Benz(a)anthracene 24 Chrysene 47 Benz(b)fluoranthene 76 Benz(k)fluoranthene 20 Benz(a)pyrene 35 Indeno(123-cd)pyrene 35 Dibenzo(ah)anthracene 10 Benzo(ghi)perylene 26

Table 35 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 4 (Essen) 0011 0302 055

Table 36 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 4

(Essen)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

nq

nq

nq

nq

nq

nq

128

191

203

18

Table 37 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 4 (Essen) 052 545 261 805 320 403 273 273 lt 005 295 781

Table 38 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 4 (Essen) 7947 442 085 06 086 007 2163 189 2019 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 4 (Essen) 045 19 42 87 683 60 462 61

Table 39 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 4 (Essen) 004

27 Long-term sludge exposed soil from Hohenheim-Stuttgart Germany

Similarly an additional sludge exposed soil was sampled at the University of Hohenheim Stuttgart were a test soil was long-term exposed to elevated concentrations of sewage sludge

Table 40 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 1 (Stuttgart) 0045 0263 1765

Table 41 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 1

(Stuttgart)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

230

006

004

004

nq

nd

nd

498

500

19

Table 42 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 1 (Stuttgart) 069 127 361 262 504 183 252 262 lt 005 266 142

Table 43 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 1 (Stuttgart) 7194 1006 133 186 366 088 7874 275 3571 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 1 (Stuttgart) 123 50 47 212 85 69 991 129

Table 44 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 1 (Stuttgart) 177

18

Annex 3

Statistical calculations

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 47)Mandels h statistics(Sludge 1 - PBD 47)

Sample Sludge 1 NUM

Element PBD 47

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00213 0001 3 -021 005 - - 10L - - NUM46L 00273 0002 4 016 021 - - 46L - - NUM64L 00059 0000 4 -116 002 NUM - 64L - - NUM12L 00188 0000 4 -036 002 - - 12L - - NUM26L 00499 0024 2 157 223 Fail - - 26L - - NUM

Totgem 0025 0005 mgkg 1-level 172 (185) NUM (10L46L64L12L26L) -1Totstd= 0016 0010 5-level 157 (162) 5

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 5 Labs rejected (10L46L64L12L26L)

000 050 100 150 200 250

k-values

10L

46L

64L

12L

26L

Mandels k statistics(Sludge 1 - PBD 47)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

10L

46L

64L

12L

26L

Labo

rato

ries

NUM

-200 -100 000 100 200

h-values

10L

46L

64L

12L

26L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 47)

Sludge 1-PBD 47

Unit mgkg

Mandels k statistics(Soil 3 - PBD 47)Mandels h statistics(Soil 3 - PBD 47)

Sample Soil 3 Soil 3 - PBD 47 -- Mean PARM = 0001 [mgkg]

Element PBD 47

General calcparmT1= 134814E-02T2= 142830E-05T3= 13T4= 45T5= 22767E-06

n= variabelp= 4

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean26L 00007 0000 2 -143 001 00007 00000 2 1 00046L 00010 0001 4 010 181 00010 00008 4 3 00010L 00011 0000 3 049 023 00011 00001 3 2 00012L 00012 0000 4 084 081 00012 00004 4 3 000

Totgem 0001 0000 mgkg 1-level 149 (177) 4 00010 () 4 3Totstd= 0000 0000 5-level 142 (159)

RESULTS Mean = 000100 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000050 --gt 5031 r = 00014Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000050 --gt 5031 R = 00014Remarks none

000 050 100 150 200

k-values

26L

46L

10L

12L

Mandels k statistics(Soil 3 - PBD 47)

00 00 00 00 00 00 00 00 00 00 00

Deviation from Mean

26L

46L

10L

12L

Labo

rato

ries

Soil 3 - PBD 47 -- Mean PARM = 0001 [mgkg]

-200 -100 000 100

h-values

26L

46L

10L

12L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 47)

Soil 3-PBD 47

Unit mgkg

Mandels k statistics(Compost 1 - PBD 99)Mandels h statistics(Compost 1 - PBD 99)

Sample Compost 1 Compost 1 - PBD 99 -- Mean PARM = 0003 [mgkg]

Element PBD 99

General calcparmT1= 492124E-02T2= 148747E-04T3= 17T4= 61T5= 93196E-06

n= variabelp= 5

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00020 0000 4 -137 053 00020 00004 4 3 000

26L 00025 0000 2 -058 024 00025 00002 2 1 00010L 00029 0000 3 012 032 00029 00003 3 2 00046L 00033 0001 4 069 161 00033 00013 4 3 00012L 00036 0001 4 114 140 00036 00011 4 3 000

Totgem 0003 0001 mgkg 1-level 172 (185) 5 00029 () 5 4Totstd= 0001 0001 5-level 157 (162)

RESULTS Mean = 000286 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000088 --gt 3086 r = 00025Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000101 --gt 3525 R = 00028Remarks none

000 050 100 150 200

k-values

4L

26L

10L

46L

12L

Mandels k statistics(Compost 1 - PBD 99)

00 00 00 00 00 00 00 00 00 00

Deviation from Mean

4L

26L

10L

46L

12L

Labo

rato

ries

Compost 1 - PBD 99 -- Mean PARM = 0003 [mgkg]

-200 -100 000 100 200

h-values

4L

26L

10L

46L

12L

Labo

rato

ries

Mandels h statistics(Compost 1 - PBD 99)

Compost 1-PBD 99

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 99)Mandels h statistics(Sludge 1 - PBD 99)

Sample Sludge 1 Sludge 1 - PBD 99 -- Mean PARM = 0024 [mgkg]

Element PBD 99

General calcparmT1= 448050E-01T2= 112113E-02T3= 19T4= 73T5= 32972E-05

n= variabelp= 5

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean64L 00173 0002 4 -118 041 Fail 00173 00019 4 3 -0014L 00183 0002 4 -104 032 00183 00015 4 3 -001

12L 00227 0001 4 -038 022 00227 00010 4 3 00010L 00290 0001 3 055 021 00290 00010 3 2 00146L 00320 0002 4 100 039 00320 00018 4 3 00126L 00323 0011 2 105 234 - - 26L - - 001

Totgem 0025 0003 mgkg 1-level 187 (177) 5 00239 (26L) 5 4Totstd= 0007 0004 5-level 166 (154) 1

RESULTS Mean = 002385 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000153 --gt 643 r = 00043Between lab variance S2L = 000004Reproducibility var S2R = 000004Reproducibility std SR = 000666 --gt 2791 R = 00186Remarks 1 Lab rejected (26L)

000 050 100 150 200 250

k-values

64L

4L

12L

10L

46L

26L

Mandels k statistics(Sludge 1 - PBD 99)

00 00 00 00 00 00 00 00 00 00

Deviation from Mean

64L

4L

12L

10L

46L

26L

Labo

rato

ries

Sludge 1 - PBD 99 -- Mean PARM = 0024 [mgkg]

-200 -100 000 100 200

h-values

64L

4L

12L

10L

46L

26L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 99)

Sludge 1-PBD 99

Unit mgkg

Mandels k statistics(Soil 3 - PBD 99)Mandels h statistics(Soil 3 - PBD 99)

Sample Soil 3 NUM

Element PBD 99

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00017 0000 4 091 068 - - 10L - - NUM46L 00017 0001 4 100 211 - - 46L - - NUM64L 00005 0000 4 -106 023 NUM - 64L - - NUM12L 00012 0000 4 015 014 - - 12L - - NUM26L 00006 0000 2 -101 012 - - 26L - - NUM

Totgem 0001 0000 mgkg 1-level 172 (173) NUM (10L46L64L12L26L) -1Totstd= 0001 0000 5-level 157 (153) 5

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 5 Labs rejected (10L46L64L12L26L)

000 050 100 150 200 250

k-values

10L

46L

64L

12L

26L

Mandels k statistics(Soil 3 - PBD 99)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

10L

46L

64L

12L

26L

Labo

rato

ries

NUM

-200 -100 000 100 200

h-values

10L

46L

64L

12L

26L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 99)

Soil 3-PBD 99

Unit mgkg

Mandels k statistics(Compost 1 - PBD 100)Mandels h statistics(Compost 1 - PBD 100)

Sample Compost 1 Compost 1 - PBD 100 -- Mean PARM = 0001 [mgkg]

Element PBD 100

General calcparmT1= 124272E-02T2= 113129E-05T3= 14T4= 52T5= 46584E-07

n= variabelp= 4

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean26L 00006 0000 2 -131 037 Fail 00006 00001 2 1 00010L 00009 0000 4 003 083 00009 00002 4 3 00046L 00009 0000 4 016 115 00009 00002 4 3 00012L 00011 0000 4 112 136 Fail 00011 00003 4 3 000

Totgem 0001 0000 mgkg 1-level 149 (167) 4 00009 () 4 3Totstd= 0000 0000 5-level 142 (15)

RESULTS Mean = 000085 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000022 --gt 2531 r = 00006Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000025 --gt 2882 R = 00007Remarks none

000 050 100 150

k-values

26L

10L

46L

12L

Mandels k statistics(Compost 1 - PBD 100)

00 00 00 00 00 00 00 00 00 00 00

Deviation from Mean

26L

10L

46L

12L

Labo

rato

ries

Compost 1 - PBD 100 -- Mean PARM = 0001 [mgkg]

-200 -100 000 100 200

h-values

26L

10L

46L

12L

Labo

rato

ries

Mandels h statistics(Compost 1 - PBD 100)

Compost 1-PBD 100

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 100)Mandels h statistics(Sludge 1 - PBD 100)

Sample Sludge 1 Sludge 1 - PBD 100 -- Mean PARM = 0005 [mgkg]

Element PBD 100

General calcparmT1= 852065E-02T2= 412762E-04T3= 18T4= 68T5= 78914E-07

n= variabelp= 5

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00039 0000 4 -042 007 Fail 00039 00002 4 3 000

12L 00044 0000 4 -041 005 Fail 00044 00001 4 3 00010L 00046 0000 4 -041 013 Fail 00046 00003 4 3 00046L 00056 0000 4 -040 012 Fail 00056 00003 4 3 00026L 00059 0000 2 -040 013 Fail 00059 00003 2 1 00038L 02168 0006 4 204 244 Fail - - 38L - - 021

Totgem 0040 0001 mgkg 1-level 187 (177) 5 00049 (38L) 5 4Totstd= 0087 0002 5-level 166 (154) 1

RESULTS Mean = 000486 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000025 --gt 507 r = 00007Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000084 --gt 1731 R = 00024Remarks 1 Lab rejected (38L)

000 050 100 150 200 250

k-values

4L

12L

10L

46L

26L

38L

Mandels k statistics(Sludge 1 - PBD 100)

-01 00 01 01 02 02 03

Deviation from Mean

4L

12L

10L

46L

26L

38L

Labo

rato

ries

Sludge 1 - PBD 100 -- Mean PARM = 0005 [mgkg]

-100 000 100 200 300

h-values

4L

12L

10L

46L

26L

38L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 100)

Sludge 1-PBD 100

Unit mgkg

Mandels k statistics(Soil 3 - PBD 100)Mandels h statistics(Soil 3 - PBD 100)

Sample Soil 3 NUM

Element PBD 100

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00003 0000 4 -050 000 Fail - - 10L - - NUM46L 00003 0000 4 -050 000 Fail NUM - 46L - - NUM3L 305500 2051 2 150 200 Fail - - 3L - - NUM

26L 00005 0000 2 -050 000 Fail - - 26L - - NUM

Totgem 7638 0513 mgkg 1-level 149 (177) NUM (10L46L3L26L) -1Totstd= 15275 1025 5-level 142 (159) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (10L46L3L26L)

000 050 100 150 200

k-values

10L

46L

3L

26L

Mandels k statistics(Soil 3 - PBD 100)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

10L

46L

3L

26L

Labo

rato

ries

NUM

-100 000 100 200

h-values

10L

46L

3L

26L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 100)

Soil 3-PBD 100

Unit mgkg

Mandels k statistics(Compost 1 - PBD 153)Mandels h statistics(Compost 1 - PBD 153)

Sample Compost 1 NUM

Element PBD 153

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean44L 00053 0001 3 150 157 Fail - - 44L - - NUM46L 00007 0000 4 -044 111 Fail - - 46L - - NUM12L 00005 0000 4 -051 055 Fail - - 12L - - NUM26L 00005 0000 2 -054 001 Fail NUM - 26L - - NUM

Totgem 0002 0000 mgkg 1-level 149 (177) NUM (44L46L12L26L) -1Totstd= 0002 0000 5-level 142 (159) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (44L46L12L26L)

000 050 100 150 200

k-values

44L

46L

12L

26L

Mandels k statistics(Compost 1 - PBD 153)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

44L

46L

12L

26L

Labo

rato

ries

NUM

-100 000 100 200

h-values

44L

46L

12L

26L

Labo

rato

ries

Mandels h statistics(Compost 1 - PBD 153)

Compost 1-PBD 153

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 153)Mandels h statistics(Sludge 1 - PBD 153)

Sample Sludge 1 Sludge 1 - PBD 153 -- Mean PARM = 0004 [mgkg]

Element PBD 153

General calcparmT1= 676738E-02T2= 267609E-04T3= 18T4= 68T5= 19626E-05

n= variabelp= 5

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00024 0000 4 -157 017 00024 00002 4 3 000

12L 00038 0002 4 006 154 00038 00018 4 3 00046L 00039 0000 4 011 026 00039 00003 4 3 00026L 00039 0000 2 018 004 00039 00000 2 1 00064L 00049 0002 4 122 159 00049 00018 4 3 000

Totgem 0004 0001 mgkg 1-level 172 (173) 5 00038 () 5 4Totstd= 0001 0001 5-level 157 (153)

RESULTS Mean = 000378 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000123 --gt 3252 r = 00034Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000142 --gt 3754 R = 00040Remarks none

000 050 100 150 200

k-values

4L

12L

46L

26L

64L

Mandels k statistics(Sludge 1 - PBD 153)

00 00 00 00 00 00 00

Deviation from Mean

4L

12L

46L

26L

64L

Labo

rato

ries

Sludge 1 - PBD 153 -- Mean PARM = 0004 [mgkg]

-200 -100 000 100 200

h-values

4L

12L

46L

26L

64L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 153)

Sludge 1-PBD 153

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 154)Mandels h statistics(Sludge 1 - PBD 154)

Sample Sludge 1 NA

Element PBD 154

General calcparmT1= NAT2= NAT3=T4=T5=

n= variabelp=

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00021 0000 3 -100 021 NA - 4L - - NA

46L 00025 0000 4 115 018 NA - 46L - - NA64L 00021 0001 4 -066 179 - - 64L - - NA12L 00023 0000 4 050 085 - - 12L - - NA

Totgem 0002 0000 mgkg 1-level 149 (167) NA (4L46L64L12L) -1Totstd= 0000 0000 5-level 142 (15) 4

RESULTS Mean = NA mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NAReproducibility var S2R = NAReproducibility std SR = NA --gt NA R = NARemarks 4 Labs rejected (4L46L64L12L)

000 050 100 150 200

k-values

4L

46L

64L

12L

Mandels k statistics(Sludge 1 - PBD 154)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

4L

46L

64L

12L

Labo

rato

ries

NA

-100 000 100 200

h-values

4L

46L

64L

12L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 154)

Sludge 1-PBD 154

Unit mgkg

Mandels k statistics(Soil 3 - PBD 154)Mandels h statistics(Soil 3 - PBD 154)

Sample Soil 3 NUM

Element PBD 154

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

4L 00010 - 1 150 Fail - - 4L - - NUM46L 00001 0000 4 -053 096 Fail - - 46L - - NUM64L 00001 0000 4 -056 105 Fail NUM - 64L - - NUM12L 00002 0000 4 -040 099 Fail - - 12L - - NUM

Totgem 000037 0000 mgkg 1-level 149 (164) NUM (4L46L64L12L) -1Totstd= 000042 0000 5-level 142 (153) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (4L46L64L12L)

000 050 100 150

k-values

4L

46L

64L

12L

Mandels k statistics(Soil 3 - PBD 154)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

4L

46L

64L

12L

Labo

rato

ries

NUM

-100 000 100 200

h-values

4L

46L

64L

12L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 154)

Soil 3-PBD 154

Unit mgkg

Mandels k statistics(Compost 1 - PBD 209)Mandels h statistics(Compost 1 - PBD 209)

Sample Compost 1 NUM

Element PBD 209

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00065 0003 2 -049 032 - - 4L - - NUM

44L 00573 0021 4 150 197 Fail - - 44L - - NUM12L 00078 0001 4 -045 011 - - 12L - - NUM26L 00049 0000 2 -056 000 NUM - 26L - - NUM

Totgem 0019 0006 mgkg 1-level 149 (177) NUM (4L44L12L26L) -1Totstd= 0025 0010 5-level 142 (159) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (4L44L12L26L)

000 050 100 150 200

k-values

4L

44L

12L

26L

Mandels k statistics(Compost 1 - PBD 209)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

4L

44L

12L

26L

Labo

rato

ries

NUM

-100 000 100 200

h-values

4L

44L

12L

26L

Labo

rato

ries

Mandels h statistics(Compost 1 - PBD 209)

Compost 1-PBD 209

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 209)Mandels h statistics(Sludge 1 - PBD 209)

Sample Sludge 1 Sludge 1 - PBD 209 -- Mean PARM = 0249 [mgkg]

Element PBD 209

General calcparmT1= 394542E+00T2= 107296E+00T3= 16T4= 56T5= 19723E-02

n= variabelp= 5

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 01550 0055 4 -112 148 Fail 01550 00551 4 3 -009

46L 02050 0007 2 -053 019 02050 00071 2 1 -00412L 02137 0058 4 -042 155 02137 00576 4 3 -00426L 03149 0021 2 078 057 Fail 03149 00210 2 1 00764L 03577 0007 4 129 020 Fail 03577 00074 4 3 011

Totgem 0249 0030 mgkg 1-level 172 (185) 5 02493 () 5 4Totstd= 0084 0025 5-level 157 (162)

RESULTS Mean = 024926 mgkg

Repeatability variance S2r = 000179Repeatability std Sr = 004234 --gt 1699 r = 01186Between lab variance S2L = 000743Reproducibility var S2R = 000922Reproducibility std SR = 009604 --gt 3853 R = 02689Remarks none

000 050 100 150 200

k-values

4L

46L

12L

26L

64L

Mandels k statistics(Sludge 1 - PBD 209)

-01 -01 00 01 01 02

Deviation from Mean

4L

46L

12L

26L

64L

Labo

rato

ries

Sludge 1 - PBD 209 -- Mean PARM = 0249 [mgkg]

-200 -100 000 100 200

h-values

4L

46L

12L

26L

64L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 209)

Sludge 1-PBD 209

Unit mgkg

Mandels k statistics(Soil 3 - PBD 209)Mandels h statistics(Soil 3 - PBD 209)

Sample Soil 3 Soil 3 - PBD 209 -- Mean PARM = 0258 [mgkg]

Element PBD 209

General calcparmT1= 596398E+00T2= 191917E+00T3= 22T4= 84T5= 13249E-02

n= variabelp= 6

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean26L 01162 0021 2 -108 074 Fail 01162 00207 2 1 -0144L 01303 0031 4 -097 111 Fail 01303 00312 4 3 -013

46L 01975 0036 4 -046 128 Fail 01975 00359 4 3 -00644L 02898 0035 4 024 124 Fail 02898 00346 4 3 00312L 03895 0018 4 100 065 Fail 03895 00181 4 3 01364L 04260 0022 4 127 078 Fail 04260 00219 4 3 017

Totgem 0258 0027 mgkg 1-level 187 (177) 6 02582 () 6 5Totstd= 0132 0008 5-level 166 (154)

RESULTS Mean = 025818 mgkg

Repeatability variance S2r = 000083Repeatability std Sr = 002878 --gt 1115 r = 00806Between lab variance S2L = 001640Reproducibility var S2R = 001723Reproducibility std SR = 013127 --gt 5084 R = 03676Remarks none

000 050 100 150

k-values

26L

4L

46L

44L

12L

64L

Mandels k statistics(Soil 3 - PBD 209)

-02 -01 -01 00 01 01 02 02

Deviation from Mean

26L

4L

46L

44L

12L

64L

Labo

rato

ries

Soil 3 - PBD 209 -- Mean PARM = 0258 [mgkg]

-200 -100 000 100 200

h-values

26L

4L

46L

44L

12L

64L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 209)

Soil 3-PBD 209

Unit mgkg

Mandels k statistics(Compost 1 - Sum PBD)Mandels h statistics(Compost 1 - Sum PBD)

Sample Compost 1 Compost 1 - Sum PBD -- Mean PARM = 0009 [mgkg]

Element Sum PBD

General calcparmT1= 154064E-01T2= 169065E-03T3= 18T4= 68T5= 11354E-04

n= variabelp= 5

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00031 0002 4 -067 016 00031 00016 4 3 -0014L 00055 0005 4 -056 048 00055 00047 4 3 000

46L 00085 0003 4 -042 031 00085 00030 4 3 00026L 00123 0000 2 -024 003 00123 00002 2 1 00012L 00154 0002 4 -011 021 00154 00021 4 3 00144L 00613 0023 4 200 237 Fail - - 44L - - 005

Totgem 0018 0006 mgkg 1-level 187 (177) 5 00089 (44L) 5 4Totstd= 0022 0009 5-level 166 (154) 1

RESULTS Mean = 000893 mgkg

Repeatability variance S2r = 000001Repeatability std Sr = 000296 --gt 3308 r = 00083Between lab variance S2L = 000002Reproducibility var S2R = 000003Reproducibility std SR = 000570 --gt 6374 R = 00159Remarks 1 Lab rejected (44L)

000 050 100 150 200 250

k-values

10L

4L

46L

26L

12L

44L

Mandels k statistics(Compost 1 - Sum PBD)

00 00 00 00 00 00 01 01

Deviation from Mean

10L

4L

46L

26L

12L

44L

Labo

rato

ries

Compost 1 - Sum PBD -- Mean PARM = 0009 [mgkg]

-100 000 100 200

h-values

10L

4L

46L

26L

12L

44L

Labo

rato

ries

Mandels h statistics(Compost 1 - Sum PBD)

Compost 1-Sum PBD

Unit mgkg

Mandels k statistics(Sludge 1 - Sum PBD)Mandels h statistics(Sludge 1 - Sum PBD)

Sample Sludge 1 Sludge 1 - Sum PBD -- Mean PARM = 0256 [mgkg]

Element Sum PBD

General calcparmT1= 531806E+00T2= 162188E+00T3= 22T4= 84T5= 25223E-02

n= variabelp= 6

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00423 0025 4 -156 044 Fail 00423 00252 4 3 -02146L 01808 0118 4 -049 205 - - 46L - - -0074L 01810 0056 4 -049 097 01810 00558 4 3 -007

38L 02168 0006 4 -022 010 02168 00059 4 3 -00412L 02890 0065 4 034 113 02890 00647 4 3 00364L 03958 0008 4 116 014 Fail 03958 00079 4 3 01426L 04094 0034 2 126 059 Fail 04094 00337 2 1 015

Totgem 0245 0044 mgkg 1-level 198 (179) 6 02557 (46L) 6 5Totstd= 0130 0039 5-level 171 (155) 1

RESULTS Mean = 025570 mgkg

Repeatability variance S2r = 000158Repeatability std Sr = 003970 --gt 1553 r = 01112Between lab variance S2L = 001807Reproducibility var S2R = 001964Reproducibility std SR = 014015 --gt 5481 R = 03924Remarks 1 Lab rejected (46L)

000 050 100 150 200 250

k-values

10L

46L

4L

38L

12L

64L

26L

Mandels k statistics(Sludge 1 - Sum PBD)

-03 -02 -02 -01 -01 00 01 01 02 02

Deviation from Mean

10L

46L

4L

38L

12L

64L

26L

Labo

rato

ries

Sludge 1 - Sum PBD -- Mean PARM = 0256 [mgkg]

-200 -100 000 100 200

h-values

10L

46L

4L

38L

12L

64L

26L

Labo

rato

ries

Mandels h statistics(Sludge 1 - Sum PBD)

Sludge 1-Sum PBD

Unit mgkg

Mandels k statistics(Soil 3 - Sum PBD)Mandels h statistics(Soil 3 - Sum PBD)

Sample Soil 3 Soil 3 - Sum PBD -- Mean PARM = 0227 [mgkg]

Element Sum PBD

General calcparmT1= 610980E+00T2= 200876E+00T3= 26T4= 100T5= 13106E-02

n= variabelp= 7

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00028 0001 4 -037 000 Fail 00028 00005 4 3 -02226L 01179 0021 2 -036 003 Fail 01179 00208 2 1 -0114L 01305 0031 4 -036 004 Fail 01305 00308 4 3 -010

46L 02065 0035 4 -036 005 Fail 02065 00350 4 3 -00244L 02923 0037 4 -035 005 Fail 02923 00365 4 3 00712L 04051 0015 4 -034 002 Fail 04051 00149 4 3 01864L 04314 0022 4 -033 003 Fail 04314 00223 4 3 0203L 305500 2051 2 247 283 Fail - - 3L - - 3032

Totgem 4017 0276 mgkg 1-level 206 (181) 7 02266 (3L) 7 6Totstd= 10722 0717 5-level 175 (156) 1

RESULTS Mean = 022663 mgkg

Repeatability variance S2r = 000069Repeatability std Sr = 002626 --gt 1159 r = 00735Between lab variance S2L = 002568Reproducibility var S2R = 002637Reproducibility std SR = 016238 --gt 7165 R = 04547Remarks 1 Lab rejected (3L)

000 050 100 150 200 250 300

k-values

10L

26L

4L

46L

44L

12L

64L

3L

Mandels k statistics(Soil 3 - Sum PBD)

-50 00 50 100 150 200 250 300 350

Deviation from Mean

10L

26L

4L

46L

44L

12L

64L

3L

Labo

rato

ries

Soil 3 - Sum PBD -- Mean PARM = 0227 [mgkg]

-100 000 100 200 300

h-values

10L

26L

4L

46L

44L

12L

64L

3L

Labo

rato

ries

Mandels h statistics(Soil 3 - Sum PBD)

Soil 3-Sum PBD

19

Annex 4

Raw data submitted

Sample Compost1 Sample Compost 1 Sample Compost 1Element PBD 99 Element PBD 100 Element PBD 153

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]4L 00021 10L 00008 44L 000504L 00024 10L 00008 44L 000604L 00014 10L 00007 44L 000504L 00020 10L 00011 46L 00004

10L 00029 46L 00007 46L 0001210L 00027 46L 00012 46L 0000410L 00032 46L 00009 46L 0000946L 00025 46L 00007 12L 0000446L 00052 12L 00008 12L 0000846L 00029 12L 00012 12L 0000446L 00026 12L 00008 12L 0000712L 00026 12L 00014 26L 0000512L 00043 26L 00007 26L 0000512L 00026 26L 0000612L 0004726L 0002626L 00024

Sample Compost 1 Sample Compost 1 Sample Compost 1Element PBD 154 Element PBD 183 Element PBD 196

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]4L 00010 46L 00002 46L 00011

46L 00003 46L 00024 46L 0000846L 00007 46L 00021 12L 0000246L 00003 46L 00003 12L 0000346L 00004 12L 00003 12L 0000112L 00003 12L 00011 12L 0000212L 00005 12L 0000312L 00031 12L 0000312L 00006

Sample Compost 1 Sample Compost 1 Sample Compost 1Element PBD 197 Element PBD 203 Element PBD 209

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00002 46L 00010 4L 0004146L 00023 12L 00002 4L 0008946L 00022 12L 00003 44L 0041012L 00004 12L 00002 44L 0084012L 00006 12L 00002 44L 0064012L 00003 44L 0040012L 00004 12L 00079

12L 0007312L 0006512L 0009326L 0004926L 00049

Sample Compost 1Element PBD 47

LAB PARM [mgkg]26L 0003826L 00039

Element PBD 99 Element PBD 47 Element PBD 209LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]

4L 00170 10L 00210 4L 010004L 00200 10L 00220 4L 018004L 00170 10L 00210 4L 012004L 00190 46L 00300 4L 0220010L 00280 46L 00280 46L 0210010L 00300 46L 00250 46L 0200010L 00290 46L 00260 64L 0351846L 00340 64L 00059 64L 0363846L 00330 64L 00057 64L 0364546L 00300 64L 00062 64L 0350846L 00310 64L 00060 12L 0220964L 00194 12L 00191 12L 0177164L 00154 12L 00187 12L 0292264L 00185 12L 00190 12L 0164664L 00159 12L 00186 26L 0329712L 00242 26L 00666 26L 0300012L 00223 26L 0033212L 0022112L 0022226L 0024626L 00400

Element PBD 203 Element PBD 197 Element PBD 196LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00022 46L 00027 46L 0002446L 00014 46L 00024 46L 0002264L 00036 12L 00161 64L 0005864L 00058 12L 00060 64L 0006512L 00063 12L 00061 12L 0004812L 00034 12L 00036 12L 0002512L 00038 12L 0003212L 00027 12L 00022

Element PBD 183 Element PBD 154 Element PBD 153LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00049 4L 00020 4L 0002246L 00035 4L 00022 4L 0002446L 00036 4L 00020 4L 0002246L 00034 46L 00025 4L 0002664L 00027 46L 00025 46L 0004064L 00023 46L 00025 46L 0004264L 00024 46L 00023 46L 0003564L 00020 64L 00034 46L 0003812L 00230 64L 00023 64L 0007412L 00032 64L 00017 64L 0004712L 00031 64L 00011 64L 0004612L 00030 12L 00030 64L 0003026L 00007 12L 00021 12L 0006526L 00008 12L 00021 12L 00029

12L 00021 12L 0003226L 00015 12L 0002926L 00019 26L 00039

26L 00040

Element PBD 100LAB PARM [mgkg]

4L 000384L 000414L 000374L 00038

38L 0219038L 0220038L 0208038L 0220010L 0004410L 0005010L 0004310L 0004646L 0005746L 0005946L 0005346L 0005312L 0004312L 0004512L 0004312L 0004326L 0006226L 00057

Sample Soil 3 Sample Soil 3 Sample Soil 3Element PBD 99 Element PBD 47 Element PBD 100

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]10L 00016 10L 00011 10L 0000310L 00019 10L 00010 10L 0000410L 00013 10L 00012 10L 0000410L 00019 46L 00007 10L 0000246L 00025 46L 00022 46L 0000246L 00025 46L 00005 46L 0000646L 00008 46L 00007 46L 0000246L 00011 12L 00010 46L 0000264L 00005 12L 00017 3L 29100064L 00005 12L 00010 3L 32000064L 00006 12L 00009 26L 0000564L 00007 26L 00007 26L 0000512L 00012 26L 0000712L 0001312L 0001312L 0001226L 0000526L 00006

Sample Soil 3 Sample Soil 3 Sample Soil 3Element PBD 153 Element PBD 154 Element PBD 196

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]44L 00050 4L 00010 46L 0000744L 00050 46L 00001 46L 0001146L 00002 46L 00002 46L 0000846L 00003 46L 00001 46L 0001146L 00002 46L 00002 64L 0002646L 00002 64L 00001 64L 0002664L 00001 64L 00001 64L 0002964L 00001 64L 00001 64L 0003464L 00001 64L 00002 12L 0004564L 00002 12L 00003 12L 00032

12L 00002 12L 0002212L 00002 12L 0002112L 00002

Sample Soil 3 Sample Soil 3 Sample Soil 3Element PBD 197 Element PBD 203 Element PBD 209

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00006 46L 00011 4L 0091046L 00013 46L 00017 4L 0150046L 00011 46L 00015 4L 0120046L 00013 46L 00018 4L 0160012L 00090 64L 00013 44L 0337012L 00056 64L 00014 44L 0281012L 00033 64L 00016 44L 0287012L 00032 64L 00015 44L 02540

12L 00055 46L 0230012L 00041 46L 0220012L 00027 46L 0150012L 00026 46L 01900

64L 0438164L 0401664L 0414464L 0449812L 0367112L 0397812L 0409112L 03838

Sample Soil 3 26L 0102Element PBD 183 26L 0131

LAB PARM [mgkg]46L 0000746L 0000846L 0005846L 0000764L 0000264L 0000364L 0000364L 0000312L 0001512L 0001112L 0000712L 00007

European Commission EUR 23003 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on polybrominated diphenylethers Author(s) E Sobiecka H van der Sloot D Barcelo B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 68 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07403-5 Abstract Project HORIZONTAL is interdisciplinary aiming at a harmonisation and horizontal standardisation of test procedures in particular for sludge soils and biowastes In the context of this standardization project a series of draft technical specification were designed upon an extensive desk study fine-tuned after expert consultations and finally validated in international intercomparisons exercise This report summarises the work performed within the validation study of the draft standard for the determination of polybrominated diphenylethers (PBDE) in soils sludge and treated bio-waste using gas-chromatography method with mass selective detection (GC-MS) It further explains the underlying statistical concept for the calculation of reproducibility and repeatability from intercomparisons data In addition all single values results of the statistical evaluation as well as background information on the validation materials used are described and explained

The mission of the JRC is to provide customer-driven scientific and technical support for the conception development implementation and monitoring of EU policies As a service of the European Commission the JRC functions as a reference centre of science and technology for the Union Close to the policy-making process it serves the common interest of the Member States while being independent of special interests whether private or national

LB

-NA

-23003-EN

-C

6

1 Introduction This report gives an overview on the available analytical information on the following raw materials to be used for the production of validation materials of the so-called Project HORIZONTAL

bull Four sludge materials from Duumlsseldorf Germany

bull An agricultural soil material from Reading United Kingdom

bull A compost material from Vienna Austria

bull A compost material from Korschenbroich Germany

bull A sludge-amended agricultural soil from Pavia Province Italy

bull A sludge-amended soil from Barcelona Spain

bull A sludge-amended soil from Essen Germany

bull A long-term sludge exposed soil from Hohenheim Germany

The following analytical information was gathered partly before and during the sampling of the raw materials to be used for the production of the HORIZONTAL validation materials The material were sampled by IES and shipped to IRMM in the course of the year 2005 The information gathered was then completed by various analytical screenings for PAHs and PCBs done by the Institute for Reference Materials and Measurements Geel Belgium for phthalates done by UBA Berlin Germany for PBDE done by IIQAB-CSIC Barcelona Spain for trace elements and some selected major and minor elements by the Institute for Environment and Sustainability Ispra Italy

The work compiled hereafter is based on the numerous additional efforts of the scientists working at various members of the consortium Project HORIZONTAL-Org and contributing organisations

This work is gratefully acknowledged

2 Overview on property values

21 Sludge materials from Duumlsseldorf Germany

The various sewage sludge materials originate from various installations in the North Rhine Westphalia and were produced and sampled by staff from the Landesumweltamt (LUA) NRW under the responsibility from Dr K Furtmann

In total four sludge materials (Sludge A and D from a major municipal WWTP Sludge B from a municipal WWTP with industrial input and Sludge C from a municipal WWTP with high PCB-Content) were obtained and will be blended to two final materials Before sampling the following analytical data for a typical sample were received

7

Table 1 ndash Analytical data obtained on an average sludge sample in LUA NRW (with courtesy of K Furtmann LUA Duumlsseldorf)

Parameter Concentration PCB 120 ugkg DEHP 110 mgkg PAH 5 mgkg (EPA) PCDDF 15 ng TEkg PBDE 400 ugkg NP 40 mgkg LAS 3 gkg AOX 300 mgkg

Subsequent screening led to the information displayed hereafter It should be stressed that the data were obtained as SCREENING information on the UNTREATED or partially treated raw materials Therefore the final target values which are relevant for the validation intercomparison can be different

Table 2 ndash Analytical data obtained on a first screening on the sludge samples from LUA NRW

Sewage sludge A

Dusseldorf

sewage sludge D

Dusseldorf PCB (ngg) 28 62 35 52 101 65 101 31 38 118 49 40 153 30 33 105 24 11 138 46 38 156 lt1 lt1 180 34 23 170 23 19 PAH (ngg) Naphtalene 34 381 Acenaphtylene 15 43 Acenaphthene 81 108 Fluorene 94 1167 Phenantrene 3440 Anthracene 22 344 Flouranthene 316 4817 Pyrene 235 3011 Benz(a)anthracene 473 791 Chrysene 691 1078 Benz(b)fluoranthene 538 1688 Benz(k)fluoranthene 228 635 Benz(a)pyrene 383 1114 Indeno(123-cd)pyrene 92 229 Dibenzo(ah)anthracene 71 70 Benzo(ghi)perylene 80 185

8

Table 3 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Sludge D (1) 0135 41474 385 Sludge B (2) 0538 0034 30634 547 Sludge A (3) 0184 0037 31399 146 Sludge C (4) 0354 1528 6678 229

Table 4 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Sludge 2

(B)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

554

959

694

591

772

509

nq

nq

970

2216

2379

Table 5 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena IES Ispra Spain) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Sludge 1 (D) 265 290 533 359 1231 338 784 438 lt 005 232 786 Sludge 2 (B) 119 311 626 202 278 299 722 251 lt 005 118 625 Sludge 3 (A) 168 360 621 332 847 416 119 451 lt 005 116 1237 Sludge 4 (C) 563 198 116 273 726 511 473 618 lt 005 444 2015

Table 6 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Sludge 1 (D) 2154 58 844 099 103 101 4367 lt15 50448 Sludge 2 (B) 1067 366 692 046 1491 077 5217 lt15 57633 Sludge 3 (A) 731 663 684 035 1287 068 3733 lt15 60369 Sludge 4 (C) 4379 965 527 163 522 107 5628 lt15 23945

Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM)Sludge 1 (D) 03 2403 101 1002 350 15 1944 132Sludge 2 (B) 031 315 97 879 172 12 514 180Sludge 3 (A) 031 1281 153 1567 265 16 1440 168Sludge 4 (C) 055 231 628 2625 371 81 1101 244

9

22 Agricultural soil material from Reading United Kingdom

The material was proposed by the University of Reading (S Nortcliff) and was sampled from a site called ldquoFrogmore Farmrdquo which was featured in the ldquoMetalsrdquo Report for HORIZONTAL This site is close to Reading with soils developed on flintyloamy periglacial materials over Chalk has a long and well documented history of sludge application The focus of the work of Nortcliff et al undertook at this site and the monitoring and control at the site (by Thames Water and the subsequent subsidiary bodies dealing with sludge application to soil) was on metals (and metal loads) with no analysis or indeed any form of investigation in to organics in the broadest sense

The analytical information produced in the context of the screening of the raw material is displayed below

Table 7 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 3

(Reading) 0032 0119 669

Table 8 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 3 (Reading) 015 706 279 138 152 901 267 300 lt 005 258 931

Table 9 ndash Analytical data obtained on a first screening on the sludge-amended soil from Reading (courtesy of IRMM)

Parameter Concentration

PCB ngg 28 lt1 52 lt1 101 lt1 118 lt1 153 lt1 105 lt1 138 lt1 156 lt1 180 lt1 170 lt1 PAH ngg Naphtalene lt10 Acenaphtylene 21 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene lt10 Flouranthene 818 Pyrene 776 Benz(a)anthracene 565

10

Parameter Concentration

Chrysene 608 Benz(b)fluoranthene 824 Benz(k)fluoranthene 329 Benz(a)pyrene 799 Indeno(123-cd)pyrene

779

Dibenzo(ah)anthracene 118 Benzo(ghi)perylene 394

Table 10 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 3

(Reading)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

103

003

nq

nq

nq

nd

nd

272

273

Table 11 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 3 (Reading) 015 706 279 138 152 901 267 300 lt 005 258 931

Table 12 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 3 (Reading) 7936 477 112 096 194 017 4107 443 2102 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 3 (Reading) 042 13 45 69 69 69 216 92

Table 13 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 3 (Reading) 012

11

23 Compost from Vienna Austria

The fresh compost material was obtained from the Austrian Federal Environment Agency (UBA Vienna) which had used a sub-batch of the raw material for national intercomparson The remainder of the material was stored at 4degC until shipment to IRMM for further processing The following analytical information was provided by UBA Austria and completed with various screenings

Table 14 ndash Analytical data on compost material received from UBA Austria Inorganic and sum parameters

Parameter Unit Sample fraction used Observed mean B CAT mgl FM Fresh sample lt10mm 61 K CAT mgl FM Fresh sample lt10mm 2624 Mg CAT mgl FM Fresh sample lt10mm 242 P CAT mgl FM Fresh sample lt10mm 49 B CAT DM Fresh sample lt10mm 00017 K CAT DM Fresh sample lt10mm 072 Mg CAT DM Fresh sample lt10mm 007 P CAT DM Fresh sample lt10mm 001 NO3-N mgkg FM Fresh sample lt10mm 35 NH4-N mgkg FM Fresh sample lt10mm 230 Ctotal DM lt45degdry milled 29 Corg DM lt45degdry milled 27 Ntotal DM lt45degdry milled 17 P mgkg DM lt45degdry milled 2596 K mgkg DM lt45degdry milled 11019 K DM lt45degdry milled 110 B mgkg DM lt45degdry milled 60 Cd mgkg DM lt45degdry milled 046 Cr mgkg DM lt45degdry milled 25 Cu mgkg DM lt45degdry milled 46 Hg mgkg DM lt45degdry milled 020 Ni mgkg DM lt45degdry milled 18 Pb mgkg DM lt45degdry milled 45 Zn mgkg DM lt45degdry milled 198 Ca mgkg DM lt45degdry milled 68776 Ca DM lt45degdry milled 69 Mo mgkg DM lt45degdry milled 08 S mgkg DM lt45degdry milled 2137 Fe mgkg DM lt45degdry milled 9959 Mn mgkg DM lt45degdry milled 418 Na mgkg DM lt45degdry milled 742 Co mgkg DM lt45degdry milled 41 AOX mgkg DM lt30deg dry milled 62

Table 15 ndash Analytical data on compost material received from UBA Austria Polycyclic aromatic hydrocarbons

PAH Unit Result Naphthaline microgkg DM 93 Acenaphthylene microgkg DM 86 Acenaphthene microgkg DM 5 Fluorene microgkg DM 80 Phenanthrene microgkg DM 89 Anthracene microgkg DM 27 Fluoranthene microgkg DM 487 Pyrene microgkg DM 380

12

PAH Unit Result Benzo(a)anthracene microgkg DM 278 Chrysene microgkg DM 317 Benzo(b)fluoranthene microgkg DM 365 Benzo(k)fluoranthene microgkg DM 193 Benz(a)pyrene microgkg DM 320 Indeno(123-cd)pyrene microgkg DM 233 Dibenz(ah)anthracene microgkg DM 67 Benzo(ghi)perylene microgkg DM 225 Sum EPA microgkg DM 3013 Sum EPA mgkg DM 30

Table 16 ndash Analytical data on compost material received from UBA Austria Sum PCDDs and PCBs

Parameter

Dioxine TEQ (ITEF) ngkg DM 73 TEQ (WHO) ngkg DM 35 PCB Σ Ballschmiter mgkg DM 005

Table 17 ndash Analytical data on compost material obtained by screening in IRMM

Parameter Result in ngg

PCB 28 2 52 2 101 4 118 3 153 10 105 1 138 8 156 1 180 5 170 lt1 PAH Naphtalene lt10 Acenaphtylene lt10 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene 26 Fluoranthene 611 Pyrene 510 Benz(a)anthracene 888 Chrysene 957 Benz(b)fluoranthene 1531 Benz(k)fluoranthene 547 Benz(a)pyrene 1101 Indeno(123-cd)pyrene 416 Dibenzo(ah)anthracene 81 Benzo(ghi)perylene 295

13

Table 18 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Compost 1

(Vienna)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

402

019

259

nq

023

004

nq

nq

144

174

259

Table 19 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Compost 1

(Vienna) 0058 1426 557

Table 20 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Compost 1 (Vienna) 039 736 319 410 365 127 495 004 079 013 208

Table 21 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Compost 1 (Vienna) 2063 431 617 426 199 249 1602 lt15 10521

Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Compost 1 (Vienna) 035 3496 81 375 79 55 653 60

Table 22 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Compost 1 (Vienna) 017

14

24 Agricultural soil sludge amended soil from Pavia Italy

This sludge-amended soil material was obtained during a monitoring campaign which aimed at a generic description of the over-all soil quality in Pavia Province Italy The material which was collected from the upper horizon originates from a small farm called ldquoCascina Novellordquo During the characterisation of the site the following analytical information was obtained on a pooled sample of a sub-area of the farm of 20 X 20 m2

Table 23 ndash Analytical data on Pavia soil

Parameter Result Al 713 Wgt As 224 mgkg Cd 079 mgkg Cr 59 mgkg Cu 308 mgkg Hg 008 mgkg Ni 344 mgkg Pb 246 mgkg Zn 95 mgkg C 091 Wgt 2378-TCDD 0047 pgg 12378-PeCDD 015 pgg 123478-HxCDD 019 pgg 123678-HxCDD 15 pgg 123789-HxCDD 074 pgg 1234678-HpCDD 26 pgg OCDD 382 pgg 2378-TCDF 068 pgg 12378-PeCDF 053 pgg 23478-PeCDF 071 pgg 123478-HxDF 100 pgg 123678-HxDF 066 pgg 234678-HxDF 16 pgg 123789-HxDF 027 pgg 1234678-HpDF 12 pgg 1234789-HpDF 068 pgg OCDF 33 pgg I-TEQ 20 pgg WHO-TEQ 17 pgg

In addition the screening performed at IRMM did not reveal significant quantities of PCBs and PAHs which were all below the LoDs (1 ngg for PCBs and 10 ngg for PAHs respectively)

Table 24 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 5 (Pavia) 0005 0011 154

15

Table 25 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 5

(Pavia)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

039

nq

nq

008

nq

nd

nd

670

671

Table 26 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 5 (Pavia) 033 184 573 225 426 305 206 200 lt 005 381 878

Table 27 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 5 (Pavia) 6939 129 145 224 425 116 6118 255 1789 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 5 (Pavia) 184 62 38 108 55 66 597 110

Table 28 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 5 (Pavia) 006

16

25 Sludge-amended-soil from Barcelona Spain

The sludge-amended soil material from Barcelona sampled upon indication from the Barcelorsquo- Group in Barcelona

Table 29 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 2 (Lleida T) 0015 0183 1138

Table 30 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 2

(Lleida T)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

159

045

nq

048

160

nq

nq

1000

1004

Table 31 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 2 (Lleida T) 059 141 327 536 405 186 184 224 lt 005 318 111

Table 32 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 2 (Lleida T) 4443 1067 1429 253 344 204 4116 780 3396 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 2 (Lleida T) 064 65 26 125 59 17 547 65

Table 33 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 2 (Lleida T) 010

17

26 Sludge amended soil from Essen Germany

The German sludge-amended soil from Essen which was provided as the three sludge materials by LUA NRW did not feature significant concentrations of the PCB congeners 28 52 101 118 153 105 138 156 180 170 but had detectable amounts of some PAHs

Table 34 ndash Analytical screening data on the German sludge-amended soil

Parameter Concentration(ngg)

Naphtalene lt10 Acenaphtylene lt10 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene lt10 Fluoranthene 28 Pyrene 20 Benz(a)anthracene 24 Chrysene 47 Benz(b)fluoranthene 76 Benz(k)fluoranthene 20 Benz(a)pyrene 35 Indeno(123-cd)pyrene 35 Dibenzo(ah)anthracene 10 Benzo(ghi)perylene 26

Table 35 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 4 (Essen) 0011 0302 055

Table 36 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 4

(Essen)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

nq

nq

nq

nq

nq

nq

128

191

203

18

Table 37 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 4 (Essen) 052 545 261 805 320 403 273 273 lt 005 295 781

Table 38 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 4 (Essen) 7947 442 085 06 086 007 2163 189 2019 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 4 (Essen) 045 19 42 87 683 60 462 61

Table 39 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 4 (Essen) 004

27 Long-term sludge exposed soil from Hohenheim-Stuttgart Germany

Similarly an additional sludge exposed soil was sampled at the University of Hohenheim Stuttgart were a test soil was long-term exposed to elevated concentrations of sewage sludge

Table 40 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 1 (Stuttgart) 0045 0263 1765

Table 41 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 1

(Stuttgart)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

230

006

004

004

nq

nd

nd

498

500

19

Table 42 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 1 (Stuttgart) 069 127 361 262 504 183 252 262 lt 005 266 142

Table 43 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 1 (Stuttgart) 7194 1006 133 186 366 088 7874 275 3571 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 1 (Stuttgart) 123 50 47 212 85 69 991 129

Table 44 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 1 (Stuttgart) 177

18

Annex 3

Statistical calculations

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 47)Mandels h statistics(Sludge 1 - PBD 47)

Sample Sludge 1 NUM

Element PBD 47

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00213 0001 3 -021 005 - - 10L - - NUM46L 00273 0002 4 016 021 - - 46L - - NUM64L 00059 0000 4 -116 002 NUM - 64L - - NUM12L 00188 0000 4 -036 002 - - 12L - - NUM26L 00499 0024 2 157 223 Fail - - 26L - - NUM

Totgem 0025 0005 mgkg 1-level 172 (185) NUM (10L46L64L12L26L) -1Totstd= 0016 0010 5-level 157 (162) 5

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 5 Labs rejected (10L46L64L12L26L)

000 050 100 150 200 250

k-values

10L

46L

64L

12L

26L

Mandels k statistics(Sludge 1 - PBD 47)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

10L

46L

64L

12L

26L

Labo

rato

ries

NUM

-200 -100 000 100 200

h-values

10L

46L

64L

12L

26L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 47)

Sludge 1-PBD 47

Unit mgkg

Mandels k statistics(Soil 3 - PBD 47)Mandels h statistics(Soil 3 - PBD 47)

Sample Soil 3 Soil 3 - PBD 47 -- Mean PARM = 0001 [mgkg]

Element PBD 47

General calcparmT1= 134814E-02T2= 142830E-05T3= 13T4= 45T5= 22767E-06

n= variabelp= 4

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean26L 00007 0000 2 -143 001 00007 00000 2 1 00046L 00010 0001 4 010 181 00010 00008 4 3 00010L 00011 0000 3 049 023 00011 00001 3 2 00012L 00012 0000 4 084 081 00012 00004 4 3 000

Totgem 0001 0000 mgkg 1-level 149 (177) 4 00010 () 4 3Totstd= 0000 0000 5-level 142 (159)

RESULTS Mean = 000100 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000050 --gt 5031 r = 00014Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000050 --gt 5031 R = 00014Remarks none

000 050 100 150 200

k-values

26L

46L

10L

12L

Mandels k statistics(Soil 3 - PBD 47)

00 00 00 00 00 00 00 00 00 00 00

Deviation from Mean

26L

46L

10L

12L

Labo

rato

ries

Soil 3 - PBD 47 -- Mean PARM = 0001 [mgkg]

-200 -100 000 100

h-values

26L

46L

10L

12L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 47)

Soil 3-PBD 47

Unit mgkg

Mandels k statistics(Compost 1 - PBD 99)Mandels h statistics(Compost 1 - PBD 99)

Sample Compost 1 Compost 1 - PBD 99 -- Mean PARM = 0003 [mgkg]

Element PBD 99

General calcparmT1= 492124E-02T2= 148747E-04T3= 17T4= 61T5= 93196E-06

n= variabelp= 5

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00020 0000 4 -137 053 00020 00004 4 3 000

26L 00025 0000 2 -058 024 00025 00002 2 1 00010L 00029 0000 3 012 032 00029 00003 3 2 00046L 00033 0001 4 069 161 00033 00013 4 3 00012L 00036 0001 4 114 140 00036 00011 4 3 000

Totgem 0003 0001 mgkg 1-level 172 (185) 5 00029 () 5 4Totstd= 0001 0001 5-level 157 (162)

RESULTS Mean = 000286 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000088 --gt 3086 r = 00025Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000101 --gt 3525 R = 00028Remarks none

000 050 100 150 200

k-values

4L

26L

10L

46L

12L

Mandels k statistics(Compost 1 - PBD 99)

00 00 00 00 00 00 00 00 00 00

Deviation from Mean

4L

26L

10L

46L

12L

Labo

rato

ries

Compost 1 - PBD 99 -- Mean PARM = 0003 [mgkg]

-200 -100 000 100 200

h-values

4L

26L

10L

46L

12L

Labo

rato

ries

Mandels h statistics(Compost 1 - PBD 99)

Compost 1-PBD 99

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 99)Mandels h statistics(Sludge 1 - PBD 99)

Sample Sludge 1 Sludge 1 - PBD 99 -- Mean PARM = 0024 [mgkg]

Element PBD 99

General calcparmT1= 448050E-01T2= 112113E-02T3= 19T4= 73T5= 32972E-05

n= variabelp= 5

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean64L 00173 0002 4 -118 041 Fail 00173 00019 4 3 -0014L 00183 0002 4 -104 032 00183 00015 4 3 -001

12L 00227 0001 4 -038 022 00227 00010 4 3 00010L 00290 0001 3 055 021 00290 00010 3 2 00146L 00320 0002 4 100 039 00320 00018 4 3 00126L 00323 0011 2 105 234 - - 26L - - 001

Totgem 0025 0003 mgkg 1-level 187 (177) 5 00239 (26L) 5 4Totstd= 0007 0004 5-level 166 (154) 1

RESULTS Mean = 002385 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000153 --gt 643 r = 00043Between lab variance S2L = 000004Reproducibility var S2R = 000004Reproducibility std SR = 000666 --gt 2791 R = 00186Remarks 1 Lab rejected (26L)

000 050 100 150 200 250

k-values

64L

4L

12L

10L

46L

26L

Mandels k statistics(Sludge 1 - PBD 99)

00 00 00 00 00 00 00 00 00 00

Deviation from Mean

64L

4L

12L

10L

46L

26L

Labo

rato

ries

Sludge 1 - PBD 99 -- Mean PARM = 0024 [mgkg]

-200 -100 000 100 200

h-values

64L

4L

12L

10L

46L

26L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 99)

Sludge 1-PBD 99

Unit mgkg

Mandels k statistics(Soil 3 - PBD 99)Mandels h statistics(Soil 3 - PBD 99)

Sample Soil 3 NUM

Element PBD 99

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00017 0000 4 091 068 - - 10L - - NUM46L 00017 0001 4 100 211 - - 46L - - NUM64L 00005 0000 4 -106 023 NUM - 64L - - NUM12L 00012 0000 4 015 014 - - 12L - - NUM26L 00006 0000 2 -101 012 - - 26L - - NUM

Totgem 0001 0000 mgkg 1-level 172 (173) NUM (10L46L64L12L26L) -1Totstd= 0001 0000 5-level 157 (153) 5

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 5 Labs rejected (10L46L64L12L26L)

000 050 100 150 200 250

k-values

10L

46L

64L

12L

26L

Mandels k statistics(Soil 3 - PBD 99)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

10L

46L

64L

12L

26L

Labo

rato

ries

NUM

-200 -100 000 100 200

h-values

10L

46L

64L

12L

26L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 99)

Soil 3-PBD 99

Unit mgkg

Mandels k statistics(Compost 1 - PBD 100)Mandels h statistics(Compost 1 - PBD 100)

Sample Compost 1 Compost 1 - PBD 100 -- Mean PARM = 0001 [mgkg]

Element PBD 100

General calcparmT1= 124272E-02T2= 113129E-05T3= 14T4= 52T5= 46584E-07

n= variabelp= 4

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean26L 00006 0000 2 -131 037 Fail 00006 00001 2 1 00010L 00009 0000 4 003 083 00009 00002 4 3 00046L 00009 0000 4 016 115 00009 00002 4 3 00012L 00011 0000 4 112 136 Fail 00011 00003 4 3 000

Totgem 0001 0000 mgkg 1-level 149 (167) 4 00009 () 4 3Totstd= 0000 0000 5-level 142 (15)

RESULTS Mean = 000085 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000022 --gt 2531 r = 00006Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000025 --gt 2882 R = 00007Remarks none

000 050 100 150

k-values

26L

10L

46L

12L

Mandels k statistics(Compost 1 - PBD 100)

00 00 00 00 00 00 00 00 00 00 00

Deviation from Mean

26L

10L

46L

12L

Labo

rato

ries

Compost 1 - PBD 100 -- Mean PARM = 0001 [mgkg]

-200 -100 000 100 200

h-values

26L

10L

46L

12L

Labo

rato

ries

Mandels h statistics(Compost 1 - PBD 100)

Compost 1-PBD 100

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 100)Mandels h statistics(Sludge 1 - PBD 100)

Sample Sludge 1 Sludge 1 - PBD 100 -- Mean PARM = 0005 [mgkg]

Element PBD 100

General calcparmT1= 852065E-02T2= 412762E-04T3= 18T4= 68T5= 78914E-07

n= variabelp= 5

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00039 0000 4 -042 007 Fail 00039 00002 4 3 000

12L 00044 0000 4 -041 005 Fail 00044 00001 4 3 00010L 00046 0000 4 -041 013 Fail 00046 00003 4 3 00046L 00056 0000 4 -040 012 Fail 00056 00003 4 3 00026L 00059 0000 2 -040 013 Fail 00059 00003 2 1 00038L 02168 0006 4 204 244 Fail - - 38L - - 021

Totgem 0040 0001 mgkg 1-level 187 (177) 5 00049 (38L) 5 4Totstd= 0087 0002 5-level 166 (154) 1

RESULTS Mean = 000486 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000025 --gt 507 r = 00007Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000084 --gt 1731 R = 00024Remarks 1 Lab rejected (38L)

000 050 100 150 200 250

k-values

4L

12L

10L

46L

26L

38L

Mandels k statistics(Sludge 1 - PBD 100)

-01 00 01 01 02 02 03

Deviation from Mean

4L

12L

10L

46L

26L

38L

Labo

rato

ries

Sludge 1 - PBD 100 -- Mean PARM = 0005 [mgkg]

-100 000 100 200 300

h-values

4L

12L

10L

46L

26L

38L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 100)

Sludge 1-PBD 100

Unit mgkg

Mandels k statistics(Soil 3 - PBD 100)Mandels h statistics(Soil 3 - PBD 100)

Sample Soil 3 NUM

Element PBD 100

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00003 0000 4 -050 000 Fail - - 10L - - NUM46L 00003 0000 4 -050 000 Fail NUM - 46L - - NUM3L 305500 2051 2 150 200 Fail - - 3L - - NUM

26L 00005 0000 2 -050 000 Fail - - 26L - - NUM

Totgem 7638 0513 mgkg 1-level 149 (177) NUM (10L46L3L26L) -1Totstd= 15275 1025 5-level 142 (159) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (10L46L3L26L)

000 050 100 150 200

k-values

10L

46L

3L

26L

Mandels k statistics(Soil 3 - PBD 100)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

10L

46L

3L

26L

Labo

rato

ries

NUM

-100 000 100 200

h-values

10L

46L

3L

26L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 100)

Soil 3-PBD 100

Unit mgkg

Mandels k statistics(Compost 1 - PBD 153)Mandels h statistics(Compost 1 - PBD 153)

Sample Compost 1 NUM

Element PBD 153

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean44L 00053 0001 3 150 157 Fail - - 44L - - NUM46L 00007 0000 4 -044 111 Fail - - 46L - - NUM12L 00005 0000 4 -051 055 Fail - - 12L - - NUM26L 00005 0000 2 -054 001 Fail NUM - 26L - - NUM

Totgem 0002 0000 mgkg 1-level 149 (177) NUM (44L46L12L26L) -1Totstd= 0002 0000 5-level 142 (159) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (44L46L12L26L)

000 050 100 150 200

k-values

44L

46L

12L

26L

Mandels k statistics(Compost 1 - PBD 153)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

44L

46L

12L

26L

Labo

rato

ries

NUM

-100 000 100 200

h-values

44L

46L

12L

26L

Labo

rato

ries

Mandels h statistics(Compost 1 - PBD 153)

Compost 1-PBD 153

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 153)Mandels h statistics(Sludge 1 - PBD 153)

Sample Sludge 1 Sludge 1 - PBD 153 -- Mean PARM = 0004 [mgkg]

Element PBD 153

General calcparmT1= 676738E-02T2= 267609E-04T3= 18T4= 68T5= 19626E-05

n= variabelp= 5

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00024 0000 4 -157 017 00024 00002 4 3 000

12L 00038 0002 4 006 154 00038 00018 4 3 00046L 00039 0000 4 011 026 00039 00003 4 3 00026L 00039 0000 2 018 004 00039 00000 2 1 00064L 00049 0002 4 122 159 00049 00018 4 3 000

Totgem 0004 0001 mgkg 1-level 172 (173) 5 00038 () 5 4Totstd= 0001 0001 5-level 157 (153)

RESULTS Mean = 000378 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000123 --gt 3252 r = 00034Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000142 --gt 3754 R = 00040Remarks none

000 050 100 150 200

k-values

4L

12L

46L

26L

64L

Mandels k statistics(Sludge 1 - PBD 153)

00 00 00 00 00 00 00

Deviation from Mean

4L

12L

46L

26L

64L

Labo

rato

ries

Sludge 1 - PBD 153 -- Mean PARM = 0004 [mgkg]

-200 -100 000 100 200

h-values

4L

12L

46L

26L

64L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 153)

Sludge 1-PBD 153

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 154)Mandels h statistics(Sludge 1 - PBD 154)

Sample Sludge 1 NA

Element PBD 154

General calcparmT1= NAT2= NAT3=T4=T5=

n= variabelp=

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00021 0000 3 -100 021 NA - 4L - - NA

46L 00025 0000 4 115 018 NA - 46L - - NA64L 00021 0001 4 -066 179 - - 64L - - NA12L 00023 0000 4 050 085 - - 12L - - NA

Totgem 0002 0000 mgkg 1-level 149 (167) NA (4L46L64L12L) -1Totstd= 0000 0000 5-level 142 (15) 4

RESULTS Mean = NA mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NAReproducibility var S2R = NAReproducibility std SR = NA --gt NA R = NARemarks 4 Labs rejected (4L46L64L12L)

000 050 100 150 200

k-values

4L

46L

64L

12L

Mandels k statistics(Sludge 1 - PBD 154)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

4L

46L

64L

12L

Labo

rato

ries

NA

-100 000 100 200

h-values

4L

46L

64L

12L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 154)

Sludge 1-PBD 154

Unit mgkg

Mandels k statistics(Soil 3 - PBD 154)Mandels h statistics(Soil 3 - PBD 154)

Sample Soil 3 NUM

Element PBD 154

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

4L 00010 - 1 150 Fail - - 4L - - NUM46L 00001 0000 4 -053 096 Fail - - 46L - - NUM64L 00001 0000 4 -056 105 Fail NUM - 64L - - NUM12L 00002 0000 4 -040 099 Fail - - 12L - - NUM

Totgem 000037 0000 mgkg 1-level 149 (164) NUM (4L46L64L12L) -1Totstd= 000042 0000 5-level 142 (153) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (4L46L64L12L)

000 050 100 150

k-values

4L

46L

64L

12L

Mandels k statistics(Soil 3 - PBD 154)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

4L

46L

64L

12L

Labo

rato

ries

NUM

-100 000 100 200

h-values

4L

46L

64L

12L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 154)

Soil 3-PBD 154

Unit mgkg

Mandels k statistics(Compost 1 - PBD 209)Mandels h statistics(Compost 1 - PBD 209)

Sample Compost 1 NUM

Element PBD 209

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00065 0003 2 -049 032 - - 4L - - NUM

44L 00573 0021 4 150 197 Fail - - 44L - - NUM12L 00078 0001 4 -045 011 - - 12L - - NUM26L 00049 0000 2 -056 000 NUM - 26L - - NUM

Totgem 0019 0006 mgkg 1-level 149 (177) NUM (4L44L12L26L) -1Totstd= 0025 0010 5-level 142 (159) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (4L44L12L26L)

000 050 100 150 200

k-values

4L

44L

12L

26L

Mandels k statistics(Compost 1 - PBD 209)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

4L

44L

12L

26L

Labo

rato

ries

NUM

-100 000 100 200

h-values

4L

44L

12L

26L

Labo

rato

ries

Mandels h statistics(Compost 1 - PBD 209)

Compost 1-PBD 209

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 209)Mandels h statistics(Sludge 1 - PBD 209)

Sample Sludge 1 Sludge 1 - PBD 209 -- Mean PARM = 0249 [mgkg]

Element PBD 209

General calcparmT1= 394542E+00T2= 107296E+00T3= 16T4= 56T5= 19723E-02

n= variabelp= 5

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 01550 0055 4 -112 148 Fail 01550 00551 4 3 -009

46L 02050 0007 2 -053 019 02050 00071 2 1 -00412L 02137 0058 4 -042 155 02137 00576 4 3 -00426L 03149 0021 2 078 057 Fail 03149 00210 2 1 00764L 03577 0007 4 129 020 Fail 03577 00074 4 3 011

Totgem 0249 0030 mgkg 1-level 172 (185) 5 02493 () 5 4Totstd= 0084 0025 5-level 157 (162)

RESULTS Mean = 024926 mgkg

Repeatability variance S2r = 000179Repeatability std Sr = 004234 --gt 1699 r = 01186Between lab variance S2L = 000743Reproducibility var S2R = 000922Reproducibility std SR = 009604 --gt 3853 R = 02689Remarks none

000 050 100 150 200

k-values

4L

46L

12L

26L

64L

Mandels k statistics(Sludge 1 - PBD 209)

-01 -01 00 01 01 02

Deviation from Mean

4L

46L

12L

26L

64L

Labo

rato

ries

Sludge 1 - PBD 209 -- Mean PARM = 0249 [mgkg]

-200 -100 000 100 200

h-values

4L

46L

12L

26L

64L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 209)

Sludge 1-PBD 209

Unit mgkg

Mandels k statistics(Soil 3 - PBD 209)Mandels h statistics(Soil 3 - PBD 209)

Sample Soil 3 Soil 3 - PBD 209 -- Mean PARM = 0258 [mgkg]

Element PBD 209

General calcparmT1= 596398E+00T2= 191917E+00T3= 22T4= 84T5= 13249E-02

n= variabelp= 6

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean26L 01162 0021 2 -108 074 Fail 01162 00207 2 1 -0144L 01303 0031 4 -097 111 Fail 01303 00312 4 3 -013

46L 01975 0036 4 -046 128 Fail 01975 00359 4 3 -00644L 02898 0035 4 024 124 Fail 02898 00346 4 3 00312L 03895 0018 4 100 065 Fail 03895 00181 4 3 01364L 04260 0022 4 127 078 Fail 04260 00219 4 3 017

Totgem 0258 0027 mgkg 1-level 187 (177) 6 02582 () 6 5Totstd= 0132 0008 5-level 166 (154)

RESULTS Mean = 025818 mgkg

Repeatability variance S2r = 000083Repeatability std Sr = 002878 --gt 1115 r = 00806Between lab variance S2L = 001640Reproducibility var S2R = 001723Reproducibility std SR = 013127 --gt 5084 R = 03676Remarks none

000 050 100 150

k-values

26L

4L

46L

44L

12L

64L

Mandels k statistics(Soil 3 - PBD 209)

-02 -01 -01 00 01 01 02 02

Deviation from Mean

26L

4L

46L

44L

12L

64L

Labo

rato

ries

Soil 3 - PBD 209 -- Mean PARM = 0258 [mgkg]

-200 -100 000 100 200

h-values

26L

4L

46L

44L

12L

64L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 209)

Soil 3-PBD 209

Unit mgkg

Mandels k statistics(Compost 1 - Sum PBD)Mandels h statistics(Compost 1 - Sum PBD)

Sample Compost 1 Compost 1 - Sum PBD -- Mean PARM = 0009 [mgkg]

Element Sum PBD

General calcparmT1= 154064E-01T2= 169065E-03T3= 18T4= 68T5= 11354E-04

n= variabelp= 5

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00031 0002 4 -067 016 00031 00016 4 3 -0014L 00055 0005 4 -056 048 00055 00047 4 3 000

46L 00085 0003 4 -042 031 00085 00030 4 3 00026L 00123 0000 2 -024 003 00123 00002 2 1 00012L 00154 0002 4 -011 021 00154 00021 4 3 00144L 00613 0023 4 200 237 Fail - - 44L - - 005

Totgem 0018 0006 mgkg 1-level 187 (177) 5 00089 (44L) 5 4Totstd= 0022 0009 5-level 166 (154) 1

RESULTS Mean = 000893 mgkg

Repeatability variance S2r = 000001Repeatability std Sr = 000296 --gt 3308 r = 00083Between lab variance S2L = 000002Reproducibility var S2R = 000003Reproducibility std SR = 000570 --gt 6374 R = 00159Remarks 1 Lab rejected (44L)

000 050 100 150 200 250

k-values

10L

4L

46L

26L

12L

44L

Mandels k statistics(Compost 1 - Sum PBD)

00 00 00 00 00 00 01 01

Deviation from Mean

10L

4L

46L

26L

12L

44L

Labo

rato

ries

Compost 1 - Sum PBD -- Mean PARM = 0009 [mgkg]

-100 000 100 200

h-values

10L

4L

46L

26L

12L

44L

Labo

rato

ries

Mandels h statistics(Compost 1 - Sum PBD)

Compost 1-Sum PBD

Unit mgkg

Mandels k statistics(Sludge 1 - Sum PBD)Mandels h statistics(Sludge 1 - Sum PBD)

Sample Sludge 1 Sludge 1 - Sum PBD -- Mean PARM = 0256 [mgkg]

Element Sum PBD

General calcparmT1= 531806E+00T2= 162188E+00T3= 22T4= 84T5= 25223E-02

n= variabelp= 6

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00423 0025 4 -156 044 Fail 00423 00252 4 3 -02146L 01808 0118 4 -049 205 - - 46L - - -0074L 01810 0056 4 -049 097 01810 00558 4 3 -007

38L 02168 0006 4 -022 010 02168 00059 4 3 -00412L 02890 0065 4 034 113 02890 00647 4 3 00364L 03958 0008 4 116 014 Fail 03958 00079 4 3 01426L 04094 0034 2 126 059 Fail 04094 00337 2 1 015

Totgem 0245 0044 mgkg 1-level 198 (179) 6 02557 (46L) 6 5Totstd= 0130 0039 5-level 171 (155) 1

RESULTS Mean = 025570 mgkg

Repeatability variance S2r = 000158Repeatability std Sr = 003970 --gt 1553 r = 01112Between lab variance S2L = 001807Reproducibility var S2R = 001964Reproducibility std SR = 014015 --gt 5481 R = 03924Remarks 1 Lab rejected (46L)

000 050 100 150 200 250

k-values

10L

46L

4L

38L

12L

64L

26L

Mandels k statistics(Sludge 1 - Sum PBD)

-03 -02 -02 -01 -01 00 01 01 02 02

Deviation from Mean

10L

46L

4L

38L

12L

64L

26L

Labo

rato

ries

Sludge 1 - Sum PBD -- Mean PARM = 0256 [mgkg]

-200 -100 000 100 200

h-values

10L

46L

4L

38L

12L

64L

26L

Labo

rato

ries

Mandels h statistics(Sludge 1 - Sum PBD)

Sludge 1-Sum PBD

Unit mgkg

Mandels k statistics(Soil 3 - Sum PBD)Mandels h statistics(Soil 3 - Sum PBD)

Sample Soil 3 Soil 3 - Sum PBD -- Mean PARM = 0227 [mgkg]

Element Sum PBD

General calcparmT1= 610980E+00T2= 200876E+00T3= 26T4= 100T5= 13106E-02

n= variabelp= 7

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00028 0001 4 -037 000 Fail 00028 00005 4 3 -02226L 01179 0021 2 -036 003 Fail 01179 00208 2 1 -0114L 01305 0031 4 -036 004 Fail 01305 00308 4 3 -010

46L 02065 0035 4 -036 005 Fail 02065 00350 4 3 -00244L 02923 0037 4 -035 005 Fail 02923 00365 4 3 00712L 04051 0015 4 -034 002 Fail 04051 00149 4 3 01864L 04314 0022 4 -033 003 Fail 04314 00223 4 3 0203L 305500 2051 2 247 283 Fail - - 3L - - 3032

Totgem 4017 0276 mgkg 1-level 206 (181) 7 02266 (3L) 7 6Totstd= 10722 0717 5-level 175 (156) 1

RESULTS Mean = 022663 mgkg

Repeatability variance S2r = 000069Repeatability std Sr = 002626 --gt 1159 r = 00735Between lab variance S2L = 002568Reproducibility var S2R = 002637Reproducibility std SR = 016238 --gt 7165 R = 04547Remarks 1 Lab rejected (3L)

000 050 100 150 200 250 300

k-values

10L

26L

4L

46L

44L

12L

64L

3L

Mandels k statistics(Soil 3 - Sum PBD)

-50 00 50 100 150 200 250 300 350

Deviation from Mean

10L

26L

4L

46L

44L

12L

64L

3L

Labo

rato

ries

Soil 3 - Sum PBD -- Mean PARM = 0227 [mgkg]

-100 000 100 200 300

h-values

10L

26L

4L

46L

44L

12L

64L

3L

Labo

rato

ries

Mandels h statistics(Soil 3 - Sum PBD)

Soil 3-Sum PBD

19

Annex 4

Raw data submitted

Sample Compost1 Sample Compost 1 Sample Compost 1Element PBD 99 Element PBD 100 Element PBD 153

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]4L 00021 10L 00008 44L 000504L 00024 10L 00008 44L 000604L 00014 10L 00007 44L 000504L 00020 10L 00011 46L 00004

10L 00029 46L 00007 46L 0001210L 00027 46L 00012 46L 0000410L 00032 46L 00009 46L 0000946L 00025 46L 00007 12L 0000446L 00052 12L 00008 12L 0000846L 00029 12L 00012 12L 0000446L 00026 12L 00008 12L 0000712L 00026 12L 00014 26L 0000512L 00043 26L 00007 26L 0000512L 00026 26L 0000612L 0004726L 0002626L 00024

Sample Compost 1 Sample Compost 1 Sample Compost 1Element PBD 154 Element PBD 183 Element PBD 196

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]4L 00010 46L 00002 46L 00011

46L 00003 46L 00024 46L 0000846L 00007 46L 00021 12L 0000246L 00003 46L 00003 12L 0000346L 00004 12L 00003 12L 0000112L 00003 12L 00011 12L 0000212L 00005 12L 0000312L 00031 12L 0000312L 00006

Sample Compost 1 Sample Compost 1 Sample Compost 1Element PBD 197 Element PBD 203 Element PBD 209

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00002 46L 00010 4L 0004146L 00023 12L 00002 4L 0008946L 00022 12L 00003 44L 0041012L 00004 12L 00002 44L 0084012L 00006 12L 00002 44L 0064012L 00003 44L 0040012L 00004 12L 00079

12L 0007312L 0006512L 0009326L 0004926L 00049

Sample Compost 1Element PBD 47

LAB PARM [mgkg]26L 0003826L 00039

Element PBD 99 Element PBD 47 Element PBD 209LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]

4L 00170 10L 00210 4L 010004L 00200 10L 00220 4L 018004L 00170 10L 00210 4L 012004L 00190 46L 00300 4L 0220010L 00280 46L 00280 46L 0210010L 00300 46L 00250 46L 0200010L 00290 46L 00260 64L 0351846L 00340 64L 00059 64L 0363846L 00330 64L 00057 64L 0364546L 00300 64L 00062 64L 0350846L 00310 64L 00060 12L 0220964L 00194 12L 00191 12L 0177164L 00154 12L 00187 12L 0292264L 00185 12L 00190 12L 0164664L 00159 12L 00186 26L 0329712L 00242 26L 00666 26L 0300012L 00223 26L 0033212L 0022112L 0022226L 0024626L 00400

Element PBD 203 Element PBD 197 Element PBD 196LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00022 46L 00027 46L 0002446L 00014 46L 00024 46L 0002264L 00036 12L 00161 64L 0005864L 00058 12L 00060 64L 0006512L 00063 12L 00061 12L 0004812L 00034 12L 00036 12L 0002512L 00038 12L 0003212L 00027 12L 00022

Element PBD 183 Element PBD 154 Element PBD 153LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00049 4L 00020 4L 0002246L 00035 4L 00022 4L 0002446L 00036 4L 00020 4L 0002246L 00034 46L 00025 4L 0002664L 00027 46L 00025 46L 0004064L 00023 46L 00025 46L 0004264L 00024 46L 00023 46L 0003564L 00020 64L 00034 46L 0003812L 00230 64L 00023 64L 0007412L 00032 64L 00017 64L 0004712L 00031 64L 00011 64L 0004612L 00030 12L 00030 64L 0003026L 00007 12L 00021 12L 0006526L 00008 12L 00021 12L 00029

12L 00021 12L 0003226L 00015 12L 0002926L 00019 26L 00039

26L 00040

Element PBD 100LAB PARM [mgkg]

4L 000384L 000414L 000374L 00038

38L 0219038L 0220038L 0208038L 0220010L 0004410L 0005010L 0004310L 0004646L 0005746L 0005946L 0005346L 0005312L 0004312L 0004512L 0004312L 0004326L 0006226L 00057

Sample Soil 3 Sample Soil 3 Sample Soil 3Element PBD 99 Element PBD 47 Element PBD 100

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]10L 00016 10L 00011 10L 0000310L 00019 10L 00010 10L 0000410L 00013 10L 00012 10L 0000410L 00019 46L 00007 10L 0000246L 00025 46L 00022 46L 0000246L 00025 46L 00005 46L 0000646L 00008 46L 00007 46L 0000246L 00011 12L 00010 46L 0000264L 00005 12L 00017 3L 29100064L 00005 12L 00010 3L 32000064L 00006 12L 00009 26L 0000564L 00007 26L 00007 26L 0000512L 00012 26L 0000712L 0001312L 0001312L 0001226L 0000526L 00006

Sample Soil 3 Sample Soil 3 Sample Soil 3Element PBD 153 Element PBD 154 Element PBD 196

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]44L 00050 4L 00010 46L 0000744L 00050 46L 00001 46L 0001146L 00002 46L 00002 46L 0000846L 00003 46L 00001 46L 0001146L 00002 46L 00002 64L 0002646L 00002 64L 00001 64L 0002664L 00001 64L 00001 64L 0002964L 00001 64L 00001 64L 0003464L 00001 64L 00002 12L 0004564L 00002 12L 00003 12L 00032

12L 00002 12L 0002212L 00002 12L 0002112L 00002

Sample Soil 3 Sample Soil 3 Sample Soil 3Element PBD 197 Element PBD 203 Element PBD 209

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00006 46L 00011 4L 0091046L 00013 46L 00017 4L 0150046L 00011 46L 00015 4L 0120046L 00013 46L 00018 4L 0160012L 00090 64L 00013 44L 0337012L 00056 64L 00014 44L 0281012L 00033 64L 00016 44L 0287012L 00032 64L 00015 44L 02540

12L 00055 46L 0230012L 00041 46L 0220012L 00027 46L 0150012L 00026 46L 01900

64L 0438164L 0401664L 0414464L 0449812L 0367112L 0397812L 0409112L 03838

Sample Soil 3 26L 0102Element PBD 183 26L 0131

LAB PARM [mgkg]46L 0000746L 0000846L 0005846L 0000764L 0000264L 0000364L 0000364L 0000312L 0001512L 0001112L 0000712L 00007

European Commission EUR 23003 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on polybrominated diphenylethers Author(s) E Sobiecka H van der Sloot D Barcelo B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 68 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07403-5 Abstract Project HORIZONTAL is interdisciplinary aiming at a harmonisation and horizontal standardisation of test procedures in particular for sludge soils and biowastes In the context of this standardization project a series of draft technical specification were designed upon an extensive desk study fine-tuned after expert consultations and finally validated in international intercomparisons exercise This report summarises the work performed within the validation study of the draft standard for the determination of polybrominated diphenylethers (PBDE) in soils sludge and treated bio-waste using gas-chromatography method with mass selective detection (GC-MS) It further explains the underlying statistical concept for the calculation of reproducibility and repeatability from intercomparisons data In addition all single values results of the statistical evaluation as well as background information on the validation materials used are described and explained

The mission of the JRC is to provide customer-driven scientific and technical support for the conception development implementation and monitoring of EU policies As a service of the European Commission the JRC functions as a reference centre of science and technology for the Union Close to the policy-making process it serves the common interest of the Member States while being independent of special interests whether private or national

LB

-NA

-23003-EN

-C

7

Table 1 ndash Analytical data obtained on an average sludge sample in LUA NRW (with courtesy of K Furtmann LUA Duumlsseldorf)

Parameter Concentration PCB 120 ugkg DEHP 110 mgkg PAH 5 mgkg (EPA) PCDDF 15 ng TEkg PBDE 400 ugkg NP 40 mgkg LAS 3 gkg AOX 300 mgkg

Subsequent screening led to the information displayed hereafter It should be stressed that the data were obtained as SCREENING information on the UNTREATED or partially treated raw materials Therefore the final target values which are relevant for the validation intercomparison can be different

Table 2 ndash Analytical data obtained on a first screening on the sludge samples from LUA NRW

Sewage sludge A

Dusseldorf

sewage sludge D

Dusseldorf PCB (ngg) 28 62 35 52 101 65 101 31 38 118 49 40 153 30 33 105 24 11 138 46 38 156 lt1 lt1 180 34 23 170 23 19 PAH (ngg) Naphtalene 34 381 Acenaphtylene 15 43 Acenaphthene 81 108 Fluorene 94 1167 Phenantrene 3440 Anthracene 22 344 Flouranthene 316 4817 Pyrene 235 3011 Benz(a)anthracene 473 791 Chrysene 691 1078 Benz(b)fluoranthene 538 1688 Benz(k)fluoranthene 228 635 Benz(a)pyrene 383 1114 Indeno(123-cd)pyrene 92 229 Dibenzo(ah)anthracene 71 70 Benzo(ghi)perylene 80 185

8

Table 3 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Sludge D (1) 0135 41474 385 Sludge B (2) 0538 0034 30634 547 Sludge A (3) 0184 0037 31399 146 Sludge C (4) 0354 1528 6678 229

Table 4 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Sludge 2

(B)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

554

959

694

591

772

509

nq

nq

970

2216

2379

Table 5 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena IES Ispra Spain) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Sludge 1 (D) 265 290 533 359 1231 338 784 438 lt 005 232 786 Sludge 2 (B) 119 311 626 202 278 299 722 251 lt 005 118 625 Sludge 3 (A) 168 360 621 332 847 416 119 451 lt 005 116 1237 Sludge 4 (C) 563 198 116 273 726 511 473 618 lt 005 444 2015

Table 6 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Sludge 1 (D) 2154 58 844 099 103 101 4367 lt15 50448 Sludge 2 (B) 1067 366 692 046 1491 077 5217 lt15 57633 Sludge 3 (A) 731 663 684 035 1287 068 3733 lt15 60369 Sludge 4 (C) 4379 965 527 163 522 107 5628 lt15 23945

Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM)Sludge 1 (D) 03 2403 101 1002 350 15 1944 132Sludge 2 (B) 031 315 97 879 172 12 514 180Sludge 3 (A) 031 1281 153 1567 265 16 1440 168Sludge 4 (C) 055 231 628 2625 371 81 1101 244

9

22 Agricultural soil material from Reading United Kingdom

The material was proposed by the University of Reading (S Nortcliff) and was sampled from a site called ldquoFrogmore Farmrdquo which was featured in the ldquoMetalsrdquo Report for HORIZONTAL This site is close to Reading with soils developed on flintyloamy periglacial materials over Chalk has a long and well documented history of sludge application The focus of the work of Nortcliff et al undertook at this site and the monitoring and control at the site (by Thames Water and the subsequent subsidiary bodies dealing with sludge application to soil) was on metals (and metal loads) with no analysis or indeed any form of investigation in to organics in the broadest sense

The analytical information produced in the context of the screening of the raw material is displayed below

Table 7 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 3

(Reading) 0032 0119 669

Table 8 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 3 (Reading) 015 706 279 138 152 901 267 300 lt 005 258 931

Table 9 ndash Analytical data obtained on a first screening on the sludge-amended soil from Reading (courtesy of IRMM)

Parameter Concentration

PCB ngg 28 lt1 52 lt1 101 lt1 118 lt1 153 lt1 105 lt1 138 lt1 156 lt1 180 lt1 170 lt1 PAH ngg Naphtalene lt10 Acenaphtylene 21 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene lt10 Flouranthene 818 Pyrene 776 Benz(a)anthracene 565

10

Parameter Concentration

Chrysene 608 Benz(b)fluoranthene 824 Benz(k)fluoranthene 329 Benz(a)pyrene 799 Indeno(123-cd)pyrene

779

Dibenzo(ah)anthracene 118 Benzo(ghi)perylene 394

Table 10 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 3

(Reading)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

103

003

nq

nq

nq

nd

nd

272

273

Table 11 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 3 (Reading) 015 706 279 138 152 901 267 300 lt 005 258 931

Table 12 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 3 (Reading) 7936 477 112 096 194 017 4107 443 2102 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 3 (Reading) 042 13 45 69 69 69 216 92

Table 13 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 3 (Reading) 012

11

23 Compost from Vienna Austria

The fresh compost material was obtained from the Austrian Federal Environment Agency (UBA Vienna) which had used a sub-batch of the raw material for national intercomparson The remainder of the material was stored at 4degC until shipment to IRMM for further processing The following analytical information was provided by UBA Austria and completed with various screenings

Table 14 ndash Analytical data on compost material received from UBA Austria Inorganic and sum parameters

Parameter Unit Sample fraction used Observed mean B CAT mgl FM Fresh sample lt10mm 61 K CAT mgl FM Fresh sample lt10mm 2624 Mg CAT mgl FM Fresh sample lt10mm 242 P CAT mgl FM Fresh sample lt10mm 49 B CAT DM Fresh sample lt10mm 00017 K CAT DM Fresh sample lt10mm 072 Mg CAT DM Fresh sample lt10mm 007 P CAT DM Fresh sample lt10mm 001 NO3-N mgkg FM Fresh sample lt10mm 35 NH4-N mgkg FM Fresh sample lt10mm 230 Ctotal DM lt45degdry milled 29 Corg DM lt45degdry milled 27 Ntotal DM lt45degdry milled 17 P mgkg DM lt45degdry milled 2596 K mgkg DM lt45degdry milled 11019 K DM lt45degdry milled 110 B mgkg DM lt45degdry milled 60 Cd mgkg DM lt45degdry milled 046 Cr mgkg DM lt45degdry milled 25 Cu mgkg DM lt45degdry milled 46 Hg mgkg DM lt45degdry milled 020 Ni mgkg DM lt45degdry milled 18 Pb mgkg DM lt45degdry milled 45 Zn mgkg DM lt45degdry milled 198 Ca mgkg DM lt45degdry milled 68776 Ca DM lt45degdry milled 69 Mo mgkg DM lt45degdry milled 08 S mgkg DM lt45degdry milled 2137 Fe mgkg DM lt45degdry milled 9959 Mn mgkg DM lt45degdry milled 418 Na mgkg DM lt45degdry milled 742 Co mgkg DM lt45degdry milled 41 AOX mgkg DM lt30deg dry milled 62

Table 15 ndash Analytical data on compost material received from UBA Austria Polycyclic aromatic hydrocarbons

PAH Unit Result Naphthaline microgkg DM 93 Acenaphthylene microgkg DM 86 Acenaphthene microgkg DM 5 Fluorene microgkg DM 80 Phenanthrene microgkg DM 89 Anthracene microgkg DM 27 Fluoranthene microgkg DM 487 Pyrene microgkg DM 380

12

PAH Unit Result Benzo(a)anthracene microgkg DM 278 Chrysene microgkg DM 317 Benzo(b)fluoranthene microgkg DM 365 Benzo(k)fluoranthene microgkg DM 193 Benz(a)pyrene microgkg DM 320 Indeno(123-cd)pyrene microgkg DM 233 Dibenz(ah)anthracene microgkg DM 67 Benzo(ghi)perylene microgkg DM 225 Sum EPA microgkg DM 3013 Sum EPA mgkg DM 30

Table 16 ndash Analytical data on compost material received from UBA Austria Sum PCDDs and PCBs

Parameter

Dioxine TEQ (ITEF) ngkg DM 73 TEQ (WHO) ngkg DM 35 PCB Σ Ballschmiter mgkg DM 005

Table 17 ndash Analytical data on compost material obtained by screening in IRMM

Parameter Result in ngg

PCB 28 2 52 2 101 4 118 3 153 10 105 1 138 8 156 1 180 5 170 lt1 PAH Naphtalene lt10 Acenaphtylene lt10 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene 26 Fluoranthene 611 Pyrene 510 Benz(a)anthracene 888 Chrysene 957 Benz(b)fluoranthene 1531 Benz(k)fluoranthene 547 Benz(a)pyrene 1101 Indeno(123-cd)pyrene 416 Dibenzo(ah)anthracene 81 Benzo(ghi)perylene 295

13

Table 18 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Compost 1

(Vienna)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

402

019

259

nq

023

004

nq

nq

144

174

259

Table 19 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Compost 1

(Vienna) 0058 1426 557

Table 20 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Compost 1 (Vienna) 039 736 319 410 365 127 495 004 079 013 208

Table 21 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Compost 1 (Vienna) 2063 431 617 426 199 249 1602 lt15 10521

Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Compost 1 (Vienna) 035 3496 81 375 79 55 653 60

Table 22 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Compost 1 (Vienna) 017

14

24 Agricultural soil sludge amended soil from Pavia Italy

This sludge-amended soil material was obtained during a monitoring campaign which aimed at a generic description of the over-all soil quality in Pavia Province Italy The material which was collected from the upper horizon originates from a small farm called ldquoCascina Novellordquo During the characterisation of the site the following analytical information was obtained on a pooled sample of a sub-area of the farm of 20 X 20 m2

Table 23 ndash Analytical data on Pavia soil

Parameter Result Al 713 Wgt As 224 mgkg Cd 079 mgkg Cr 59 mgkg Cu 308 mgkg Hg 008 mgkg Ni 344 mgkg Pb 246 mgkg Zn 95 mgkg C 091 Wgt 2378-TCDD 0047 pgg 12378-PeCDD 015 pgg 123478-HxCDD 019 pgg 123678-HxCDD 15 pgg 123789-HxCDD 074 pgg 1234678-HpCDD 26 pgg OCDD 382 pgg 2378-TCDF 068 pgg 12378-PeCDF 053 pgg 23478-PeCDF 071 pgg 123478-HxDF 100 pgg 123678-HxDF 066 pgg 234678-HxDF 16 pgg 123789-HxDF 027 pgg 1234678-HpDF 12 pgg 1234789-HpDF 068 pgg OCDF 33 pgg I-TEQ 20 pgg WHO-TEQ 17 pgg

In addition the screening performed at IRMM did not reveal significant quantities of PCBs and PAHs which were all below the LoDs (1 ngg for PCBs and 10 ngg for PAHs respectively)

Table 24 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 5 (Pavia) 0005 0011 154

15

Table 25 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 5

(Pavia)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

039

nq

nq

008

nq

nd

nd

670

671

Table 26 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 5 (Pavia) 033 184 573 225 426 305 206 200 lt 005 381 878

Table 27 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 5 (Pavia) 6939 129 145 224 425 116 6118 255 1789 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 5 (Pavia) 184 62 38 108 55 66 597 110

Table 28 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 5 (Pavia) 006

16

25 Sludge-amended-soil from Barcelona Spain

The sludge-amended soil material from Barcelona sampled upon indication from the Barcelorsquo- Group in Barcelona

Table 29 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 2 (Lleida T) 0015 0183 1138

Table 30 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 2

(Lleida T)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

159

045

nq

048

160

nq

nq

1000

1004

Table 31 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 2 (Lleida T) 059 141 327 536 405 186 184 224 lt 005 318 111

Table 32 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 2 (Lleida T) 4443 1067 1429 253 344 204 4116 780 3396 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 2 (Lleida T) 064 65 26 125 59 17 547 65

Table 33 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 2 (Lleida T) 010

17

26 Sludge amended soil from Essen Germany

The German sludge-amended soil from Essen which was provided as the three sludge materials by LUA NRW did not feature significant concentrations of the PCB congeners 28 52 101 118 153 105 138 156 180 170 but had detectable amounts of some PAHs

Table 34 ndash Analytical screening data on the German sludge-amended soil

Parameter Concentration(ngg)

Naphtalene lt10 Acenaphtylene lt10 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene lt10 Fluoranthene 28 Pyrene 20 Benz(a)anthracene 24 Chrysene 47 Benz(b)fluoranthene 76 Benz(k)fluoranthene 20 Benz(a)pyrene 35 Indeno(123-cd)pyrene 35 Dibenzo(ah)anthracene 10 Benzo(ghi)perylene 26

Table 35 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 4 (Essen) 0011 0302 055

Table 36 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 4

(Essen)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

nq

nq

nq

nq

nq

nq

128

191

203

18

Table 37 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 4 (Essen) 052 545 261 805 320 403 273 273 lt 005 295 781

Table 38 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 4 (Essen) 7947 442 085 06 086 007 2163 189 2019 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 4 (Essen) 045 19 42 87 683 60 462 61

Table 39 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 4 (Essen) 004

27 Long-term sludge exposed soil from Hohenheim-Stuttgart Germany

Similarly an additional sludge exposed soil was sampled at the University of Hohenheim Stuttgart were a test soil was long-term exposed to elevated concentrations of sewage sludge

Table 40 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 1 (Stuttgart) 0045 0263 1765

Table 41 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 1

(Stuttgart)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

230

006

004

004

nq

nd

nd

498

500

19

Table 42 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 1 (Stuttgart) 069 127 361 262 504 183 252 262 lt 005 266 142

Table 43 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 1 (Stuttgart) 7194 1006 133 186 366 088 7874 275 3571 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 1 (Stuttgart) 123 50 47 212 85 69 991 129

Table 44 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 1 (Stuttgart) 177

18

Annex 3

Statistical calculations

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 47)Mandels h statistics(Sludge 1 - PBD 47)

Sample Sludge 1 NUM

Element PBD 47

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00213 0001 3 -021 005 - - 10L - - NUM46L 00273 0002 4 016 021 - - 46L - - NUM64L 00059 0000 4 -116 002 NUM - 64L - - NUM12L 00188 0000 4 -036 002 - - 12L - - NUM26L 00499 0024 2 157 223 Fail - - 26L - - NUM

Totgem 0025 0005 mgkg 1-level 172 (185) NUM (10L46L64L12L26L) -1Totstd= 0016 0010 5-level 157 (162) 5

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 5 Labs rejected (10L46L64L12L26L)

000 050 100 150 200 250

k-values

10L

46L

64L

12L

26L

Mandels k statistics(Sludge 1 - PBD 47)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

10L

46L

64L

12L

26L

Labo

rato

ries

NUM

-200 -100 000 100 200

h-values

10L

46L

64L

12L

26L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 47)

Sludge 1-PBD 47

Unit mgkg

Mandels k statistics(Soil 3 - PBD 47)Mandels h statistics(Soil 3 - PBD 47)

Sample Soil 3 Soil 3 - PBD 47 -- Mean PARM = 0001 [mgkg]

Element PBD 47

General calcparmT1= 134814E-02T2= 142830E-05T3= 13T4= 45T5= 22767E-06

n= variabelp= 4

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean26L 00007 0000 2 -143 001 00007 00000 2 1 00046L 00010 0001 4 010 181 00010 00008 4 3 00010L 00011 0000 3 049 023 00011 00001 3 2 00012L 00012 0000 4 084 081 00012 00004 4 3 000

Totgem 0001 0000 mgkg 1-level 149 (177) 4 00010 () 4 3Totstd= 0000 0000 5-level 142 (159)

RESULTS Mean = 000100 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000050 --gt 5031 r = 00014Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000050 --gt 5031 R = 00014Remarks none

000 050 100 150 200

k-values

26L

46L

10L

12L

Mandels k statistics(Soil 3 - PBD 47)

00 00 00 00 00 00 00 00 00 00 00

Deviation from Mean

26L

46L

10L

12L

Labo

rato

ries

Soil 3 - PBD 47 -- Mean PARM = 0001 [mgkg]

-200 -100 000 100

h-values

26L

46L

10L

12L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 47)

Soil 3-PBD 47

Unit mgkg

Mandels k statistics(Compost 1 - PBD 99)Mandels h statistics(Compost 1 - PBD 99)

Sample Compost 1 Compost 1 - PBD 99 -- Mean PARM = 0003 [mgkg]

Element PBD 99

General calcparmT1= 492124E-02T2= 148747E-04T3= 17T4= 61T5= 93196E-06

n= variabelp= 5

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00020 0000 4 -137 053 00020 00004 4 3 000

26L 00025 0000 2 -058 024 00025 00002 2 1 00010L 00029 0000 3 012 032 00029 00003 3 2 00046L 00033 0001 4 069 161 00033 00013 4 3 00012L 00036 0001 4 114 140 00036 00011 4 3 000

Totgem 0003 0001 mgkg 1-level 172 (185) 5 00029 () 5 4Totstd= 0001 0001 5-level 157 (162)

RESULTS Mean = 000286 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000088 --gt 3086 r = 00025Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000101 --gt 3525 R = 00028Remarks none

000 050 100 150 200

k-values

4L

26L

10L

46L

12L

Mandels k statistics(Compost 1 - PBD 99)

00 00 00 00 00 00 00 00 00 00

Deviation from Mean

4L

26L

10L

46L

12L

Labo

rato

ries

Compost 1 - PBD 99 -- Mean PARM = 0003 [mgkg]

-200 -100 000 100 200

h-values

4L

26L

10L

46L

12L

Labo

rato

ries

Mandels h statistics(Compost 1 - PBD 99)

Compost 1-PBD 99

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 99)Mandels h statistics(Sludge 1 - PBD 99)

Sample Sludge 1 Sludge 1 - PBD 99 -- Mean PARM = 0024 [mgkg]

Element PBD 99

General calcparmT1= 448050E-01T2= 112113E-02T3= 19T4= 73T5= 32972E-05

n= variabelp= 5

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean64L 00173 0002 4 -118 041 Fail 00173 00019 4 3 -0014L 00183 0002 4 -104 032 00183 00015 4 3 -001

12L 00227 0001 4 -038 022 00227 00010 4 3 00010L 00290 0001 3 055 021 00290 00010 3 2 00146L 00320 0002 4 100 039 00320 00018 4 3 00126L 00323 0011 2 105 234 - - 26L - - 001

Totgem 0025 0003 mgkg 1-level 187 (177) 5 00239 (26L) 5 4Totstd= 0007 0004 5-level 166 (154) 1

RESULTS Mean = 002385 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000153 --gt 643 r = 00043Between lab variance S2L = 000004Reproducibility var S2R = 000004Reproducibility std SR = 000666 --gt 2791 R = 00186Remarks 1 Lab rejected (26L)

000 050 100 150 200 250

k-values

64L

4L

12L

10L

46L

26L

Mandels k statistics(Sludge 1 - PBD 99)

00 00 00 00 00 00 00 00 00 00

Deviation from Mean

64L

4L

12L

10L

46L

26L

Labo

rato

ries

Sludge 1 - PBD 99 -- Mean PARM = 0024 [mgkg]

-200 -100 000 100 200

h-values

64L

4L

12L

10L

46L

26L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 99)

Sludge 1-PBD 99

Unit mgkg

Mandels k statistics(Soil 3 - PBD 99)Mandels h statistics(Soil 3 - PBD 99)

Sample Soil 3 NUM

Element PBD 99

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00017 0000 4 091 068 - - 10L - - NUM46L 00017 0001 4 100 211 - - 46L - - NUM64L 00005 0000 4 -106 023 NUM - 64L - - NUM12L 00012 0000 4 015 014 - - 12L - - NUM26L 00006 0000 2 -101 012 - - 26L - - NUM

Totgem 0001 0000 mgkg 1-level 172 (173) NUM (10L46L64L12L26L) -1Totstd= 0001 0000 5-level 157 (153) 5

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 5 Labs rejected (10L46L64L12L26L)

000 050 100 150 200 250

k-values

10L

46L

64L

12L

26L

Mandels k statistics(Soil 3 - PBD 99)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

10L

46L

64L

12L

26L

Labo

rato

ries

NUM

-200 -100 000 100 200

h-values

10L

46L

64L

12L

26L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 99)

Soil 3-PBD 99

Unit mgkg

Mandels k statistics(Compost 1 - PBD 100)Mandels h statistics(Compost 1 - PBD 100)

Sample Compost 1 Compost 1 - PBD 100 -- Mean PARM = 0001 [mgkg]

Element PBD 100

General calcparmT1= 124272E-02T2= 113129E-05T3= 14T4= 52T5= 46584E-07

n= variabelp= 4

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean26L 00006 0000 2 -131 037 Fail 00006 00001 2 1 00010L 00009 0000 4 003 083 00009 00002 4 3 00046L 00009 0000 4 016 115 00009 00002 4 3 00012L 00011 0000 4 112 136 Fail 00011 00003 4 3 000

Totgem 0001 0000 mgkg 1-level 149 (167) 4 00009 () 4 3Totstd= 0000 0000 5-level 142 (15)

RESULTS Mean = 000085 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000022 --gt 2531 r = 00006Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000025 --gt 2882 R = 00007Remarks none

000 050 100 150

k-values

26L

10L

46L

12L

Mandels k statistics(Compost 1 - PBD 100)

00 00 00 00 00 00 00 00 00 00 00

Deviation from Mean

26L

10L

46L

12L

Labo

rato

ries

Compost 1 - PBD 100 -- Mean PARM = 0001 [mgkg]

-200 -100 000 100 200

h-values

26L

10L

46L

12L

Labo

rato

ries

Mandels h statistics(Compost 1 - PBD 100)

Compost 1-PBD 100

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 100)Mandels h statistics(Sludge 1 - PBD 100)

Sample Sludge 1 Sludge 1 - PBD 100 -- Mean PARM = 0005 [mgkg]

Element PBD 100

General calcparmT1= 852065E-02T2= 412762E-04T3= 18T4= 68T5= 78914E-07

n= variabelp= 5

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00039 0000 4 -042 007 Fail 00039 00002 4 3 000

12L 00044 0000 4 -041 005 Fail 00044 00001 4 3 00010L 00046 0000 4 -041 013 Fail 00046 00003 4 3 00046L 00056 0000 4 -040 012 Fail 00056 00003 4 3 00026L 00059 0000 2 -040 013 Fail 00059 00003 2 1 00038L 02168 0006 4 204 244 Fail - - 38L - - 021

Totgem 0040 0001 mgkg 1-level 187 (177) 5 00049 (38L) 5 4Totstd= 0087 0002 5-level 166 (154) 1

RESULTS Mean = 000486 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000025 --gt 507 r = 00007Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000084 --gt 1731 R = 00024Remarks 1 Lab rejected (38L)

000 050 100 150 200 250

k-values

4L

12L

10L

46L

26L

38L

Mandels k statistics(Sludge 1 - PBD 100)

-01 00 01 01 02 02 03

Deviation from Mean

4L

12L

10L

46L

26L

38L

Labo

rato

ries

Sludge 1 - PBD 100 -- Mean PARM = 0005 [mgkg]

-100 000 100 200 300

h-values

4L

12L

10L

46L

26L

38L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 100)

Sludge 1-PBD 100

Unit mgkg

Mandels k statistics(Soil 3 - PBD 100)Mandels h statistics(Soil 3 - PBD 100)

Sample Soil 3 NUM

Element PBD 100

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00003 0000 4 -050 000 Fail - - 10L - - NUM46L 00003 0000 4 -050 000 Fail NUM - 46L - - NUM3L 305500 2051 2 150 200 Fail - - 3L - - NUM

26L 00005 0000 2 -050 000 Fail - - 26L - - NUM

Totgem 7638 0513 mgkg 1-level 149 (177) NUM (10L46L3L26L) -1Totstd= 15275 1025 5-level 142 (159) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (10L46L3L26L)

000 050 100 150 200

k-values

10L

46L

3L

26L

Mandels k statistics(Soil 3 - PBD 100)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

10L

46L

3L

26L

Labo

rato

ries

NUM

-100 000 100 200

h-values

10L

46L

3L

26L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 100)

Soil 3-PBD 100

Unit mgkg

Mandels k statistics(Compost 1 - PBD 153)Mandels h statistics(Compost 1 - PBD 153)

Sample Compost 1 NUM

Element PBD 153

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean44L 00053 0001 3 150 157 Fail - - 44L - - NUM46L 00007 0000 4 -044 111 Fail - - 46L - - NUM12L 00005 0000 4 -051 055 Fail - - 12L - - NUM26L 00005 0000 2 -054 001 Fail NUM - 26L - - NUM

Totgem 0002 0000 mgkg 1-level 149 (177) NUM (44L46L12L26L) -1Totstd= 0002 0000 5-level 142 (159) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (44L46L12L26L)

000 050 100 150 200

k-values

44L

46L

12L

26L

Mandels k statistics(Compost 1 - PBD 153)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

44L

46L

12L

26L

Labo

rato

ries

NUM

-100 000 100 200

h-values

44L

46L

12L

26L

Labo

rato

ries

Mandels h statistics(Compost 1 - PBD 153)

Compost 1-PBD 153

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 153)Mandels h statistics(Sludge 1 - PBD 153)

Sample Sludge 1 Sludge 1 - PBD 153 -- Mean PARM = 0004 [mgkg]

Element PBD 153

General calcparmT1= 676738E-02T2= 267609E-04T3= 18T4= 68T5= 19626E-05

n= variabelp= 5

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00024 0000 4 -157 017 00024 00002 4 3 000

12L 00038 0002 4 006 154 00038 00018 4 3 00046L 00039 0000 4 011 026 00039 00003 4 3 00026L 00039 0000 2 018 004 00039 00000 2 1 00064L 00049 0002 4 122 159 00049 00018 4 3 000

Totgem 0004 0001 mgkg 1-level 172 (173) 5 00038 () 5 4Totstd= 0001 0001 5-level 157 (153)

RESULTS Mean = 000378 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000123 --gt 3252 r = 00034Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000142 --gt 3754 R = 00040Remarks none

000 050 100 150 200

k-values

4L

12L

46L

26L

64L

Mandels k statistics(Sludge 1 - PBD 153)

00 00 00 00 00 00 00

Deviation from Mean

4L

12L

46L

26L

64L

Labo

rato

ries

Sludge 1 - PBD 153 -- Mean PARM = 0004 [mgkg]

-200 -100 000 100 200

h-values

4L

12L

46L

26L

64L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 153)

Sludge 1-PBD 153

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 154)Mandels h statistics(Sludge 1 - PBD 154)

Sample Sludge 1 NA

Element PBD 154

General calcparmT1= NAT2= NAT3=T4=T5=

n= variabelp=

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00021 0000 3 -100 021 NA - 4L - - NA

46L 00025 0000 4 115 018 NA - 46L - - NA64L 00021 0001 4 -066 179 - - 64L - - NA12L 00023 0000 4 050 085 - - 12L - - NA

Totgem 0002 0000 mgkg 1-level 149 (167) NA (4L46L64L12L) -1Totstd= 0000 0000 5-level 142 (15) 4

RESULTS Mean = NA mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NAReproducibility var S2R = NAReproducibility std SR = NA --gt NA R = NARemarks 4 Labs rejected (4L46L64L12L)

000 050 100 150 200

k-values

4L

46L

64L

12L

Mandels k statistics(Sludge 1 - PBD 154)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

4L

46L

64L

12L

Labo

rato

ries

NA

-100 000 100 200

h-values

4L

46L

64L

12L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 154)

Sludge 1-PBD 154

Unit mgkg

Mandels k statistics(Soil 3 - PBD 154)Mandels h statistics(Soil 3 - PBD 154)

Sample Soil 3 NUM

Element PBD 154

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

4L 00010 - 1 150 Fail - - 4L - - NUM46L 00001 0000 4 -053 096 Fail - - 46L - - NUM64L 00001 0000 4 -056 105 Fail NUM - 64L - - NUM12L 00002 0000 4 -040 099 Fail - - 12L - - NUM

Totgem 000037 0000 mgkg 1-level 149 (164) NUM (4L46L64L12L) -1Totstd= 000042 0000 5-level 142 (153) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (4L46L64L12L)

000 050 100 150

k-values

4L

46L

64L

12L

Mandels k statistics(Soil 3 - PBD 154)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

4L

46L

64L

12L

Labo

rato

ries

NUM

-100 000 100 200

h-values

4L

46L

64L

12L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 154)

Soil 3-PBD 154

Unit mgkg

Mandels k statistics(Compost 1 - PBD 209)Mandels h statistics(Compost 1 - PBD 209)

Sample Compost 1 NUM

Element PBD 209

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00065 0003 2 -049 032 - - 4L - - NUM

44L 00573 0021 4 150 197 Fail - - 44L - - NUM12L 00078 0001 4 -045 011 - - 12L - - NUM26L 00049 0000 2 -056 000 NUM - 26L - - NUM

Totgem 0019 0006 mgkg 1-level 149 (177) NUM (4L44L12L26L) -1Totstd= 0025 0010 5-level 142 (159) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (4L44L12L26L)

000 050 100 150 200

k-values

4L

44L

12L

26L

Mandels k statistics(Compost 1 - PBD 209)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

4L

44L

12L

26L

Labo

rato

ries

NUM

-100 000 100 200

h-values

4L

44L

12L

26L

Labo

rato

ries

Mandels h statistics(Compost 1 - PBD 209)

Compost 1-PBD 209

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 209)Mandels h statistics(Sludge 1 - PBD 209)

Sample Sludge 1 Sludge 1 - PBD 209 -- Mean PARM = 0249 [mgkg]

Element PBD 209

General calcparmT1= 394542E+00T2= 107296E+00T3= 16T4= 56T5= 19723E-02

n= variabelp= 5

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 01550 0055 4 -112 148 Fail 01550 00551 4 3 -009

46L 02050 0007 2 -053 019 02050 00071 2 1 -00412L 02137 0058 4 -042 155 02137 00576 4 3 -00426L 03149 0021 2 078 057 Fail 03149 00210 2 1 00764L 03577 0007 4 129 020 Fail 03577 00074 4 3 011

Totgem 0249 0030 mgkg 1-level 172 (185) 5 02493 () 5 4Totstd= 0084 0025 5-level 157 (162)

RESULTS Mean = 024926 mgkg

Repeatability variance S2r = 000179Repeatability std Sr = 004234 --gt 1699 r = 01186Between lab variance S2L = 000743Reproducibility var S2R = 000922Reproducibility std SR = 009604 --gt 3853 R = 02689Remarks none

000 050 100 150 200

k-values

4L

46L

12L

26L

64L

Mandels k statistics(Sludge 1 - PBD 209)

-01 -01 00 01 01 02

Deviation from Mean

4L

46L

12L

26L

64L

Labo

rato

ries

Sludge 1 - PBD 209 -- Mean PARM = 0249 [mgkg]

-200 -100 000 100 200

h-values

4L

46L

12L

26L

64L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 209)

Sludge 1-PBD 209

Unit mgkg

Mandels k statistics(Soil 3 - PBD 209)Mandels h statistics(Soil 3 - PBD 209)

Sample Soil 3 Soil 3 - PBD 209 -- Mean PARM = 0258 [mgkg]

Element PBD 209

General calcparmT1= 596398E+00T2= 191917E+00T3= 22T4= 84T5= 13249E-02

n= variabelp= 6

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean26L 01162 0021 2 -108 074 Fail 01162 00207 2 1 -0144L 01303 0031 4 -097 111 Fail 01303 00312 4 3 -013

46L 01975 0036 4 -046 128 Fail 01975 00359 4 3 -00644L 02898 0035 4 024 124 Fail 02898 00346 4 3 00312L 03895 0018 4 100 065 Fail 03895 00181 4 3 01364L 04260 0022 4 127 078 Fail 04260 00219 4 3 017

Totgem 0258 0027 mgkg 1-level 187 (177) 6 02582 () 6 5Totstd= 0132 0008 5-level 166 (154)

RESULTS Mean = 025818 mgkg

Repeatability variance S2r = 000083Repeatability std Sr = 002878 --gt 1115 r = 00806Between lab variance S2L = 001640Reproducibility var S2R = 001723Reproducibility std SR = 013127 --gt 5084 R = 03676Remarks none

000 050 100 150

k-values

26L

4L

46L

44L

12L

64L

Mandels k statistics(Soil 3 - PBD 209)

-02 -01 -01 00 01 01 02 02

Deviation from Mean

26L

4L

46L

44L

12L

64L

Labo

rato

ries

Soil 3 - PBD 209 -- Mean PARM = 0258 [mgkg]

-200 -100 000 100 200

h-values

26L

4L

46L

44L

12L

64L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 209)

Soil 3-PBD 209

Unit mgkg

Mandels k statistics(Compost 1 - Sum PBD)Mandels h statistics(Compost 1 - Sum PBD)

Sample Compost 1 Compost 1 - Sum PBD -- Mean PARM = 0009 [mgkg]

Element Sum PBD

General calcparmT1= 154064E-01T2= 169065E-03T3= 18T4= 68T5= 11354E-04

n= variabelp= 5

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00031 0002 4 -067 016 00031 00016 4 3 -0014L 00055 0005 4 -056 048 00055 00047 4 3 000

46L 00085 0003 4 -042 031 00085 00030 4 3 00026L 00123 0000 2 -024 003 00123 00002 2 1 00012L 00154 0002 4 -011 021 00154 00021 4 3 00144L 00613 0023 4 200 237 Fail - - 44L - - 005

Totgem 0018 0006 mgkg 1-level 187 (177) 5 00089 (44L) 5 4Totstd= 0022 0009 5-level 166 (154) 1

RESULTS Mean = 000893 mgkg

Repeatability variance S2r = 000001Repeatability std Sr = 000296 --gt 3308 r = 00083Between lab variance S2L = 000002Reproducibility var S2R = 000003Reproducibility std SR = 000570 --gt 6374 R = 00159Remarks 1 Lab rejected (44L)

000 050 100 150 200 250

k-values

10L

4L

46L

26L

12L

44L

Mandels k statistics(Compost 1 - Sum PBD)

00 00 00 00 00 00 01 01

Deviation from Mean

10L

4L

46L

26L

12L

44L

Labo

rato

ries

Compost 1 - Sum PBD -- Mean PARM = 0009 [mgkg]

-100 000 100 200

h-values

10L

4L

46L

26L

12L

44L

Labo

rato

ries

Mandels h statistics(Compost 1 - Sum PBD)

Compost 1-Sum PBD

Unit mgkg

Mandels k statistics(Sludge 1 - Sum PBD)Mandels h statistics(Sludge 1 - Sum PBD)

Sample Sludge 1 Sludge 1 - Sum PBD -- Mean PARM = 0256 [mgkg]

Element Sum PBD

General calcparmT1= 531806E+00T2= 162188E+00T3= 22T4= 84T5= 25223E-02

n= variabelp= 6

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00423 0025 4 -156 044 Fail 00423 00252 4 3 -02146L 01808 0118 4 -049 205 - - 46L - - -0074L 01810 0056 4 -049 097 01810 00558 4 3 -007

38L 02168 0006 4 -022 010 02168 00059 4 3 -00412L 02890 0065 4 034 113 02890 00647 4 3 00364L 03958 0008 4 116 014 Fail 03958 00079 4 3 01426L 04094 0034 2 126 059 Fail 04094 00337 2 1 015

Totgem 0245 0044 mgkg 1-level 198 (179) 6 02557 (46L) 6 5Totstd= 0130 0039 5-level 171 (155) 1

RESULTS Mean = 025570 mgkg

Repeatability variance S2r = 000158Repeatability std Sr = 003970 --gt 1553 r = 01112Between lab variance S2L = 001807Reproducibility var S2R = 001964Reproducibility std SR = 014015 --gt 5481 R = 03924Remarks 1 Lab rejected (46L)

000 050 100 150 200 250

k-values

10L

46L

4L

38L

12L

64L

26L

Mandels k statistics(Sludge 1 - Sum PBD)

-03 -02 -02 -01 -01 00 01 01 02 02

Deviation from Mean

10L

46L

4L

38L

12L

64L

26L

Labo

rato

ries

Sludge 1 - Sum PBD -- Mean PARM = 0256 [mgkg]

-200 -100 000 100 200

h-values

10L

46L

4L

38L

12L

64L

26L

Labo

rato

ries

Mandels h statistics(Sludge 1 - Sum PBD)

Sludge 1-Sum PBD

Unit mgkg

Mandels k statistics(Soil 3 - Sum PBD)Mandels h statistics(Soil 3 - Sum PBD)

Sample Soil 3 Soil 3 - Sum PBD -- Mean PARM = 0227 [mgkg]

Element Sum PBD

General calcparmT1= 610980E+00T2= 200876E+00T3= 26T4= 100T5= 13106E-02

n= variabelp= 7

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00028 0001 4 -037 000 Fail 00028 00005 4 3 -02226L 01179 0021 2 -036 003 Fail 01179 00208 2 1 -0114L 01305 0031 4 -036 004 Fail 01305 00308 4 3 -010

46L 02065 0035 4 -036 005 Fail 02065 00350 4 3 -00244L 02923 0037 4 -035 005 Fail 02923 00365 4 3 00712L 04051 0015 4 -034 002 Fail 04051 00149 4 3 01864L 04314 0022 4 -033 003 Fail 04314 00223 4 3 0203L 305500 2051 2 247 283 Fail - - 3L - - 3032

Totgem 4017 0276 mgkg 1-level 206 (181) 7 02266 (3L) 7 6Totstd= 10722 0717 5-level 175 (156) 1

RESULTS Mean = 022663 mgkg

Repeatability variance S2r = 000069Repeatability std Sr = 002626 --gt 1159 r = 00735Between lab variance S2L = 002568Reproducibility var S2R = 002637Reproducibility std SR = 016238 --gt 7165 R = 04547Remarks 1 Lab rejected (3L)

000 050 100 150 200 250 300

k-values

10L

26L

4L

46L

44L

12L

64L

3L

Mandels k statistics(Soil 3 - Sum PBD)

-50 00 50 100 150 200 250 300 350

Deviation from Mean

10L

26L

4L

46L

44L

12L

64L

3L

Labo

rato

ries

Soil 3 - Sum PBD -- Mean PARM = 0227 [mgkg]

-100 000 100 200 300

h-values

10L

26L

4L

46L

44L

12L

64L

3L

Labo

rato

ries

Mandels h statistics(Soil 3 - Sum PBD)

Soil 3-Sum PBD

19

Annex 4

Raw data submitted

Sample Compost1 Sample Compost 1 Sample Compost 1Element PBD 99 Element PBD 100 Element PBD 153

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]4L 00021 10L 00008 44L 000504L 00024 10L 00008 44L 000604L 00014 10L 00007 44L 000504L 00020 10L 00011 46L 00004

10L 00029 46L 00007 46L 0001210L 00027 46L 00012 46L 0000410L 00032 46L 00009 46L 0000946L 00025 46L 00007 12L 0000446L 00052 12L 00008 12L 0000846L 00029 12L 00012 12L 0000446L 00026 12L 00008 12L 0000712L 00026 12L 00014 26L 0000512L 00043 26L 00007 26L 0000512L 00026 26L 0000612L 0004726L 0002626L 00024

Sample Compost 1 Sample Compost 1 Sample Compost 1Element PBD 154 Element PBD 183 Element PBD 196

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]4L 00010 46L 00002 46L 00011

46L 00003 46L 00024 46L 0000846L 00007 46L 00021 12L 0000246L 00003 46L 00003 12L 0000346L 00004 12L 00003 12L 0000112L 00003 12L 00011 12L 0000212L 00005 12L 0000312L 00031 12L 0000312L 00006

Sample Compost 1 Sample Compost 1 Sample Compost 1Element PBD 197 Element PBD 203 Element PBD 209

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00002 46L 00010 4L 0004146L 00023 12L 00002 4L 0008946L 00022 12L 00003 44L 0041012L 00004 12L 00002 44L 0084012L 00006 12L 00002 44L 0064012L 00003 44L 0040012L 00004 12L 00079

12L 0007312L 0006512L 0009326L 0004926L 00049

Sample Compost 1Element PBD 47

LAB PARM [mgkg]26L 0003826L 00039

Element PBD 99 Element PBD 47 Element PBD 209LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]

4L 00170 10L 00210 4L 010004L 00200 10L 00220 4L 018004L 00170 10L 00210 4L 012004L 00190 46L 00300 4L 0220010L 00280 46L 00280 46L 0210010L 00300 46L 00250 46L 0200010L 00290 46L 00260 64L 0351846L 00340 64L 00059 64L 0363846L 00330 64L 00057 64L 0364546L 00300 64L 00062 64L 0350846L 00310 64L 00060 12L 0220964L 00194 12L 00191 12L 0177164L 00154 12L 00187 12L 0292264L 00185 12L 00190 12L 0164664L 00159 12L 00186 26L 0329712L 00242 26L 00666 26L 0300012L 00223 26L 0033212L 0022112L 0022226L 0024626L 00400

Element PBD 203 Element PBD 197 Element PBD 196LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00022 46L 00027 46L 0002446L 00014 46L 00024 46L 0002264L 00036 12L 00161 64L 0005864L 00058 12L 00060 64L 0006512L 00063 12L 00061 12L 0004812L 00034 12L 00036 12L 0002512L 00038 12L 0003212L 00027 12L 00022

Element PBD 183 Element PBD 154 Element PBD 153LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00049 4L 00020 4L 0002246L 00035 4L 00022 4L 0002446L 00036 4L 00020 4L 0002246L 00034 46L 00025 4L 0002664L 00027 46L 00025 46L 0004064L 00023 46L 00025 46L 0004264L 00024 46L 00023 46L 0003564L 00020 64L 00034 46L 0003812L 00230 64L 00023 64L 0007412L 00032 64L 00017 64L 0004712L 00031 64L 00011 64L 0004612L 00030 12L 00030 64L 0003026L 00007 12L 00021 12L 0006526L 00008 12L 00021 12L 00029

12L 00021 12L 0003226L 00015 12L 0002926L 00019 26L 00039

26L 00040

Element PBD 100LAB PARM [mgkg]

4L 000384L 000414L 000374L 00038

38L 0219038L 0220038L 0208038L 0220010L 0004410L 0005010L 0004310L 0004646L 0005746L 0005946L 0005346L 0005312L 0004312L 0004512L 0004312L 0004326L 0006226L 00057

Sample Soil 3 Sample Soil 3 Sample Soil 3Element PBD 99 Element PBD 47 Element PBD 100

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]10L 00016 10L 00011 10L 0000310L 00019 10L 00010 10L 0000410L 00013 10L 00012 10L 0000410L 00019 46L 00007 10L 0000246L 00025 46L 00022 46L 0000246L 00025 46L 00005 46L 0000646L 00008 46L 00007 46L 0000246L 00011 12L 00010 46L 0000264L 00005 12L 00017 3L 29100064L 00005 12L 00010 3L 32000064L 00006 12L 00009 26L 0000564L 00007 26L 00007 26L 0000512L 00012 26L 0000712L 0001312L 0001312L 0001226L 0000526L 00006

Sample Soil 3 Sample Soil 3 Sample Soil 3Element PBD 153 Element PBD 154 Element PBD 196

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]44L 00050 4L 00010 46L 0000744L 00050 46L 00001 46L 0001146L 00002 46L 00002 46L 0000846L 00003 46L 00001 46L 0001146L 00002 46L 00002 64L 0002646L 00002 64L 00001 64L 0002664L 00001 64L 00001 64L 0002964L 00001 64L 00001 64L 0003464L 00001 64L 00002 12L 0004564L 00002 12L 00003 12L 00032

12L 00002 12L 0002212L 00002 12L 0002112L 00002

Sample Soil 3 Sample Soil 3 Sample Soil 3Element PBD 197 Element PBD 203 Element PBD 209

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00006 46L 00011 4L 0091046L 00013 46L 00017 4L 0150046L 00011 46L 00015 4L 0120046L 00013 46L 00018 4L 0160012L 00090 64L 00013 44L 0337012L 00056 64L 00014 44L 0281012L 00033 64L 00016 44L 0287012L 00032 64L 00015 44L 02540

12L 00055 46L 0230012L 00041 46L 0220012L 00027 46L 0150012L 00026 46L 01900

64L 0438164L 0401664L 0414464L 0449812L 0367112L 0397812L 0409112L 03838

Sample Soil 3 26L 0102Element PBD 183 26L 0131

LAB PARM [mgkg]46L 0000746L 0000846L 0005846L 0000764L 0000264L 0000364L 0000364L 0000312L 0001512L 0001112L 0000712L 00007

European Commission EUR 23003 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on polybrominated diphenylethers Author(s) E Sobiecka H van der Sloot D Barcelo B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 68 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07403-5 Abstract Project HORIZONTAL is interdisciplinary aiming at a harmonisation and horizontal standardisation of test procedures in particular for sludge soils and biowastes In the context of this standardization project a series of draft technical specification were designed upon an extensive desk study fine-tuned after expert consultations and finally validated in international intercomparisons exercise This report summarises the work performed within the validation study of the draft standard for the determination of polybrominated diphenylethers (PBDE) in soils sludge and treated bio-waste using gas-chromatography method with mass selective detection (GC-MS) It further explains the underlying statistical concept for the calculation of reproducibility and repeatability from intercomparisons data In addition all single values results of the statistical evaluation as well as background information on the validation materials used are described and explained

The mission of the JRC is to provide customer-driven scientific and technical support for the conception development implementation and monitoring of EU policies As a service of the European Commission the JRC functions as a reference centre of science and technology for the Union Close to the policy-making process it serves the common interest of the Member States while being independent of special interests whether private or national

LB

-NA

-23003-EN

-C

8

Table 3 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Sludge D (1) 0135 41474 385 Sludge B (2) 0538 0034 30634 547 Sludge A (3) 0184 0037 31399 146 Sludge C (4) 0354 1528 6678 229

Table 4 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Sludge 2

(B)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

554

959

694

591

772

509

nq

nq

970

2216

2379

Table 5 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena IES Ispra Spain) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Sludge 1 (D) 265 290 533 359 1231 338 784 438 lt 005 232 786 Sludge 2 (B) 119 311 626 202 278 299 722 251 lt 005 118 625 Sludge 3 (A) 168 360 621 332 847 416 119 451 lt 005 116 1237 Sludge 4 (C) 563 198 116 273 726 511 473 618 lt 005 444 2015

Table 6 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Sludge 1 (D) 2154 58 844 099 103 101 4367 lt15 50448 Sludge 2 (B) 1067 366 692 046 1491 077 5217 lt15 57633 Sludge 3 (A) 731 663 684 035 1287 068 3733 lt15 60369 Sludge 4 (C) 4379 965 527 163 522 107 5628 lt15 23945

Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM)Sludge 1 (D) 03 2403 101 1002 350 15 1944 132Sludge 2 (B) 031 315 97 879 172 12 514 180Sludge 3 (A) 031 1281 153 1567 265 16 1440 168Sludge 4 (C) 055 231 628 2625 371 81 1101 244

9

22 Agricultural soil material from Reading United Kingdom

The material was proposed by the University of Reading (S Nortcliff) and was sampled from a site called ldquoFrogmore Farmrdquo which was featured in the ldquoMetalsrdquo Report for HORIZONTAL This site is close to Reading with soils developed on flintyloamy periglacial materials over Chalk has a long and well documented history of sludge application The focus of the work of Nortcliff et al undertook at this site and the monitoring and control at the site (by Thames Water and the subsequent subsidiary bodies dealing with sludge application to soil) was on metals (and metal loads) with no analysis or indeed any form of investigation in to organics in the broadest sense

The analytical information produced in the context of the screening of the raw material is displayed below

Table 7 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 3

(Reading) 0032 0119 669

Table 8 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 3 (Reading) 015 706 279 138 152 901 267 300 lt 005 258 931

Table 9 ndash Analytical data obtained on a first screening on the sludge-amended soil from Reading (courtesy of IRMM)

Parameter Concentration

PCB ngg 28 lt1 52 lt1 101 lt1 118 lt1 153 lt1 105 lt1 138 lt1 156 lt1 180 lt1 170 lt1 PAH ngg Naphtalene lt10 Acenaphtylene 21 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene lt10 Flouranthene 818 Pyrene 776 Benz(a)anthracene 565

10

Parameter Concentration

Chrysene 608 Benz(b)fluoranthene 824 Benz(k)fluoranthene 329 Benz(a)pyrene 799 Indeno(123-cd)pyrene

779

Dibenzo(ah)anthracene 118 Benzo(ghi)perylene 394

Table 10 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 3

(Reading)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

103

003

nq

nq

nq

nd

nd

272

273

Table 11 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 3 (Reading) 015 706 279 138 152 901 267 300 lt 005 258 931

Table 12 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 3 (Reading) 7936 477 112 096 194 017 4107 443 2102 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 3 (Reading) 042 13 45 69 69 69 216 92

Table 13 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 3 (Reading) 012

11

23 Compost from Vienna Austria

The fresh compost material was obtained from the Austrian Federal Environment Agency (UBA Vienna) which had used a sub-batch of the raw material for national intercomparson The remainder of the material was stored at 4degC until shipment to IRMM for further processing The following analytical information was provided by UBA Austria and completed with various screenings

Table 14 ndash Analytical data on compost material received from UBA Austria Inorganic and sum parameters

Parameter Unit Sample fraction used Observed mean B CAT mgl FM Fresh sample lt10mm 61 K CAT mgl FM Fresh sample lt10mm 2624 Mg CAT mgl FM Fresh sample lt10mm 242 P CAT mgl FM Fresh sample lt10mm 49 B CAT DM Fresh sample lt10mm 00017 K CAT DM Fresh sample lt10mm 072 Mg CAT DM Fresh sample lt10mm 007 P CAT DM Fresh sample lt10mm 001 NO3-N mgkg FM Fresh sample lt10mm 35 NH4-N mgkg FM Fresh sample lt10mm 230 Ctotal DM lt45degdry milled 29 Corg DM lt45degdry milled 27 Ntotal DM lt45degdry milled 17 P mgkg DM lt45degdry milled 2596 K mgkg DM lt45degdry milled 11019 K DM lt45degdry milled 110 B mgkg DM lt45degdry milled 60 Cd mgkg DM lt45degdry milled 046 Cr mgkg DM lt45degdry milled 25 Cu mgkg DM lt45degdry milled 46 Hg mgkg DM lt45degdry milled 020 Ni mgkg DM lt45degdry milled 18 Pb mgkg DM lt45degdry milled 45 Zn mgkg DM lt45degdry milled 198 Ca mgkg DM lt45degdry milled 68776 Ca DM lt45degdry milled 69 Mo mgkg DM lt45degdry milled 08 S mgkg DM lt45degdry milled 2137 Fe mgkg DM lt45degdry milled 9959 Mn mgkg DM lt45degdry milled 418 Na mgkg DM lt45degdry milled 742 Co mgkg DM lt45degdry milled 41 AOX mgkg DM lt30deg dry milled 62

Table 15 ndash Analytical data on compost material received from UBA Austria Polycyclic aromatic hydrocarbons

PAH Unit Result Naphthaline microgkg DM 93 Acenaphthylene microgkg DM 86 Acenaphthene microgkg DM 5 Fluorene microgkg DM 80 Phenanthrene microgkg DM 89 Anthracene microgkg DM 27 Fluoranthene microgkg DM 487 Pyrene microgkg DM 380

12

PAH Unit Result Benzo(a)anthracene microgkg DM 278 Chrysene microgkg DM 317 Benzo(b)fluoranthene microgkg DM 365 Benzo(k)fluoranthene microgkg DM 193 Benz(a)pyrene microgkg DM 320 Indeno(123-cd)pyrene microgkg DM 233 Dibenz(ah)anthracene microgkg DM 67 Benzo(ghi)perylene microgkg DM 225 Sum EPA microgkg DM 3013 Sum EPA mgkg DM 30

Table 16 ndash Analytical data on compost material received from UBA Austria Sum PCDDs and PCBs

Parameter

Dioxine TEQ (ITEF) ngkg DM 73 TEQ (WHO) ngkg DM 35 PCB Σ Ballschmiter mgkg DM 005

Table 17 ndash Analytical data on compost material obtained by screening in IRMM

Parameter Result in ngg

PCB 28 2 52 2 101 4 118 3 153 10 105 1 138 8 156 1 180 5 170 lt1 PAH Naphtalene lt10 Acenaphtylene lt10 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene 26 Fluoranthene 611 Pyrene 510 Benz(a)anthracene 888 Chrysene 957 Benz(b)fluoranthene 1531 Benz(k)fluoranthene 547 Benz(a)pyrene 1101 Indeno(123-cd)pyrene 416 Dibenzo(ah)anthracene 81 Benzo(ghi)perylene 295

13

Table 18 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Compost 1

(Vienna)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

402

019

259

nq

023

004

nq

nq

144

174

259

Table 19 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Compost 1

(Vienna) 0058 1426 557

Table 20 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Compost 1 (Vienna) 039 736 319 410 365 127 495 004 079 013 208

Table 21 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Compost 1 (Vienna) 2063 431 617 426 199 249 1602 lt15 10521

Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Compost 1 (Vienna) 035 3496 81 375 79 55 653 60

Table 22 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Compost 1 (Vienna) 017

14

24 Agricultural soil sludge amended soil from Pavia Italy

This sludge-amended soil material was obtained during a monitoring campaign which aimed at a generic description of the over-all soil quality in Pavia Province Italy The material which was collected from the upper horizon originates from a small farm called ldquoCascina Novellordquo During the characterisation of the site the following analytical information was obtained on a pooled sample of a sub-area of the farm of 20 X 20 m2

Table 23 ndash Analytical data on Pavia soil

Parameter Result Al 713 Wgt As 224 mgkg Cd 079 mgkg Cr 59 mgkg Cu 308 mgkg Hg 008 mgkg Ni 344 mgkg Pb 246 mgkg Zn 95 mgkg C 091 Wgt 2378-TCDD 0047 pgg 12378-PeCDD 015 pgg 123478-HxCDD 019 pgg 123678-HxCDD 15 pgg 123789-HxCDD 074 pgg 1234678-HpCDD 26 pgg OCDD 382 pgg 2378-TCDF 068 pgg 12378-PeCDF 053 pgg 23478-PeCDF 071 pgg 123478-HxDF 100 pgg 123678-HxDF 066 pgg 234678-HxDF 16 pgg 123789-HxDF 027 pgg 1234678-HpDF 12 pgg 1234789-HpDF 068 pgg OCDF 33 pgg I-TEQ 20 pgg WHO-TEQ 17 pgg

In addition the screening performed at IRMM did not reveal significant quantities of PCBs and PAHs which were all below the LoDs (1 ngg for PCBs and 10 ngg for PAHs respectively)

Table 24 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 5 (Pavia) 0005 0011 154

15

Table 25 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 5

(Pavia)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

039

nq

nq

008

nq

nd

nd

670

671

Table 26 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 5 (Pavia) 033 184 573 225 426 305 206 200 lt 005 381 878

Table 27 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 5 (Pavia) 6939 129 145 224 425 116 6118 255 1789 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 5 (Pavia) 184 62 38 108 55 66 597 110

Table 28 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 5 (Pavia) 006

16

25 Sludge-amended-soil from Barcelona Spain

The sludge-amended soil material from Barcelona sampled upon indication from the Barcelorsquo- Group in Barcelona

Table 29 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 2 (Lleida T) 0015 0183 1138

Table 30 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 2

(Lleida T)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

159

045

nq

048

160

nq

nq

1000

1004

Table 31 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 2 (Lleida T) 059 141 327 536 405 186 184 224 lt 005 318 111

Table 32 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 2 (Lleida T) 4443 1067 1429 253 344 204 4116 780 3396 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 2 (Lleida T) 064 65 26 125 59 17 547 65

Table 33 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 2 (Lleida T) 010

17

26 Sludge amended soil from Essen Germany

The German sludge-amended soil from Essen which was provided as the three sludge materials by LUA NRW did not feature significant concentrations of the PCB congeners 28 52 101 118 153 105 138 156 180 170 but had detectable amounts of some PAHs

Table 34 ndash Analytical screening data on the German sludge-amended soil

Parameter Concentration(ngg)

Naphtalene lt10 Acenaphtylene lt10 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene lt10 Fluoranthene 28 Pyrene 20 Benz(a)anthracene 24 Chrysene 47 Benz(b)fluoranthene 76 Benz(k)fluoranthene 20 Benz(a)pyrene 35 Indeno(123-cd)pyrene 35 Dibenzo(ah)anthracene 10 Benzo(ghi)perylene 26

Table 35 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 4 (Essen) 0011 0302 055

Table 36 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 4

(Essen)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

nq

nq

nq

nq

nq

nq

128

191

203

18

Table 37 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 4 (Essen) 052 545 261 805 320 403 273 273 lt 005 295 781

Table 38 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 4 (Essen) 7947 442 085 06 086 007 2163 189 2019 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 4 (Essen) 045 19 42 87 683 60 462 61

Table 39 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 4 (Essen) 004

27 Long-term sludge exposed soil from Hohenheim-Stuttgart Germany

Similarly an additional sludge exposed soil was sampled at the University of Hohenheim Stuttgart were a test soil was long-term exposed to elevated concentrations of sewage sludge

Table 40 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 1 (Stuttgart) 0045 0263 1765

Table 41 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 1

(Stuttgart)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

230

006

004

004

nq

nd

nd

498

500

19

Table 42 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 1 (Stuttgart) 069 127 361 262 504 183 252 262 lt 005 266 142

Table 43 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 1 (Stuttgart) 7194 1006 133 186 366 088 7874 275 3571 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 1 (Stuttgart) 123 50 47 212 85 69 991 129

Table 44 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 1 (Stuttgart) 177

18

Annex 3

Statistical calculations

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 47)Mandels h statistics(Sludge 1 - PBD 47)

Sample Sludge 1 NUM

Element PBD 47

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00213 0001 3 -021 005 - - 10L - - NUM46L 00273 0002 4 016 021 - - 46L - - NUM64L 00059 0000 4 -116 002 NUM - 64L - - NUM12L 00188 0000 4 -036 002 - - 12L - - NUM26L 00499 0024 2 157 223 Fail - - 26L - - NUM

Totgem 0025 0005 mgkg 1-level 172 (185) NUM (10L46L64L12L26L) -1Totstd= 0016 0010 5-level 157 (162) 5

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 5 Labs rejected (10L46L64L12L26L)

000 050 100 150 200 250

k-values

10L

46L

64L

12L

26L

Mandels k statistics(Sludge 1 - PBD 47)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

10L

46L

64L

12L

26L

Labo

rato

ries

NUM

-200 -100 000 100 200

h-values

10L

46L

64L

12L

26L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 47)

Sludge 1-PBD 47

Unit mgkg

Mandels k statistics(Soil 3 - PBD 47)Mandels h statistics(Soil 3 - PBD 47)

Sample Soil 3 Soil 3 - PBD 47 -- Mean PARM = 0001 [mgkg]

Element PBD 47

General calcparmT1= 134814E-02T2= 142830E-05T3= 13T4= 45T5= 22767E-06

n= variabelp= 4

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean26L 00007 0000 2 -143 001 00007 00000 2 1 00046L 00010 0001 4 010 181 00010 00008 4 3 00010L 00011 0000 3 049 023 00011 00001 3 2 00012L 00012 0000 4 084 081 00012 00004 4 3 000

Totgem 0001 0000 mgkg 1-level 149 (177) 4 00010 () 4 3Totstd= 0000 0000 5-level 142 (159)

RESULTS Mean = 000100 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000050 --gt 5031 r = 00014Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000050 --gt 5031 R = 00014Remarks none

000 050 100 150 200

k-values

26L

46L

10L

12L

Mandels k statistics(Soil 3 - PBD 47)

00 00 00 00 00 00 00 00 00 00 00

Deviation from Mean

26L

46L

10L

12L

Labo

rato

ries

Soil 3 - PBD 47 -- Mean PARM = 0001 [mgkg]

-200 -100 000 100

h-values

26L

46L

10L

12L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 47)

Soil 3-PBD 47

Unit mgkg

Mandels k statistics(Compost 1 - PBD 99)Mandels h statistics(Compost 1 - PBD 99)

Sample Compost 1 Compost 1 - PBD 99 -- Mean PARM = 0003 [mgkg]

Element PBD 99

General calcparmT1= 492124E-02T2= 148747E-04T3= 17T4= 61T5= 93196E-06

n= variabelp= 5

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00020 0000 4 -137 053 00020 00004 4 3 000

26L 00025 0000 2 -058 024 00025 00002 2 1 00010L 00029 0000 3 012 032 00029 00003 3 2 00046L 00033 0001 4 069 161 00033 00013 4 3 00012L 00036 0001 4 114 140 00036 00011 4 3 000

Totgem 0003 0001 mgkg 1-level 172 (185) 5 00029 () 5 4Totstd= 0001 0001 5-level 157 (162)

RESULTS Mean = 000286 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000088 --gt 3086 r = 00025Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000101 --gt 3525 R = 00028Remarks none

000 050 100 150 200

k-values

4L

26L

10L

46L

12L

Mandels k statistics(Compost 1 - PBD 99)

00 00 00 00 00 00 00 00 00 00

Deviation from Mean

4L

26L

10L

46L

12L

Labo

rato

ries

Compost 1 - PBD 99 -- Mean PARM = 0003 [mgkg]

-200 -100 000 100 200

h-values

4L

26L

10L

46L

12L

Labo

rato

ries

Mandels h statistics(Compost 1 - PBD 99)

Compost 1-PBD 99

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 99)Mandels h statistics(Sludge 1 - PBD 99)

Sample Sludge 1 Sludge 1 - PBD 99 -- Mean PARM = 0024 [mgkg]

Element PBD 99

General calcparmT1= 448050E-01T2= 112113E-02T3= 19T4= 73T5= 32972E-05

n= variabelp= 5

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean64L 00173 0002 4 -118 041 Fail 00173 00019 4 3 -0014L 00183 0002 4 -104 032 00183 00015 4 3 -001

12L 00227 0001 4 -038 022 00227 00010 4 3 00010L 00290 0001 3 055 021 00290 00010 3 2 00146L 00320 0002 4 100 039 00320 00018 4 3 00126L 00323 0011 2 105 234 - - 26L - - 001

Totgem 0025 0003 mgkg 1-level 187 (177) 5 00239 (26L) 5 4Totstd= 0007 0004 5-level 166 (154) 1

RESULTS Mean = 002385 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000153 --gt 643 r = 00043Between lab variance S2L = 000004Reproducibility var S2R = 000004Reproducibility std SR = 000666 --gt 2791 R = 00186Remarks 1 Lab rejected (26L)

000 050 100 150 200 250

k-values

64L

4L

12L

10L

46L

26L

Mandels k statistics(Sludge 1 - PBD 99)

00 00 00 00 00 00 00 00 00 00

Deviation from Mean

64L

4L

12L

10L

46L

26L

Labo

rato

ries

Sludge 1 - PBD 99 -- Mean PARM = 0024 [mgkg]

-200 -100 000 100 200

h-values

64L

4L

12L

10L

46L

26L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 99)

Sludge 1-PBD 99

Unit mgkg

Mandels k statistics(Soil 3 - PBD 99)Mandels h statistics(Soil 3 - PBD 99)

Sample Soil 3 NUM

Element PBD 99

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00017 0000 4 091 068 - - 10L - - NUM46L 00017 0001 4 100 211 - - 46L - - NUM64L 00005 0000 4 -106 023 NUM - 64L - - NUM12L 00012 0000 4 015 014 - - 12L - - NUM26L 00006 0000 2 -101 012 - - 26L - - NUM

Totgem 0001 0000 mgkg 1-level 172 (173) NUM (10L46L64L12L26L) -1Totstd= 0001 0000 5-level 157 (153) 5

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 5 Labs rejected (10L46L64L12L26L)

000 050 100 150 200 250

k-values

10L

46L

64L

12L

26L

Mandels k statistics(Soil 3 - PBD 99)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

10L

46L

64L

12L

26L

Labo

rato

ries

NUM

-200 -100 000 100 200

h-values

10L

46L

64L

12L

26L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 99)

Soil 3-PBD 99

Unit mgkg

Mandels k statistics(Compost 1 - PBD 100)Mandels h statistics(Compost 1 - PBD 100)

Sample Compost 1 Compost 1 - PBD 100 -- Mean PARM = 0001 [mgkg]

Element PBD 100

General calcparmT1= 124272E-02T2= 113129E-05T3= 14T4= 52T5= 46584E-07

n= variabelp= 4

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean26L 00006 0000 2 -131 037 Fail 00006 00001 2 1 00010L 00009 0000 4 003 083 00009 00002 4 3 00046L 00009 0000 4 016 115 00009 00002 4 3 00012L 00011 0000 4 112 136 Fail 00011 00003 4 3 000

Totgem 0001 0000 mgkg 1-level 149 (167) 4 00009 () 4 3Totstd= 0000 0000 5-level 142 (15)

RESULTS Mean = 000085 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000022 --gt 2531 r = 00006Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000025 --gt 2882 R = 00007Remarks none

000 050 100 150

k-values

26L

10L

46L

12L

Mandels k statistics(Compost 1 - PBD 100)

00 00 00 00 00 00 00 00 00 00 00

Deviation from Mean

26L

10L

46L

12L

Labo

rato

ries

Compost 1 - PBD 100 -- Mean PARM = 0001 [mgkg]

-200 -100 000 100 200

h-values

26L

10L

46L

12L

Labo

rato

ries

Mandels h statistics(Compost 1 - PBD 100)

Compost 1-PBD 100

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 100)Mandels h statistics(Sludge 1 - PBD 100)

Sample Sludge 1 Sludge 1 - PBD 100 -- Mean PARM = 0005 [mgkg]

Element PBD 100

General calcparmT1= 852065E-02T2= 412762E-04T3= 18T4= 68T5= 78914E-07

n= variabelp= 5

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00039 0000 4 -042 007 Fail 00039 00002 4 3 000

12L 00044 0000 4 -041 005 Fail 00044 00001 4 3 00010L 00046 0000 4 -041 013 Fail 00046 00003 4 3 00046L 00056 0000 4 -040 012 Fail 00056 00003 4 3 00026L 00059 0000 2 -040 013 Fail 00059 00003 2 1 00038L 02168 0006 4 204 244 Fail - - 38L - - 021

Totgem 0040 0001 mgkg 1-level 187 (177) 5 00049 (38L) 5 4Totstd= 0087 0002 5-level 166 (154) 1

RESULTS Mean = 000486 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000025 --gt 507 r = 00007Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000084 --gt 1731 R = 00024Remarks 1 Lab rejected (38L)

000 050 100 150 200 250

k-values

4L

12L

10L

46L

26L

38L

Mandels k statistics(Sludge 1 - PBD 100)

-01 00 01 01 02 02 03

Deviation from Mean

4L

12L

10L

46L

26L

38L

Labo

rato

ries

Sludge 1 - PBD 100 -- Mean PARM = 0005 [mgkg]

-100 000 100 200 300

h-values

4L

12L

10L

46L

26L

38L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 100)

Sludge 1-PBD 100

Unit mgkg

Mandels k statistics(Soil 3 - PBD 100)Mandels h statistics(Soil 3 - PBD 100)

Sample Soil 3 NUM

Element PBD 100

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00003 0000 4 -050 000 Fail - - 10L - - NUM46L 00003 0000 4 -050 000 Fail NUM - 46L - - NUM3L 305500 2051 2 150 200 Fail - - 3L - - NUM

26L 00005 0000 2 -050 000 Fail - - 26L - - NUM

Totgem 7638 0513 mgkg 1-level 149 (177) NUM (10L46L3L26L) -1Totstd= 15275 1025 5-level 142 (159) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (10L46L3L26L)

000 050 100 150 200

k-values

10L

46L

3L

26L

Mandels k statistics(Soil 3 - PBD 100)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

10L

46L

3L

26L

Labo

rato

ries

NUM

-100 000 100 200

h-values

10L

46L

3L

26L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 100)

Soil 3-PBD 100

Unit mgkg

Mandels k statistics(Compost 1 - PBD 153)Mandels h statistics(Compost 1 - PBD 153)

Sample Compost 1 NUM

Element PBD 153

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean44L 00053 0001 3 150 157 Fail - - 44L - - NUM46L 00007 0000 4 -044 111 Fail - - 46L - - NUM12L 00005 0000 4 -051 055 Fail - - 12L - - NUM26L 00005 0000 2 -054 001 Fail NUM - 26L - - NUM

Totgem 0002 0000 mgkg 1-level 149 (177) NUM (44L46L12L26L) -1Totstd= 0002 0000 5-level 142 (159) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (44L46L12L26L)

000 050 100 150 200

k-values

44L

46L

12L

26L

Mandels k statistics(Compost 1 - PBD 153)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

44L

46L

12L

26L

Labo

rato

ries

NUM

-100 000 100 200

h-values

44L

46L

12L

26L

Labo

rato

ries

Mandels h statistics(Compost 1 - PBD 153)

Compost 1-PBD 153

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 153)Mandels h statistics(Sludge 1 - PBD 153)

Sample Sludge 1 Sludge 1 - PBD 153 -- Mean PARM = 0004 [mgkg]

Element PBD 153

General calcparmT1= 676738E-02T2= 267609E-04T3= 18T4= 68T5= 19626E-05

n= variabelp= 5

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00024 0000 4 -157 017 00024 00002 4 3 000

12L 00038 0002 4 006 154 00038 00018 4 3 00046L 00039 0000 4 011 026 00039 00003 4 3 00026L 00039 0000 2 018 004 00039 00000 2 1 00064L 00049 0002 4 122 159 00049 00018 4 3 000

Totgem 0004 0001 mgkg 1-level 172 (173) 5 00038 () 5 4Totstd= 0001 0001 5-level 157 (153)

RESULTS Mean = 000378 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000123 --gt 3252 r = 00034Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000142 --gt 3754 R = 00040Remarks none

000 050 100 150 200

k-values

4L

12L

46L

26L

64L

Mandels k statistics(Sludge 1 - PBD 153)

00 00 00 00 00 00 00

Deviation from Mean

4L

12L

46L

26L

64L

Labo

rato

ries

Sludge 1 - PBD 153 -- Mean PARM = 0004 [mgkg]

-200 -100 000 100 200

h-values

4L

12L

46L

26L

64L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 153)

Sludge 1-PBD 153

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 154)Mandels h statistics(Sludge 1 - PBD 154)

Sample Sludge 1 NA

Element PBD 154

General calcparmT1= NAT2= NAT3=T4=T5=

n= variabelp=

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00021 0000 3 -100 021 NA - 4L - - NA

46L 00025 0000 4 115 018 NA - 46L - - NA64L 00021 0001 4 -066 179 - - 64L - - NA12L 00023 0000 4 050 085 - - 12L - - NA

Totgem 0002 0000 mgkg 1-level 149 (167) NA (4L46L64L12L) -1Totstd= 0000 0000 5-level 142 (15) 4

RESULTS Mean = NA mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NAReproducibility var S2R = NAReproducibility std SR = NA --gt NA R = NARemarks 4 Labs rejected (4L46L64L12L)

000 050 100 150 200

k-values

4L

46L

64L

12L

Mandels k statistics(Sludge 1 - PBD 154)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

4L

46L

64L

12L

Labo

rato

ries

NA

-100 000 100 200

h-values

4L

46L

64L

12L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 154)

Sludge 1-PBD 154

Unit mgkg

Mandels k statistics(Soil 3 - PBD 154)Mandels h statistics(Soil 3 - PBD 154)

Sample Soil 3 NUM

Element PBD 154

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

4L 00010 - 1 150 Fail - - 4L - - NUM46L 00001 0000 4 -053 096 Fail - - 46L - - NUM64L 00001 0000 4 -056 105 Fail NUM - 64L - - NUM12L 00002 0000 4 -040 099 Fail - - 12L - - NUM

Totgem 000037 0000 mgkg 1-level 149 (164) NUM (4L46L64L12L) -1Totstd= 000042 0000 5-level 142 (153) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (4L46L64L12L)

000 050 100 150

k-values

4L

46L

64L

12L

Mandels k statistics(Soil 3 - PBD 154)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

4L

46L

64L

12L

Labo

rato

ries

NUM

-100 000 100 200

h-values

4L

46L

64L

12L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 154)

Soil 3-PBD 154

Unit mgkg

Mandels k statistics(Compost 1 - PBD 209)Mandels h statistics(Compost 1 - PBD 209)

Sample Compost 1 NUM

Element PBD 209

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00065 0003 2 -049 032 - - 4L - - NUM

44L 00573 0021 4 150 197 Fail - - 44L - - NUM12L 00078 0001 4 -045 011 - - 12L - - NUM26L 00049 0000 2 -056 000 NUM - 26L - - NUM

Totgem 0019 0006 mgkg 1-level 149 (177) NUM (4L44L12L26L) -1Totstd= 0025 0010 5-level 142 (159) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (4L44L12L26L)

000 050 100 150 200

k-values

4L

44L

12L

26L

Mandels k statistics(Compost 1 - PBD 209)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

4L

44L

12L

26L

Labo

rato

ries

NUM

-100 000 100 200

h-values

4L

44L

12L

26L

Labo

rato

ries

Mandels h statistics(Compost 1 - PBD 209)

Compost 1-PBD 209

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 209)Mandels h statistics(Sludge 1 - PBD 209)

Sample Sludge 1 Sludge 1 - PBD 209 -- Mean PARM = 0249 [mgkg]

Element PBD 209

General calcparmT1= 394542E+00T2= 107296E+00T3= 16T4= 56T5= 19723E-02

n= variabelp= 5

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 01550 0055 4 -112 148 Fail 01550 00551 4 3 -009

46L 02050 0007 2 -053 019 02050 00071 2 1 -00412L 02137 0058 4 -042 155 02137 00576 4 3 -00426L 03149 0021 2 078 057 Fail 03149 00210 2 1 00764L 03577 0007 4 129 020 Fail 03577 00074 4 3 011

Totgem 0249 0030 mgkg 1-level 172 (185) 5 02493 () 5 4Totstd= 0084 0025 5-level 157 (162)

RESULTS Mean = 024926 mgkg

Repeatability variance S2r = 000179Repeatability std Sr = 004234 --gt 1699 r = 01186Between lab variance S2L = 000743Reproducibility var S2R = 000922Reproducibility std SR = 009604 --gt 3853 R = 02689Remarks none

000 050 100 150 200

k-values

4L

46L

12L

26L

64L

Mandels k statistics(Sludge 1 - PBD 209)

-01 -01 00 01 01 02

Deviation from Mean

4L

46L

12L

26L

64L

Labo

rato

ries

Sludge 1 - PBD 209 -- Mean PARM = 0249 [mgkg]

-200 -100 000 100 200

h-values

4L

46L

12L

26L

64L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 209)

Sludge 1-PBD 209

Unit mgkg

Mandels k statistics(Soil 3 - PBD 209)Mandels h statistics(Soil 3 - PBD 209)

Sample Soil 3 Soil 3 - PBD 209 -- Mean PARM = 0258 [mgkg]

Element PBD 209

General calcparmT1= 596398E+00T2= 191917E+00T3= 22T4= 84T5= 13249E-02

n= variabelp= 6

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean26L 01162 0021 2 -108 074 Fail 01162 00207 2 1 -0144L 01303 0031 4 -097 111 Fail 01303 00312 4 3 -013

46L 01975 0036 4 -046 128 Fail 01975 00359 4 3 -00644L 02898 0035 4 024 124 Fail 02898 00346 4 3 00312L 03895 0018 4 100 065 Fail 03895 00181 4 3 01364L 04260 0022 4 127 078 Fail 04260 00219 4 3 017

Totgem 0258 0027 mgkg 1-level 187 (177) 6 02582 () 6 5Totstd= 0132 0008 5-level 166 (154)

RESULTS Mean = 025818 mgkg

Repeatability variance S2r = 000083Repeatability std Sr = 002878 --gt 1115 r = 00806Between lab variance S2L = 001640Reproducibility var S2R = 001723Reproducibility std SR = 013127 --gt 5084 R = 03676Remarks none

000 050 100 150

k-values

26L

4L

46L

44L

12L

64L

Mandels k statistics(Soil 3 - PBD 209)

-02 -01 -01 00 01 01 02 02

Deviation from Mean

26L

4L

46L

44L

12L

64L

Labo

rato

ries

Soil 3 - PBD 209 -- Mean PARM = 0258 [mgkg]

-200 -100 000 100 200

h-values

26L

4L

46L

44L

12L

64L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 209)

Soil 3-PBD 209

Unit mgkg

Mandels k statistics(Compost 1 - Sum PBD)Mandels h statistics(Compost 1 - Sum PBD)

Sample Compost 1 Compost 1 - Sum PBD -- Mean PARM = 0009 [mgkg]

Element Sum PBD

General calcparmT1= 154064E-01T2= 169065E-03T3= 18T4= 68T5= 11354E-04

n= variabelp= 5

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00031 0002 4 -067 016 00031 00016 4 3 -0014L 00055 0005 4 -056 048 00055 00047 4 3 000

46L 00085 0003 4 -042 031 00085 00030 4 3 00026L 00123 0000 2 -024 003 00123 00002 2 1 00012L 00154 0002 4 -011 021 00154 00021 4 3 00144L 00613 0023 4 200 237 Fail - - 44L - - 005

Totgem 0018 0006 mgkg 1-level 187 (177) 5 00089 (44L) 5 4Totstd= 0022 0009 5-level 166 (154) 1

RESULTS Mean = 000893 mgkg

Repeatability variance S2r = 000001Repeatability std Sr = 000296 --gt 3308 r = 00083Between lab variance S2L = 000002Reproducibility var S2R = 000003Reproducibility std SR = 000570 --gt 6374 R = 00159Remarks 1 Lab rejected (44L)

000 050 100 150 200 250

k-values

10L

4L

46L

26L

12L

44L

Mandels k statistics(Compost 1 - Sum PBD)

00 00 00 00 00 00 01 01

Deviation from Mean

10L

4L

46L

26L

12L

44L

Labo

rato

ries

Compost 1 - Sum PBD -- Mean PARM = 0009 [mgkg]

-100 000 100 200

h-values

10L

4L

46L

26L

12L

44L

Labo

rato

ries

Mandels h statistics(Compost 1 - Sum PBD)

Compost 1-Sum PBD

Unit mgkg

Mandels k statistics(Sludge 1 - Sum PBD)Mandels h statistics(Sludge 1 - Sum PBD)

Sample Sludge 1 Sludge 1 - Sum PBD -- Mean PARM = 0256 [mgkg]

Element Sum PBD

General calcparmT1= 531806E+00T2= 162188E+00T3= 22T4= 84T5= 25223E-02

n= variabelp= 6

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00423 0025 4 -156 044 Fail 00423 00252 4 3 -02146L 01808 0118 4 -049 205 - - 46L - - -0074L 01810 0056 4 -049 097 01810 00558 4 3 -007

38L 02168 0006 4 -022 010 02168 00059 4 3 -00412L 02890 0065 4 034 113 02890 00647 4 3 00364L 03958 0008 4 116 014 Fail 03958 00079 4 3 01426L 04094 0034 2 126 059 Fail 04094 00337 2 1 015

Totgem 0245 0044 mgkg 1-level 198 (179) 6 02557 (46L) 6 5Totstd= 0130 0039 5-level 171 (155) 1

RESULTS Mean = 025570 mgkg

Repeatability variance S2r = 000158Repeatability std Sr = 003970 --gt 1553 r = 01112Between lab variance S2L = 001807Reproducibility var S2R = 001964Reproducibility std SR = 014015 --gt 5481 R = 03924Remarks 1 Lab rejected (46L)

000 050 100 150 200 250

k-values

10L

46L

4L

38L

12L

64L

26L

Mandels k statistics(Sludge 1 - Sum PBD)

-03 -02 -02 -01 -01 00 01 01 02 02

Deviation from Mean

10L

46L

4L

38L

12L

64L

26L

Labo

rato

ries

Sludge 1 - Sum PBD -- Mean PARM = 0256 [mgkg]

-200 -100 000 100 200

h-values

10L

46L

4L

38L

12L

64L

26L

Labo

rato

ries

Mandels h statistics(Sludge 1 - Sum PBD)

Sludge 1-Sum PBD

Unit mgkg

Mandels k statistics(Soil 3 - Sum PBD)Mandels h statistics(Soil 3 - Sum PBD)

Sample Soil 3 Soil 3 - Sum PBD -- Mean PARM = 0227 [mgkg]

Element Sum PBD

General calcparmT1= 610980E+00T2= 200876E+00T3= 26T4= 100T5= 13106E-02

n= variabelp= 7

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00028 0001 4 -037 000 Fail 00028 00005 4 3 -02226L 01179 0021 2 -036 003 Fail 01179 00208 2 1 -0114L 01305 0031 4 -036 004 Fail 01305 00308 4 3 -010

46L 02065 0035 4 -036 005 Fail 02065 00350 4 3 -00244L 02923 0037 4 -035 005 Fail 02923 00365 4 3 00712L 04051 0015 4 -034 002 Fail 04051 00149 4 3 01864L 04314 0022 4 -033 003 Fail 04314 00223 4 3 0203L 305500 2051 2 247 283 Fail - - 3L - - 3032

Totgem 4017 0276 mgkg 1-level 206 (181) 7 02266 (3L) 7 6Totstd= 10722 0717 5-level 175 (156) 1

RESULTS Mean = 022663 mgkg

Repeatability variance S2r = 000069Repeatability std Sr = 002626 --gt 1159 r = 00735Between lab variance S2L = 002568Reproducibility var S2R = 002637Reproducibility std SR = 016238 --gt 7165 R = 04547Remarks 1 Lab rejected (3L)

000 050 100 150 200 250 300

k-values

10L

26L

4L

46L

44L

12L

64L

3L

Mandels k statistics(Soil 3 - Sum PBD)

-50 00 50 100 150 200 250 300 350

Deviation from Mean

10L

26L

4L

46L

44L

12L

64L

3L

Labo

rato

ries

Soil 3 - Sum PBD -- Mean PARM = 0227 [mgkg]

-100 000 100 200 300

h-values

10L

26L

4L

46L

44L

12L

64L

3L

Labo

rato

ries

Mandels h statistics(Soil 3 - Sum PBD)

Soil 3-Sum PBD

19

Annex 4

Raw data submitted

Sample Compost1 Sample Compost 1 Sample Compost 1Element PBD 99 Element PBD 100 Element PBD 153

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]4L 00021 10L 00008 44L 000504L 00024 10L 00008 44L 000604L 00014 10L 00007 44L 000504L 00020 10L 00011 46L 00004

10L 00029 46L 00007 46L 0001210L 00027 46L 00012 46L 0000410L 00032 46L 00009 46L 0000946L 00025 46L 00007 12L 0000446L 00052 12L 00008 12L 0000846L 00029 12L 00012 12L 0000446L 00026 12L 00008 12L 0000712L 00026 12L 00014 26L 0000512L 00043 26L 00007 26L 0000512L 00026 26L 0000612L 0004726L 0002626L 00024

Sample Compost 1 Sample Compost 1 Sample Compost 1Element PBD 154 Element PBD 183 Element PBD 196

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]4L 00010 46L 00002 46L 00011

46L 00003 46L 00024 46L 0000846L 00007 46L 00021 12L 0000246L 00003 46L 00003 12L 0000346L 00004 12L 00003 12L 0000112L 00003 12L 00011 12L 0000212L 00005 12L 0000312L 00031 12L 0000312L 00006

Sample Compost 1 Sample Compost 1 Sample Compost 1Element PBD 197 Element PBD 203 Element PBD 209

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00002 46L 00010 4L 0004146L 00023 12L 00002 4L 0008946L 00022 12L 00003 44L 0041012L 00004 12L 00002 44L 0084012L 00006 12L 00002 44L 0064012L 00003 44L 0040012L 00004 12L 00079

12L 0007312L 0006512L 0009326L 0004926L 00049

Sample Compost 1Element PBD 47

LAB PARM [mgkg]26L 0003826L 00039

Element PBD 99 Element PBD 47 Element PBD 209LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]

4L 00170 10L 00210 4L 010004L 00200 10L 00220 4L 018004L 00170 10L 00210 4L 012004L 00190 46L 00300 4L 0220010L 00280 46L 00280 46L 0210010L 00300 46L 00250 46L 0200010L 00290 46L 00260 64L 0351846L 00340 64L 00059 64L 0363846L 00330 64L 00057 64L 0364546L 00300 64L 00062 64L 0350846L 00310 64L 00060 12L 0220964L 00194 12L 00191 12L 0177164L 00154 12L 00187 12L 0292264L 00185 12L 00190 12L 0164664L 00159 12L 00186 26L 0329712L 00242 26L 00666 26L 0300012L 00223 26L 0033212L 0022112L 0022226L 0024626L 00400

Element PBD 203 Element PBD 197 Element PBD 196LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00022 46L 00027 46L 0002446L 00014 46L 00024 46L 0002264L 00036 12L 00161 64L 0005864L 00058 12L 00060 64L 0006512L 00063 12L 00061 12L 0004812L 00034 12L 00036 12L 0002512L 00038 12L 0003212L 00027 12L 00022

Element PBD 183 Element PBD 154 Element PBD 153LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00049 4L 00020 4L 0002246L 00035 4L 00022 4L 0002446L 00036 4L 00020 4L 0002246L 00034 46L 00025 4L 0002664L 00027 46L 00025 46L 0004064L 00023 46L 00025 46L 0004264L 00024 46L 00023 46L 0003564L 00020 64L 00034 46L 0003812L 00230 64L 00023 64L 0007412L 00032 64L 00017 64L 0004712L 00031 64L 00011 64L 0004612L 00030 12L 00030 64L 0003026L 00007 12L 00021 12L 0006526L 00008 12L 00021 12L 00029

12L 00021 12L 0003226L 00015 12L 0002926L 00019 26L 00039

26L 00040

Element PBD 100LAB PARM [mgkg]

4L 000384L 000414L 000374L 00038

38L 0219038L 0220038L 0208038L 0220010L 0004410L 0005010L 0004310L 0004646L 0005746L 0005946L 0005346L 0005312L 0004312L 0004512L 0004312L 0004326L 0006226L 00057

Sample Soil 3 Sample Soil 3 Sample Soil 3Element PBD 99 Element PBD 47 Element PBD 100

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]10L 00016 10L 00011 10L 0000310L 00019 10L 00010 10L 0000410L 00013 10L 00012 10L 0000410L 00019 46L 00007 10L 0000246L 00025 46L 00022 46L 0000246L 00025 46L 00005 46L 0000646L 00008 46L 00007 46L 0000246L 00011 12L 00010 46L 0000264L 00005 12L 00017 3L 29100064L 00005 12L 00010 3L 32000064L 00006 12L 00009 26L 0000564L 00007 26L 00007 26L 0000512L 00012 26L 0000712L 0001312L 0001312L 0001226L 0000526L 00006

Sample Soil 3 Sample Soil 3 Sample Soil 3Element PBD 153 Element PBD 154 Element PBD 196

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]44L 00050 4L 00010 46L 0000744L 00050 46L 00001 46L 0001146L 00002 46L 00002 46L 0000846L 00003 46L 00001 46L 0001146L 00002 46L 00002 64L 0002646L 00002 64L 00001 64L 0002664L 00001 64L 00001 64L 0002964L 00001 64L 00001 64L 0003464L 00001 64L 00002 12L 0004564L 00002 12L 00003 12L 00032

12L 00002 12L 0002212L 00002 12L 0002112L 00002

Sample Soil 3 Sample Soil 3 Sample Soil 3Element PBD 197 Element PBD 203 Element PBD 209

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00006 46L 00011 4L 0091046L 00013 46L 00017 4L 0150046L 00011 46L 00015 4L 0120046L 00013 46L 00018 4L 0160012L 00090 64L 00013 44L 0337012L 00056 64L 00014 44L 0281012L 00033 64L 00016 44L 0287012L 00032 64L 00015 44L 02540

12L 00055 46L 0230012L 00041 46L 0220012L 00027 46L 0150012L 00026 46L 01900

64L 0438164L 0401664L 0414464L 0449812L 0367112L 0397812L 0409112L 03838

Sample Soil 3 26L 0102Element PBD 183 26L 0131

LAB PARM [mgkg]46L 0000746L 0000846L 0005846L 0000764L 0000264L 0000364L 0000364L 0000312L 0001512L 0001112L 0000712L 00007

European Commission EUR 23003 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on polybrominated diphenylethers Author(s) E Sobiecka H van der Sloot D Barcelo B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 68 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07403-5 Abstract Project HORIZONTAL is interdisciplinary aiming at a harmonisation and horizontal standardisation of test procedures in particular for sludge soils and biowastes In the context of this standardization project a series of draft technical specification were designed upon an extensive desk study fine-tuned after expert consultations and finally validated in international intercomparisons exercise This report summarises the work performed within the validation study of the draft standard for the determination of polybrominated diphenylethers (PBDE) in soils sludge and treated bio-waste using gas-chromatography method with mass selective detection (GC-MS) It further explains the underlying statistical concept for the calculation of reproducibility and repeatability from intercomparisons data In addition all single values results of the statistical evaluation as well as background information on the validation materials used are described and explained

The mission of the JRC is to provide customer-driven scientific and technical support for the conception development implementation and monitoring of EU policies As a service of the European Commission the JRC functions as a reference centre of science and technology for the Union Close to the policy-making process it serves the common interest of the Member States while being independent of special interests whether private or national

LB

-NA

-23003-EN

-C

9

22 Agricultural soil material from Reading United Kingdom

The material was proposed by the University of Reading (S Nortcliff) and was sampled from a site called ldquoFrogmore Farmrdquo which was featured in the ldquoMetalsrdquo Report for HORIZONTAL This site is close to Reading with soils developed on flintyloamy periglacial materials over Chalk has a long and well documented history of sludge application The focus of the work of Nortcliff et al undertook at this site and the monitoring and control at the site (by Thames Water and the subsequent subsidiary bodies dealing with sludge application to soil) was on metals (and metal loads) with no analysis or indeed any form of investigation in to organics in the broadest sense

The analytical information produced in the context of the screening of the raw material is displayed below

Table 7 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 3

(Reading) 0032 0119 669

Table 8 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 3 (Reading) 015 706 279 138 152 901 267 300 lt 005 258 931

Table 9 ndash Analytical data obtained on a first screening on the sludge-amended soil from Reading (courtesy of IRMM)

Parameter Concentration

PCB ngg 28 lt1 52 lt1 101 lt1 118 lt1 153 lt1 105 lt1 138 lt1 156 lt1 180 lt1 170 lt1 PAH ngg Naphtalene lt10 Acenaphtylene 21 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene lt10 Flouranthene 818 Pyrene 776 Benz(a)anthracene 565

10

Parameter Concentration

Chrysene 608 Benz(b)fluoranthene 824 Benz(k)fluoranthene 329 Benz(a)pyrene 799 Indeno(123-cd)pyrene

779

Dibenzo(ah)anthracene 118 Benzo(ghi)perylene 394

Table 10 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 3

(Reading)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

103

003

nq

nq

nq

nd

nd

272

273

Table 11 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 3 (Reading) 015 706 279 138 152 901 267 300 lt 005 258 931

Table 12 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 3 (Reading) 7936 477 112 096 194 017 4107 443 2102 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 3 (Reading) 042 13 45 69 69 69 216 92

Table 13 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 3 (Reading) 012

11

23 Compost from Vienna Austria

The fresh compost material was obtained from the Austrian Federal Environment Agency (UBA Vienna) which had used a sub-batch of the raw material for national intercomparson The remainder of the material was stored at 4degC until shipment to IRMM for further processing The following analytical information was provided by UBA Austria and completed with various screenings

Table 14 ndash Analytical data on compost material received from UBA Austria Inorganic and sum parameters

Parameter Unit Sample fraction used Observed mean B CAT mgl FM Fresh sample lt10mm 61 K CAT mgl FM Fresh sample lt10mm 2624 Mg CAT mgl FM Fresh sample lt10mm 242 P CAT mgl FM Fresh sample lt10mm 49 B CAT DM Fresh sample lt10mm 00017 K CAT DM Fresh sample lt10mm 072 Mg CAT DM Fresh sample lt10mm 007 P CAT DM Fresh sample lt10mm 001 NO3-N mgkg FM Fresh sample lt10mm 35 NH4-N mgkg FM Fresh sample lt10mm 230 Ctotal DM lt45degdry milled 29 Corg DM lt45degdry milled 27 Ntotal DM lt45degdry milled 17 P mgkg DM lt45degdry milled 2596 K mgkg DM lt45degdry milled 11019 K DM lt45degdry milled 110 B mgkg DM lt45degdry milled 60 Cd mgkg DM lt45degdry milled 046 Cr mgkg DM lt45degdry milled 25 Cu mgkg DM lt45degdry milled 46 Hg mgkg DM lt45degdry milled 020 Ni mgkg DM lt45degdry milled 18 Pb mgkg DM lt45degdry milled 45 Zn mgkg DM lt45degdry milled 198 Ca mgkg DM lt45degdry milled 68776 Ca DM lt45degdry milled 69 Mo mgkg DM lt45degdry milled 08 S mgkg DM lt45degdry milled 2137 Fe mgkg DM lt45degdry milled 9959 Mn mgkg DM lt45degdry milled 418 Na mgkg DM lt45degdry milled 742 Co mgkg DM lt45degdry milled 41 AOX mgkg DM lt30deg dry milled 62

Table 15 ndash Analytical data on compost material received from UBA Austria Polycyclic aromatic hydrocarbons

PAH Unit Result Naphthaline microgkg DM 93 Acenaphthylene microgkg DM 86 Acenaphthene microgkg DM 5 Fluorene microgkg DM 80 Phenanthrene microgkg DM 89 Anthracene microgkg DM 27 Fluoranthene microgkg DM 487 Pyrene microgkg DM 380

12

PAH Unit Result Benzo(a)anthracene microgkg DM 278 Chrysene microgkg DM 317 Benzo(b)fluoranthene microgkg DM 365 Benzo(k)fluoranthene microgkg DM 193 Benz(a)pyrene microgkg DM 320 Indeno(123-cd)pyrene microgkg DM 233 Dibenz(ah)anthracene microgkg DM 67 Benzo(ghi)perylene microgkg DM 225 Sum EPA microgkg DM 3013 Sum EPA mgkg DM 30

Table 16 ndash Analytical data on compost material received from UBA Austria Sum PCDDs and PCBs

Parameter

Dioxine TEQ (ITEF) ngkg DM 73 TEQ (WHO) ngkg DM 35 PCB Σ Ballschmiter mgkg DM 005

Table 17 ndash Analytical data on compost material obtained by screening in IRMM

Parameter Result in ngg

PCB 28 2 52 2 101 4 118 3 153 10 105 1 138 8 156 1 180 5 170 lt1 PAH Naphtalene lt10 Acenaphtylene lt10 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene 26 Fluoranthene 611 Pyrene 510 Benz(a)anthracene 888 Chrysene 957 Benz(b)fluoranthene 1531 Benz(k)fluoranthene 547 Benz(a)pyrene 1101 Indeno(123-cd)pyrene 416 Dibenzo(ah)anthracene 81 Benzo(ghi)perylene 295

13

Table 18 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Compost 1

(Vienna)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

402

019

259

nq

023

004

nq

nq

144

174

259

Table 19 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Compost 1

(Vienna) 0058 1426 557

Table 20 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Compost 1 (Vienna) 039 736 319 410 365 127 495 004 079 013 208

Table 21 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Compost 1 (Vienna) 2063 431 617 426 199 249 1602 lt15 10521

Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Compost 1 (Vienna) 035 3496 81 375 79 55 653 60

Table 22 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Compost 1 (Vienna) 017

14

24 Agricultural soil sludge amended soil from Pavia Italy

This sludge-amended soil material was obtained during a monitoring campaign which aimed at a generic description of the over-all soil quality in Pavia Province Italy The material which was collected from the upper horizon originates from a small farm called ldquoCascina Novellordquo During the characterisation of the site the following analytical information was obtained on a pooled sample of a sub-area of the farm of 20 X 20 m2

Table 23 ndash Analytical data on Pavia soil

Parameter Result Al 713 Wgt As 224 mgkg Cd 079 mgkg Cr 59 mgkg Cu 308 mgkg Hg 008 mgkg Ni 344 mgkg Pb 246 mgkg Zn 95 mgkg C 091 Wgt 2378-TCDD 0047 pgg 12378-PeCDD 015 pgg 123478-HxCDD 019 pgg 123678-HxCDD 15 pgg 123789-HxCDD 074 pgg 1234678-HpCDD 26 pgg OCDD 382 pgg 2378-TCDF 068 pgg 12378-PeCDF 053 pgg 23478-PeCDF 071 pgg 123478-HxDF 100 pgg 123678-HxDF 066 pgg 234678-HxDF 16 pgg 123789-HxDF 027 pgg 1234678-HpDF 12 pgg 1234789-HpDF 068 pgg OCDF 33 pgg I-TEQ 20 pgg WHO-TEQ 17 pgg

In addition the screening performed at IRMM did not reveal significant quantities of PCBs and PAHs which were all below the LoDs (1 ngg for PCBs and 10 ngg for PAHs respectively)

Table 24 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 5 (Pavia) 0005 0011 154

15

Table 25 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 5

(Pavia)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

039

nq

nq

008

nq

nd

nd

670

671

Table 26 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 5 (Pavia) 033 184 573 225 426 305 206 200 lt 005 381 878

Table 27 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 5 (Pavia) 6939 129 145 224 425 116 6118 255 1789 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 5 (Pavia) 184 62 38 108 55 66 597 110

Table 28 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 5 (Pavia) 006

16

25 Sludge-amended-soil from Barcelona Spain

The sludge-amended soil material from Barcelona sampled upon indication from the Barcelorsquo- Group in Barcelona

Table 29 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 2 (Lleida T) 0015 0183 1138

Table 30 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 2

(Lleida T)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

159

045

nq

048

160

nq

nq

1000

1004

Table 31 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 2 (Lleida T) 059 141 327 536 405 186 184 224 lt 005 318 111

Table 32 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 2 (Lleida T) 4443 1067 1429 253 344 204 4116 780 3396 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 2 (Lleida T) 064 65 26 125 59 17 547 65

Table 33 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 2 (Lleida T) 010

17

26 Sludge amended soil from Essen Germany

The German sludge-amended soil from Essen which was provided as the three sludge materials by LUA NRW did not feature significant concentrations of the PCB congeners 28 52 101 118 153 105 138 156 180 170 but had detectable amounts of some PAHs

Table 34 ndash Analytical screening data on the German sludge-amended soil

Parameter Concentration(ngg)

Naphtalene lt10 Acenaphtylene lt10 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene lt10 Fluoranthene 28 Pyrene 20 Benz(a)anthracene 24 Chrysene 47 Benz(b)fluoranthene 76 Benz(k)fluoranthene 20 Benz(a)pyrene 35 Indeno(123-cd)pyrene 35 Dibenzo(ah)anthracene 10 Benzo(ghi)perylene 26

Table 35 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 4 (Essen) 0011 0302 055

Table 36 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 4

(Essen)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

nq

nq

nq

nq

nq

nq

128

191

203

18

Table 37 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 4 (Essen) 052 545 261 805 320 403 273 273 lt 005 295 781

Table 38 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 4 (Essen) 7947 442 085 06 086 007 2163 189 2019 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 4 (Essen) 045 19 42 87 683 60 462 61

Table 39 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 4 (Essen) 004

27 Long-term sludge exposed soil from Hohenheim-Stuttgart Germany

Similarly an additional sludge exposed soil was sampled at the University of Hohenheim Stuttgart were a test soil was long-term exposed to elevated concentrations of sewage sludge

Table 40 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 1 (Stuttgart) 0045 0263 1765

Table 41 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 1

(Stuttgart)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

230

006

004

004

nq

nd

nd

498

500

19

Table 42 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 1 (Stuttgart) 069 127 361 262 504 183 252 262 lt 005 266 142

Table 43 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 1 (Stuttgart) 7194 1006 133 186 366 088 7874 275 3571 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 1 (Stuttgart) 123 50 47 212 85 69 991 129

Table 44 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 1 (Stuttgart) 177

18

Annex 3

Statistical calculations

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 47)Mandels h statistics(Sludge 1 - PBD 47)

Sample Sludge 1 NUM

Element PBD 47

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00213 0001 3 -021 005 - - 10L - - NUM46L 00273 0002 4 016 021 - - 46L - - NUM64L 00059 0000 4 -116 002 NUM - 64L - - NUM12L 00188 0000 4 -036 002 - - 12L - - NUM26L 00499 0024 2 157 223 Fail - - 26L - - NUM

Totgem 0025 0005 mgkg 1-level 172 (185) NUM (10L46L64L12L26L) -1Totstd= 0016 0010 5-level 157 (162) 5

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 5 Labs rejected (10L46L64L12L26L)

000 050 100 150 200 250

k-values

10L

46L

64L

12L

26L

Mandels k statistics(Sludge 1 - PBD 47)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

10L

46L

64L

12L

26L

Labo

rato

ries

NUM

-200 -100 000 100 200

h-values

10L

46L

64L

12L

26L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 47)

Sludge 1-PBD 47

Unit mgkg

Mandels k statistics(Soil 3 - PBD 47)Mandels h statistics(Soil 3 - PBD 47)

Sample Soil 3 Soil 3 - PBD 47 -- Mean PARM = 0001 [mgkg]

Element PBD 47

General calcparmT1= 134814E-02T2= 142830E-05T3= 13T4= 45T5= 22767E-06

n= variabelp= 4

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean26L 00007 0000 2 -143 001 00007 00000 2 1 00046L 00010 0001 4 010 181 00010 00008 4 3 00010L 00011 0000 3 049 023 00011 00001 3 2 00012L 00012 0000 4 084 081 00012 00004 4 3 000

Totgem 0001 0000 mgkg 1-level 149 (177) 4 00010 () 4 3Totstd= 0000 0000 5-level 142 (159)

RESULTS Mean = 000100 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000050 --gt 5031 r = 00014Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000050 --gt 5031 R = 00014Remarks none

000 050 100 150 200

k-values

26L

46L

10L

12L

Mandels k statistics(Soil 3 - PBD 47)

00 00 00 00 00 00 00 00 00 00 00

Deviation from Mean

26L

46L

10L

12L

Labo

rato

ries

Soil 3 - PBD 47 -- Mean PARM = 0001 [mgkg]

-200 -100 000 100

h-values

26L

46L

10L

12L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 47)

Soil 3-PBD 47

Unit mgkg

Mandels k statistics(Compost 1 - PBD 99)Mandels h statistics(Compost 1 - PBD 99)

Sample Compost 1 Compost 1 - PBD 99 -- Mean PARM = 0003 [mgkg]

Element PBD 99

General calcparmT1= 492124E-02T2= 148747E-04T3= 17T4= 61T5= 93196E-06

n= variabelp= 5

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00020 0000 4 -137 053 00020 00004 4 3 000

26L 00025 0000 2 -058 024 00025 00002 2 1 00010L 00029 0000 3 012 032 00029 00003 3 2 00046L 00033 0001 4 069 161 00033 00013 4 3 00012L 00036 0001 4 114 140 00036 00011 4 3 000

Totgem 0003 0001 mgkg 1-level 172 (185) 5 00029 () 5 4Totstd= 0001 0001 5-level 157 (162)

RESULTS Mean = 000286 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000088 --gt 3086 r = 00025Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000101 --gt 3525 R = 00028Remarks none

000 050 100 150 200

k-values

4L

26L

10L

46L

12L

Mandels k statistics(Compost 1 - PBD 99)

00 00 00 00 00 00 00 00 00 00

Deviation from Mean

4L

26L

10L

46L

12L

Labo

rato

ries

Compost 1 - PBD 99 -- Mean PARM = 0003 [mgkg]

-200 -100 000 100 200

h-values

4L

26L

10L

46L

12L

Labo

rato

ries

Mandels h statistics(Compost 1 - PBD 99)

Compost 1-PBD 99

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 99)Mandels h statistics(Sludge 1 - PBD 99)

Sample Sludge 1 Sludge 1 - PBD 99 -- Mean PARM = 0024 [mgkg]

Element PBD 99

General calcparmT1= 448050E-01T2= 112113E-02T3= 19T4= 73T5= 32972E-05

n= variabelp= 5

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean64L 00173 0002 4 -118 041 Fail 00173 00019 4 3 -0014L 00183 0002 4 -104 032 00183 00015 4 3 -001

12L 00227 0001 4 -038 022 00227 00010 4 3 00010L 00290 0001 3 055 021 00290 00010 3 2 00146L 00320 0002 4 100 039 00320 00018 4 3 00126L 00323 0011 2 105 234 - - 26L - - 001

Totgem 0025 0003 mgkg 1-level 187 (177) 5 00239 (26L) 5 4Totstd= 0007 0004 5-level 166 (154) 1

RESULTS Mean = 002385 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000153 --gt 643 r = 00043Between lab variance S2L = 000004Reproducibility var S2R = 000004Reproducibility std SR = 000666 --gt 2791 R = 00186Remarks 1 Lab rejected (26L)

000 050 100 150 200 250

k-values

64L

4L

12L

10L

46L

26L

Mandels k statistics(Sludge 1 - PBD 99)

00 00 00 00 00 00 00 00 00 00

Deviation from Mean

64L

4L

12L

10L

46L

26L

Labo

rato

ries

Sludge 1 - PBD 99 -- Mean PARM = 0024 [mgkg]

-200 -100 000 100 200

h-values

64L

4L

12L

10L

46L

26L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 99)

Sludge 1-PBD 99

Unit mgkg

Mandels k statistics(Soil 3 - PBD 99)Mandels h statistics(Soil 3 - PBD 99)

Sample Soil 3 NUM

Element PBD 99

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00017 0000 4 091 068 - - 10L - - NUM46L 00017 0001 4 100 211 - - 46L - - NUM64L 00005 0000 4 -106 023 NUM - 64L - - NUM12L 00012 0000 4 015 014 - - 12L - - NUM26L 00006 0000 2 -101 012 - - 26L - - NUM

Totgem 0001 0000 mgkg 1-level 172 (173) NUM (10L46L64L12L26L) -1Totstd= 0001 0000 5-level 157 (153) 5

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 5 Labs rejected (10L46L64L12L26L)

000 050 100 150 200 250

k-values

10L

46L

64L

12L

26L

Mandels k statistics(Soil 3 - PBD 99)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

10L

46L

64L

12L

26L

Labo

rato

ries

NUM

-200 -100 000 100 200

h-values

10L

46L

64L

12L

26L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 99)

Soil 3-PBD 99

Unit mgkg

Mandels k statistics(Compost 1 - PBD 100)Mandels h statistics(Compost 1 - PBD 100)

Sample Compost 1 Compost 1 - PBD 100 -- Mean PARM = 0001 [mgkg]

Element PBD 100

General calcparmT1= 124272E-02T2= 113129E-05T3= 14T4= 52T5= 46584E-07

n= variabelp= 4

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean26L 00006 0000 2 -131 037 Fail 00006 00001 2 1 00010L 00009 0000 4 003 083 00009 00002 4 3 00046L 00009 0000 4 016 115 00009 00002 4 3 00012L 00011 0000 4 112 136 Fail 00011 00003 4 3 000

Totgem 0001 0000 mgkg 1-level 149 (167) 4 00009 () 4 3Totstd= 0000 0000 5-level 142 (15)

RESULTS Mean = 000085 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000022 --gt 2531 r = 00006Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000025 --gt 2882 R = 00007Remarks none

000 050 100 150

k-values

26L

10L

46L

12L

Mandels k statistics(Compost 1 - PBD 100)

00 00 00 00 00 00 00 00 00 00 00

Deviation from Mean

26L

10L

46L

12L

Labo

rato

ries

Compost 1 - PBD 100 -- Mean PARM = 0001 [mgkg]

-200 -100 000 100 200

h-values

26L

10L

46L

12L

Labo

rato

ries

Mandels h statistics(Compost 1 - PBD 100)

Compost 1-PBD 100

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 100)Mandels h statistics(Sludge 1 - PBD 100)

Sample Sludge 1 Sludge 1 - PBD 100 -- Mean PARM = 0005 [mgkg]

Element PBD 100

General calcparmT1= 852065E-02T2= 412762E-04T3= 18T4= 68T5= 78914E-07

n= variabelp= 5

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00039 0000 4 -042 007 Fail 00039 00002 4 3 000

12L 00044 0000 4 -041 005 Fail 00044 00001 4 3 00010L 00046 0000 4 -041 013 Fail 00046 00003 4 3 00046L 00056 0000 4 -040 012 Fail 00056 00003 4 3 00026L 00059 0000 2 -040 013 Fail 00059 00003 2 1 00038L 02168 0006 4 204 244 Fail - - 38L - - 021

Totgem 0040 0001 mgkg 1-level 187 (177) 5 00049 (38L) 5 4Totstd= 0087 0002 5-level 166 (154) 1

RESULTS Mean = 000486 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000025 --gt 507 r = 00007Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000084 --gt 1731 R = 00024Remarks 1 Lab rejected (38L)

000 050 100 150 200 250

k-values

4L

12L

10L

46L

26L

38L

Mandels k statistics(Sludge 1 - PBD 100)

-01 00 01 01 02 02 03

Deviation from Mean

4L

12L

10L

46L

26L

38L

Labo

rato

ries

Sludge 1 - PBD 100 -- Mean PARM = 0005 [mgkg]

-100 000 100 200 300

h-values

4L

12L

10L

46L

26L

38L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 100)

Sludge 1-PBD 100

Unit mgkg

Mandels k statistics(Soil 3 - PBD 100)Mandels h statistics(Soil 3 - PBD 100)

Sample Soil 3 NUM

Element PBD 100

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00003 0000 4 -050 000 Fail - - 10L - - NUM46L 00003 0000 4 -050 000 Fail NUM - 46L - - NUM3L 305500 2051 2 150 200 Fail - - 3L - - NUM

26L 00005 0000 2 -050 000 Fail - - 26L - - NUM

Totgem 7638 0513 mgkg 1-level 149 (177) NUM (10L46L3L26L) -1Totstd= 15275 1025 5-level 142 (159) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (10L46L3L26L)

000 050 100 150 200

k-values

10L

46L

3L

26L

Mandels k statistics(Soil 3 - PBD 100)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

10L

46L

3L

26L

Labo

rato

ries

NUM

-100 000 100 200

h-values

10L

46L

3L

26L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 100)

Soil 3-PBD 100

Unit mgkg

Mandels k statistics(Compost 1 - PBD 153)Mandels h statistics(Compost 1 - PBD 153)

Sample Compost 1 NUM

Element PBD 153

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean44L 00053 0001 3 150 157 Fail - - 44L - - NUM46L 00007 0000 4 -044 111 Fail - - 46L - - NUM12L 00005 0000 4 -051 055 Fail - - 12L - - NUM26L 00005 0000 2 -054 001 Fail NUM - 26L - - NUM

Totgem 0002 0000 mgkg 1-level 149 (177) NUM (44L46L12L26L) -1Totstd= 0002 0000 5-level 142 (159) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (44L46L12L26L)

000 050 100 150 200

k-values

44L

46L

12L

26L

Mandels k statistics(Compost 1 - PBD 153)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

44L

46L

12L

26L

Labo

rato

ries

NUM

-100 000 100 200

h-values

44L

46L

12L

26L

Labo

rato

ries

Mandels h statistics(Compost 1 - PBD 153)

Compost 1-PBD 153

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 153)Mandels h statistics(Sludge 1 - PBD 153)

Sample Sludge 1 Sludge 1 - PBD 153 -- Mean PARM = 0004 [mgkg]

Element PBD 153

General calcparmT1= 676738E-02T2= 267609E-04T3= 18T4= 68T5= 19626E-05

n= variabelp= 5

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00024 0000 4 -157 017 00024 00002 4 3 000

12L 00038 0002 4 006 154 00038 00018 4 3 00046L 00039 0000 4 011 026 00039 00003 4 3 00026L 00039 0000 2 018 004 00039 00000 2 1 00064L 00049 0002 4 122 159 00049 00018 4 3 000

Totgem 0004 0001 mgkg 1-level 172 (173) 5 00038 () 5 4Totstd= 0001 0001 5-level 157 (153)

RESULTS Mean = 000378 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000123 --gt 3252 r = 00034Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000142 --gt 3754 R = 00040Remarks none

000 050 100 150 200

k-values

4L

12L

46L

26L

64L

Mandels k statistics(Sludge 1 - PBD 153)

00 00 00 00 00 00 00

Deviation from Mean

4L

12L

46L

26L

64L

Labo

rato

ries

Sludge 1 - PBD 153 -- Mean PARM = 0004 [mgkg]

-200 -100 000 100 200

h-values

4L

12L

46L

26L

64L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 153)

Sludge 1-PBD 153

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 154)Mandels h statistics(Sludge 1 - PBD 154)

Sample Sludge 1 NA

Element PBD 154

General calcparmT1= NAT2= NAT3=T4=T5=

n= variabelp=

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00021 0000 3 -100 021 NA - 4L - - NA

46L 00025 0000 4 115 018 NA - 46L - - NA64L 00021 0001 4 -066 179 - - 64L - - NA12L 00023 0000 4 050 085 - - 12L - - NA

Totgem 0002 0000 mgkg 1-level 149 (167) NA (4L46L64L12L) -1Totstd= 0000 0000 5-level 142 (15) 4

RESULTS Mean = NA mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NAReproducibility var S2R = NAReproducibility std SR = NA --gt NA R = NARemarks 4 Labs rejected (4L46L64L12L)

000 050 100 150 200

k-values

4L

46L

64L

12L

Mandels k statistics(Sludge 1 - PBD 154)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

4L

46L

64L

12L

Labo

rato

ries

NA

-100 000 100 200

h-values

4L

46L

64L

12L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 154)

Sludge 1-PBD 154

Unit mgkg

Mandels k statistics(Soil 3 - PBD 154)Mandels h statistics(Soil 3 - PBD 154)

Sample Soil 3 NUM

Element PBD 154

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

4L 00010 - 1 150 Fail - - 4L - - NUM46L 00001 0000 4 -053 096 Fail - - 46L - - NUM64L 00001 0000 4 -056 105 Fail NUM - 64L - - NUM12L 00002 0000 4 -040 099 Fail - - 12L - - NUM

Totgem 000037 0000 mgkg 1-level 149 (164) NUM (4L46L64L12L) -1Totstd= 000042 0000 5-level 142 (153) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (4L46L64L12L)

000 050 100 150

k-values

4L

46L

64L

12L

Mandels k statistics(Soil 3 - PBD 154)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

4L

46L

64L

12L

Labo

rato

ries

NUM

-100 000 100 200

h-values

4L

46L

64L

12L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 154)

Soil 3-PBD 154

Unit mgkg

Mandels k statistics(Compost 1 - PBD 209)Mandels h statistics(Compost 1 - PBD 209)

Sample Compost 1 NUM

Element PBD 209

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00065 0003 2 -049 032 - - 4L - - NUM

44L 00573 0021 4 150 197 Fail - - 44L - - NUM12L 00078 0001 4 -045 011 - - 12L - - NUM26L 00049 0000 2 -056 000 NUM - 26L - - NUM

Totgem 0019 0006 mgkg 1-level 149 (177) NUM (4L44L12L26L) -1Totstd= 0025 0010 5-level 142 (159) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (4L44L12L26L)

000 050 100 150 200

k-values

4L

44L

12L

26L

Mandels k statistics(Compost 1 - PBD 209)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

4L

44L

12L

26L

Labo

rato

ries

NUM

-100 000 100 200

h-values

4L

44L

12L

26L

Labo

rato

ries

Mandels h statistics(Compost 1 - PBD 209)

Compost 1-PBD 209

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 209)Mandels h statistics(Sludge 1 - PBD 209)

Sample Sludge 1 Sludge 1 - PBD 209 -- Mean PARM = 0249 [mgkg]

Element PBD 209

General calcparmT1= 394542E+00T2= 107296E+00T3= 16T4= 56T5= 19723E-02

n= variabelp= 5

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 01550 0055 4 -112 148 Fail 01550 00551 4 3 -009

46L 02050 0007 2 -053 019 02050 00071 2 1 -00412L 02137 0058 4 -042 155 02137 00576 4 3 -00426L 03149 0021 2 078 057 Fail 03149 00210 2 1 00764L 03577 0007 4 129 020 Fail 03577 00074 4 3 011

Totgem 0249 0030 mgkg 1-level 172 (185) 5 02493 () 5 4Totstd= 0084 0025 5-level 157 (162)

RESULTS Mean = 024926 mgkg

Repeatability variance S2r = 000179Repeatability std Sr = 004234 --gt 1699 r = 01186Between lab variance S2L = 000743Reproducibility var S2R = 000922Reproducibility std SR = 009604 --gt 3853 R = 02689Remarks none

000 050 100 150 200

k-values

4L

46L

12L

26L

64L

Mandels k statistics(Sludge 1 - PBD 209)

-01 -01 00 01 01 02

Deviation from Mean

4L

46L

12L

26L

64L

Labo

rato

ries

Sludge 1 - PBD 209 -- Mean PARM = 0249 [mgkg]

-200 -100 000 100 200

h-values

4L

46L

12L

26L

64L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 209)

Sludge 1-PBD 209

Unit mgkg

Mandels k statistics(Soil 3 - PBD 209)Mandels h statistics(Soil 3 - PBD 209)

Sample Soil 3 Soil 3 - PBD 209 -- Mean PARM = 0258 [mgkg]

Element PBD 209

General calcparmT1= 596398E+00T2= 191917E+00T3= 22T4= 84T5= 13249E-02

n= variabelp= 6

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean26L 01162 0021 2 -108 074 Fail 01162 00207 2 1 -0144L 01303 0031 4 -097 111 Fail 01303 00312 4 3 -013

46L 01975 0036 4 -046 128 Fail 01975 00359 4 3 -00644L 02898 0035 4 024 124 Fail 02898 00346 4 3 00312L 03895 0018 4 100 065 Fail 03895 00181 4 3 01364L 04260 0022 4 127 078 Fail 04260 00219 4 3 017

Totgem 0258 0027 mgkg 1-level 187 (177) 6 02582 () 6 5Totstd= 0132 0008 5-level 166 (154)

RESULTS Mean = 025818 mgkg

Repeatability variance S2r = 000083Repeatability std Sr = 002878 --gt 1115 r = 00806Between lab variance S2L = 001640Reproducibility var S2R = 001723Reproducibility std SR = 013127 --gt 5084 R = 03676Remarks none

000 050 100 150

k-values

26L

4L

46L

44L

12L

64L

Mandels k statistics(Soil 3 - PBD 209)

-02 -01 -01 00 01 01 02 02

Deviation from Mean

26L

4L

46L

44L

12L

64L

Labo

rato

ries

Soil 3 - PBD 209 -- Mean PARM = 0258 [mgkg]

-200 -100 000 100 200

h-values

26L

4L

46L

44L

12L

64L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 209)

Soil 3-PBD 209

Unit mgkg

Mandels k statistics(Compost 1 - Sum PBD)Mandels h statistics(Compost 1 - Sum PBD)

Sample Compost 1 Compost 1 - Sum PBD -- Mean PARM = 0009 [mgkg]

Element Sum PBD

General calcparmT1= 154064E-01T2= 169065E-03T3= 18T4= 68T5= 11354E-04

n= variabelp= 5

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00031 0002 4 -067 016 00031 00016 4 3 -0014L 00055 0005 4 -056 048 00055 00047 4 3 000

46L 00085 0003 4 -042 031 00085 00030 4 3 00026L 00123 0000 2 -024 003 00123 00002 2 1 00012L 00154 0002 4 -011 021 00154 00021 4 3 00144L 00613 0023 4 200 237 Fail - - 44L - - 005

Totgem 0018 0006 mgkg 1-level 187 (177) 5 00089 (44L) 5 4Totstd= 0022 0009 5-level 166 (154) 1

RESULTS Mean = 000893 mgkg

Repeatability variance S2r = 000001Repeatability std Sr = 000296 --gt 3308 r = 00083Between lab variance S2L = 000002Reproducibility var S2R = 000003Reproducibility std SR = 000570 --gt 6374 R = 00159Remarks 1 Lab rejected (44L)

000 050 100 150 200 250

k-values

10L

4L

46L

26L

12L

44L

Mandels k statistics(Compost 1 - Sum PBD)

00 00 00 00 00 00 01 01

Deviation from Mean

10L

4L

46L

26L

12L

44L

Labo

rato

ries

Compost 1 - Sum PBD -- Mean PARM = 0009 [mgkg]

-100 000 100 200

h-values

10L

4L

46L

26L

12L

44L

Labo

rato

ries

Mandels h statistics(Compost 1 - Sum PBD)

Compost 1-Sum PBD

Unit mgkg

Mandels k statistics(Sludge 1 - Sum PBD)Mandels h statistics(Sludge 1 - Sum PBD)

Sample Sludge 1 Sludge 1 - Sum PBD -- Mean PARM = 0256 [mgkg]

Element Sum PBD

General calcparmT1= 531806E+00T2= 162188E+00T3= 22T4= 84T5= 25223E-02

n= variabelp= 6

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00423 0025 4 -156 044 Fail 00423 00252 4 3 -02146L 01808 0118 4 -049 205 - - 46L - - -0074L 01810 0056 4 -049 097 01810 00558 4 3 -007

38L 02168 0006 4 -022 010 02168 00059 4 3 -00412L 02890 0065 4 034 113 02890 00647 4 3 00364L 03958 0008 4 116 014 Fail 03958 00079 4 3 01426L 04094 0034 2 126 059 Fail 04094 00337 2 1 015

Totgem 0245 0044 mgkg 1-level 198 (179) 6 02557 (46L) 6 5Totstd= 0130 0039 5-level 171 (155) 1

RESULTS Mean = 025570 mgkg

Repeatability variance S2r = 000158Repeatability std Sr = 003970 --gt 1553 r = 01112Between lab variance S2L = 001807Reproducibility var S2R = 001964Reproducibility std SR = 014015 --gt 5481 R = 03924Remarks 1 Lab rejected (46L)

000 050 100 150 200 250

k-values

10L

46L

4L

38L

12L

64L

26L

Mandels k statistics(Sludge 1 - Sum PBD)

-03 -02 -02 -01 -01 00 01 01 02 02

Deviation from Mean

10L

46L

4L

38L

12L

64L

26L

Labo

rato

ries

Sludge 1 - Sum PBD -- Mean PARM = 0256 [mgkg]

-200 -100 000 100 200

h-values

10L

46L

4L

38L

12L

64L

26L

Labo

rato

ries

Mandels h statistics(Sludge 1 - Sum PBD)

Sludge 1-Sum PBD

Unit mgkg

Mandels k statistics(Soil 3 - Sum PBD)Mandels h statistics(Soil 3 - Sum PBD)

Sample Soil 3 Soil 3 - Sum PBD -- Mean PARM = 0227 [mgkg]

Element Sum PBD

General calcparmT1= 610980E+00T2= 200876E+00T3= 26T4= 100T5= 13106E-02

n= variabelp= 7

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00028 0001 4 -037 000 Fail 00028 00005 4 3 -02226L 01179 0021 2 -036 003 Fail 01179 00208 2 1 -0114L 01305 0031 4 -036 004 Fail 01305 00308 4 3 -010

46L 02065 0035 4 -036 005 Fail 02065 00350 4 3 -00244L 02923 0037 4 -035 005 Fail 02923 00365 4 3 00712L 04051 0015 4 -034 002 Fail 04051 00149 4 3 01864L 04314 0022 4 -033 003 Fail 04314 00223 4 3 0203L 305500 2051 2 247 283 Fail - - 3L - - 3032

Totgem 4017 0276 mgkg 1-level 206 (181) 7 02266 (3L) 7 6Totstd= 10722 0717 5-level 175 (156) 1

RESULTS Mean = 022663 mgkg

Repeatability variance S2r = 000069Repeatability std Sr = 002626 --gt 1159 r = 00735Between lab variance S2L = 002568Reproducibility var S2R = 002637Reproducibility std SR = 016238 --gt 7165 R = 04547Remarks 1 Lab rejected (3L)

000 050 100 150 200 250 300

k-values

10L

26L

4L

46L

44L

12L

64L

3L

Mandels k statistics(Soil 3 - Sum PBD)

-50 00 50 100 150 200 250 300 350

Deviation from Mean

10L

26L

4L

46L

44L

12L

64L

3L

Labo

rato

ries

Soil 3 - Sum PBD -- Mean PARM = 0227 [mgkg]

-100 000 100 200 300

h-values

10L

26L

4L

46L

44L

12L

64L

3L

Labo

rato

ries

Mandels h statistics(Soil 3 - Sum PBD)

Soil 3-Sum PBD

19

Annex 4

Raw data submitted

Sample Compost1 Sample Compost 1 Sample Compost 1Element PBD 99 Element PBD 100 Element PBD 153

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]4L 00021 10L 00008 44L 000504L 00024 10L 00008 44L 000604L 00014 10L 00007 44L 000504L 00020 10L 00011 46L 00004

10L 00029 46L 00007 46L 0001210L 00027 46L 00012 46L 0000410L 00032 46L 00009 46L 0000946L 00025 46L 00007 12L 0000446L 00052 12L 00008 12L 0000846L 00029 12L 00012 12L 0000446L 00026 12L 00008 12L 0000712L 00026 12L 00014 26L 0000512L 00043 26L 00007 26L 0000512L 00026 26L 0000612L 0004726L 0002626L 00024

Sample Compost 1 Sample Compost 1 Sample Compost 1Element PBD 154 Element PBD 183 Element PBD 196

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]4L 00010 46L 00002 46L 00011

46L 00003 46L 00024 46L 0000846L 00007 46L 00021 12L 0000246L 00003 46L 00003 12L 0000346L 00004 12L 00003 12L 0000112L 00003 12L 00011 12L 0000212L 00005 12L 0000312L 00031 12L 0000312L 00006

Sample Compost 1 Sample Compost 1 Sample Compost 1Element PBD 197 Element PBD 203 Element PBD 209

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00002 46L 00010 4L 0004146L 00023 12L 00002 4L 0008946L 00022 12L 00003 44L 0041012L 00004 12L 00002 44L 0084012L 00006 12L 00002 44L 0064012L 00003 44L 0040012L 00004 12L 00079

12L 0007312L 0006512L 0009326L 0004926L 00049

Sample Compost 1Element PBD 47

LAB PARM [mgkg]26L 0003826L 00039

Element PBD 99 Element PBD 47 Element PBD 209LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]

4L 00170 10L 00210 4L 010004L 00200 10L 00220 4L 018004L 00170 10L 00210 4L 012004L 00190 46L 00300 4L 0220010L 00280 46L 00280 46L 0210010L 00300 46L 00250 46L 0200010L 00290 46L 00260 64L 0351846L 00340 64L 00059 64L 0363846L 00330 64L 00057 64L 0364546L 00300 64L 00062 64L 0350846L 00310 64L 00060 12L 0220964L 00194 12L 00191 12L 0177164L 00154 12L 00187 12L 0292264L 00185 12L 00190 12L 0164664L 00159 12L 00186 26L 0329712L 00242 26L 00666 26L 0300012L 00223 26L 0033212L 0022112L 0022226L 0024626L 00400

Element PBD 203 Element PBD 197 Element PBD 196LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00022 46L 00027 46L 0002446L 00014 46L 00024 46L 0002264L 00036 12L 00161 64L 0005864L 00058 12L 00060 64L 0006512L 00063 12L 00061 12L 0004812L 00034 12L 00036 12L 0002512L 00038 12L 0003212L 00027 12L 00022

Element PBD 183 Element PBD 154 Element PBD 153LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00049 4L 00020 4L 0002246L 00035 4L 00022 4L 0002446L 00036 4L 00020 4L 0002246L 00034 46L 00025 4L 0002664L 00027 46L 00025 46L 0004064L 00023 46L 00025 46L 0004264L 00024 46L 00023 46L 0003564L 00020 64L 00034 46L 0003812L 00230 64L 00023 64L 0007412L 00032 64L 00017 64L 0004712L 00031 64L 00011 64L 0004612L 00030 12L 00030 64L 0003026L 00007 12L 00021 12L 0006526L 00008 12L 00021 12L 00029

12L 00021 12L 0003226L 00015 12L 0002926L 00019 26L 00039

26L 00040

Element PBD 100LAB PARM [mgkg]

4L 000384L 000414L 000374L 00038

38L 0219038L 0220038L 0208038L 0220010L 0004410L 0005010L 0004310L 0004646L 0005746L 0005946L 0005346L 0005312L 0004312L 0004512L 0004312L 0004326L 0006226L 00057

Sample Soil 3 Sample Soil 3 Sample Soil 3Element PBD 99 Element PBD 47 Element PBD 100

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]10L 00016 10L 00011 10L 0000310L 00019 10L 00010 10L 0000410L 00013 10L 00012 10L 0000410L 00019 46L 00007 10L 0000246L 00025 46L 00022 46L 0000246L 00025 46L 00005 46L 0000646L 00008 46L 00007 46L 0000246L 00011 12L 00010 46L 0000264L 00005 12L 00017 3L 29100064L 00005 12L 00010 3L 32000064L 00006 12L 00009 26L 0000564L 00007 26L 00007 26L 0000512L 00012 26L 0000712L 0001312L 0001312L 0001226L 0000526L 00006

Sample Soil 3 Sample Soil 3 Sample Soil 3Element PBD 153 Element PBD 154 Element PBD 196

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]44L 00050 4L 00010 46L 0000744L 00050 46L 00001 46L 0001146L 00002 46L 00002 46L 0000846L 00003 46L 00001 46L 0001146L 00002 46L 00002 64L 0002646L 00002 64L 00001 64L 0002664L 00001 64L 00001 64L 0002964L 00001 64L 00001 64L 0003464L 00001 64L 00002 12L 0004564L 00002 12L 00003 12L 00032

12L 00002 12L 0002212L 00002 12L 0002112L 00002

Sample Soil 3 Sample Soil 3 Sample Soil 3Element PBD 197 Element PBD 203 Element PBD 209

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00006 46L 00011 4L 0091046L 00013 46L 00017 4L 0150046L 00011 46L 00015 4L 0120046L 00013 46L 00018 4L 0160012L 00090 64L 00013 44L 0337012L 00056 64L 00014 44L 0281012L 00033 64L 00016 44L 0287012L 00032 64L 00015 44L 02540

12L 00055 46L 0230012L 00041 46L 0220012L 00027 46L 0150012L 00026 46L 01900

64L 0438164L 0401664L 0414464L 0449812L 0367112L 0397812L 0409112L 03838

Sample Soil 3 26L 0102Element PBD 183 26L 0131

LAB PARM [mgkg]46L 0000746L 0000846L 0005846L 0000764L 0000264L 0000364L 0000364L 0000312L 0001512L 0001112L 0000712L 00007

European Commission EUR 23003 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on polybrominated diphenylethers Author(s) E Sobiecka H van der Sloot D Barcelo B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 68 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07403-5 Abstract Project HORIZONTAL is interdisciplinary aiming at a harmonisation and horizontal standardisation of test procedures in particular for sludge soils and biowastes In the context of this standardization project a series of draft technical specification were designed upon an extensive desk study fine-tuned after expert consultations and finally validated in international intercomparisons exercise This report summarises the work performed within the validation study of the draft standard for the determination of polybrominated diphenylethers (PBDE) in soils sludge and treated bio-waste using gas-chromatography method with mass selective detection (GC-MS) It further explains the underlying statistical concept for the calculation of reproducibility and repeatability from intercomparisons data In addition all single values results of the statistical evaluation as well as background information on the validation materials used are described and explained

The mission of the JRC is to provide customer-driven scientific and technical support for the conception development implementation and monitoring of EU policies As a service of the European Commission the JRC functions as a reference centre of science and technology for the Union Close to the policy-making process it serves the common interest of the Member States while being independent of special interests whether private or national

LB

-NA

-23003-EN

-C

10

Parameter Concentration

Chrysene 608 Benz(b)fluoranthene 824 Benz(k)fluoranthene 329 Benz(a)pyrene 799 Indeno(123-cd)pyrene

779

Dibenzo(ah)anthracene 118 Benzo(ghi)perylene 394

Table 10 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 3

(Reading)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

103

003

nq

nq

nq

nd

nd

272

273

Table 11 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 3 (Reading) 015 706 279 138 152 901 267 300 lt 005 258 931

Table 12 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 3 (Reading) 7936 477 112 096 194 017 4107 443 2102 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 3 (Reading) 042 13 45 69 69 69 216 92

Table 13 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 3 (Reading) 012

11

23 Compost from Vienna Austria

The fresh compost material was obtained from the Austrian Federal Environment Agency (UBA Vienna) which had used a sub-batch of the raw material for national intercomparson The remainder of the material was stored at 4degC until shipment to IRMM for further processing The following analytical information was provided by UBA Austria and completed with various screenings

Table 14 ndash Analytical data on compost material received from UBA Austria Inorganic and sum parameters

Parameter Unit Sample fraction used Observed mean B CAT mgl FM Fresh sample lt10mm 61 K CAT mgl FM Fresh sample lt10mm 2624 Mg CAT mgl FM Fresh sample lt10mm 242 P CAT mgl FM Fresh sample lt10mm 49 B CAT DM Fresh sample lt10mm 00017 K CAT DM Fresh sample lt10mm 072 Mg CAT DM Fresh sample lt10mm 007 P CAT DM Fresh sample lt10mm 001 NO3-N mgkg FM Fresh sample lt10mm 35 NH4-N mgkg FM Fresh sample lt10mm 230 Ctotal DM lt45degdry milled 29 Corg DM lt45degdry milled 27 Ntotal DM lt45degdry milled 17 P mgkg DM lt45degdry milled 2596 K mgkg DM lt45degdry milled 11019 K DM lt45degdry milled 110 B mgkg DM lt45degdry milled 60 Cd mgkg DM lt45degdry milled 046 Cr mgkg DM lt45degdry milled 25 Cu mgkg DM lt45degdry milled 46 Hg mgkg DM lt45degdry milled 020 Ni mgkg DM lt45degdry milled 18 Pb mgkg DM lt45degdry milled 45 Zn mgkg DM lt45degdry milled 198 Ca mgkg DM lt45degdry milled 68776 Ca DM lt45degdry milled 69 Mo mgkg DM lt45degdry milled 08 S mgkg DM lt45degdry milled 2137 Fe mgkg DM lt45degdry milled 9959 Mn mgkg DM lt45degdry milled 418 Na mgkg DM lt45degdry milled 742 Co mgkg DM lt45degdry milled 41 AOX mgkg DM lt30deg dry milled 62

Table 15 ndash Analytical data on compost material received from UBA Austria Polycyclic aromatic hydrocarbons

PAH Unit Result Naphthaline microgkg DM 93 Acenaphthylene microgkg DM 86 Acenaphthene microgkg DM 5 Fluorene microgkg DM 80 Phenanthrene microgkg DM 89 Anthracene microgkg DM 27 Fluoranthene microgkg DM 487 Pyrene microgkg DM 380

12

PAH Unit Result Benzo(a)anthracene microgkg DM 278 Chrysene microgkg DM 317 Benzo(b)fluoranthene microgkg DM 365 Benzo(k)fluoranthene microgkg DM 193 Benz(a)pyrene microgkg DM 320 Indeno(123-cd)pyrene microgkg DM 233 Dibenz(ah)anthracene microgkg DM 67 Benzo(ghi)perylene microgkg DM 225 Sum EPA microgkg DM 3013 Sum EPA mgkg DM 30

Table 16 ndash Analytical data on compost material received from UBA Austria Sum PCDDs and PCBs

Parameter

Dioxine TEQ (ITEF) ngkg DM 73 TEQ (WHO) ngkg DM 35 PCB Σ Ballschmiter mgkg DM 005

Table 17 ndash Analytical data on compost material obtained by screening in IRMM

Parameter Result in ngg

PCB 28 2 52 2 101 4 118 3 153 10 105 1 138 8 156 1 180 5 170 lt1 PAH Naphtalene lt10 Acenaphtylene lt10 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene 26 Fluoranthene 611 Pyrene 510 Benz(a)anthracene 888 Chrysene 957 Benz(b)fluoranthene 1531 Benz(k)fluoranthene 547 Benz(a)pyrene 1101 Indeno(123-cd)pyrene 416 Dibenzo(ah)anthracene 81 Benzo(ghi)perylene 295

13

Table 18 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Compost 1

(Vienna)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

402

019

259

nq

023

004

nq

nq

144

174

259

Table 19 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Compost 1

(Vienna) 0058 1426 557

Table 20 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Compost 1 (Vienna) 039 736 319 410 365 127 495 004 079 013 208

Table 21 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Compost 1 (Vienna) 2063 431 617 426 199 249 1602 lt15 10521

Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Compost 1 (Vienna) 035 3496 81 375 79 55 653 60

Table 22 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Compost 1 (Vienna) 017

14

24 Agricultural soil sludge amended soil from Pavia Italy

This sludge-amended soil material was obtained during a monitoring campaign which aimed at a generic description of the over-all soil quality in Pavia Province Italy The material which was collected from the upper horizon originates from a small farm called ldquoCascina Novellordquo During the characterisation of the site the following analytical information was obtained on a pooled sample of a sub-area of the farm of 20 X 20 m2

Table 23 ndash Analytical data on Pavia soil

Parameter Result Al 713 Wgt As 224 mgkg Cd 079 mgkg Cr 59 mgkg Cu 308 mgkg Hg 008 mgkg Ni 344 mgkg Pb 246 mgkg Zn 95 mgkg C 091 Wgt 2378-TCDD 0047 pgg 12378-PeCDD 015 pgg 123478-HxCDD 019 pgg 123678-HxCDD 15 pgg 123789-HxCDD 074 pgg 1234678-HpCDD 26 pgg OCDD 382 pgg 2378-TCDF 068 pgg 12378-PeCDF 053 pgg 23478-PeCDF 071 pgg 123478-HxDF 100 pgg 123678-HxDF 066 pgg 234678-HxDF 16 pgg 123789-HxDF 027 pgg 1234678-HpDF 12 pgg 1234789-HpDF 068 pgg OCDF 33 pgg I-TEQ 20 pgg WHO-TEQ 17 pgg

In addition the screening performed at IRMM did not reveal significant quantities of PCBs and PAHs which were all below the LoDs (1 ngg for PCBs and 10 ngg for PAHs respectively)

Table 24 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 5 (Pavia) 0005 0011 154

15

Table 25 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 5

(Pavia)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

039

nq

nq

008

nq

nd

nd

670

671

Table 26 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 5 (Pavia) 033 184 573 225 426 305 206 200 lt 005 381 878

Table 27 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 5 (Pavia) 6939 129 145 224 425 116 6118 255 1789 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 5 (Pavia) 184 62 38 108 55 66 597 110

Table 28 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 5 (Pavia) 006

16

25 Sludge-amended-soil from Barcelona Spain

The sludge-amended soil material from Barcelona sampled upon indication from the Barcelorsquo- Group in Barcelona

Table 29 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 2 (Lleida T) 0015 0183 1138

Table 30 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 2

(Lleida T)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

159

045

nq

048

160

nq

nq

1000

1004

Table 31 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 2 (Lleida T) 059 141 327 536 405 186 184 224 lt 005 318 111

Table 32 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 2 (Lleida T) 4443 1067 1429 253 344 204 4116 780 3396 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 2 (Lleida T) 064 65 26 125 59 17 547 65

Table 33 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 2 (Lleida T) 010

17

26 Sludge amended soil from Essen Germany

The German sludge-amended soil from Essen which was provided as the three sludge materials by LUA NRW did not feature significant concentrations of the PCB congeners 28 52 101 118 153 105 138 156 180 170 but had detectable amounts of some PAHs

Table 34 ndash Analytical screening data on the German sludge-amended soil

Parameter Concentration(ngg)

Naphtalene lt10 Acenaphtylene lt10 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene lt10 Fluoranthene 28 Pyrene 20 Benz(a)anthracene 24 Chrysene 47 Benz(b)fluoranthene 76 Benz(k)fluoranthene 20 Benz(a)pyrene 35 Indeno(123-cd)pyrene 35 Dibenzo(ah)anthracene 10 Benzo(ghi)perylene 26

Table 35 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 4 (Essen) 0011 0302 055

Table 36 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 4

(Essen)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

nq

nq

nq

nq

nq

nq

128

191

203

18

Table 37 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 4 (Essen) 052 545 261 805 320 403 273 273 lt 005 295 781

Table 38 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 4 (Essen) 7947 442 085 06 086 007 2163 189 2019 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 4 (Essen) 045 19 42 87 683 60 462 61

Table 39 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 4 (Essen) 004

27 Long-term sludge exposed soil from Hohenheim-Stuttgart Germany

Similarly an additional sludge exposed soil was sampled at the University of Hohenheim Stuttgart were a test soil was long-term exposed to elevated concentrations of sewage sludge

Table 40 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 1 (Stuttgart) 0045 0263 1765

Table 41 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 1

(Stuttgart)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

230

006

004

004

nq

nd

nd

498

500

19

Table 42 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 1 (Stuttgart) 069 127 361 262 504 183 252 262 lt 005 266 142

Table 43 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 1 (Stuttgart) 7194 1006 133 186 366 088 7874 275 3571 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 1 (Stuttgart) 123 50 47 212 85 69 991 129

Table 44 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 1 (Stuttgart) 177

18

Annex 3

Statistical calculations

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 47)Mandels h statistics(Sludge 1 - PBD 47)

Sample Sludge 1 NUM

Element PBD 47

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00213 0001 3 -021 005 - - 10L - - NUM46L 00273 0002 4 016 021 - - 46L - - NUM64L 00059 0000 4 -116 002 NUM - 64L - - NUM12L 00188 0000 4 -036 002 - - 12L - - NUM26L 00499 0024 2 157 223 Fail - - 26L - - NUM

Totgem 0025 0005 mgkg 1-level 172 (185) NUM (10L46L64L12L26L) -1Totstd= 0016 0010 5-level 157 (162) 5

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 5 Labs rejected (10L46L64L12L26L)

000 050 100 150 200 250

k-values

10L

46L

64L

12L

26L

Mandels k statistics(Sludge 1 - PBD 47)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

10L

46L

64L

12L

26L

Labo

rato

ries

NUM

-200 -100 000 100 200

h-values

10L

46L

64L

12L

26L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 47)

Sludge 1-PBD 47

Unit mgkg

Mandels k statistics(Soil 3 - PBD 47)Mandels h statistics(Soil 3 - PBD 47)

Sample Soil 3 Soil 3 - PBD 47 -- Mean PARM = 0001 [mgkg]

Element PBD 47

General calcparmT1= 134814E-02T2= 142830E-05T3= 13T4= 45T5= 22767E-06

n= variabelp= 4

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean26L 00007 0000 2 -143 001 00007 00000 2 1 00046L 00010 0001 4 010 181 00010 00008 4 3 00010L 00011 0000 3 049 023 00011 00001 3 2 00012L 00012 0000 4 084 081 00012 00004 4 3 000

Totgem 0001 0000 mgkg 1-level 149 (177) 4 00010 () 4 3Totstd= 0000 0000 5-level 142 (159)

RESULTS Mean = 000100 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000050 --gt 5031 r = 00014Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000050 --gt 5031 R = 00014Remarks none

000 050 100 150 200

k-values

26L

46L

10L

12L

Mandels k statistics(Soil 3 - PBD 47)

00 00 00 00 00 00 00 00 00 00 00

Deviation from Mean

26L

46L

10L

12L

Labo

rato

ries

Soil 3 - PBD 47 -- Mean PARM = 0001 [mgkg]

-200 -100 000 100

h-values

26L

46L

10L

12L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 47)

Soil 3-PBD 47

Unit mgkg

Mandels k statistics(Compost 1 - PBD 99)Mandels h statistics(Compost 1 - PBD 99)

Sample Compost 1 Compost 1 - PBD 99 -- Mean PARM = 0003 [mgkg]

Element PBD 99

General calcparmT1= 492124E-02T2= 148747E-04T3= 17T4= 61T5= 93196E-06

n= variabelp= 5

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00020 0000 4 -137 053 00020 00004 4 3 000

26L 00025 0000 2 -058 024 00025 00002 2 1 00010L 00029 0000 3 012 032 00029 00003 3 2 00046L 00033 0001 4 069 161 00033 00013 4 3 00012L 00036 0001 4 114 140 00036 00011 4 3 000

Totgem 0003 0001 mgkg 1-level 172 (185) 5 00029 () 5 4Totstd= 0001 0001 5-level 157 (162)

RESULTS Mean = 000286 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000088 --gt 3086 r = 00025Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000101 --gt 3525 R = 00028Remarks none

000 050 100 150 200

k-values

4L

26L

10L

46L

12L

Mandels k statistics(Compost 1 - PBD 99)

00 00 00 00 00 00 00 00 00 00

Deviation from Mean

4L

26L

10L

46L

12L

Labo

rato

ries

Compost 1 - PBD 99 -- Mean PARM = 0003 [mgkg]

-200 -100 000 100 200

h-values

4L

26L

10L

46L

12L

Labo

rato

ries

Mandels h statistics(Compost 1 - PBD 99)

Compost 1-PBD 99

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 99)Mandels h statistics(Sludge 1 - PBD 99)

Sample Sludge 1 Sludge 1 - PBD 99 -- Mean PARM = 0024 [mgkg]

Element PBD 99

General calcparmT1= 448050E-01T2= 112113E-02T3= 19T4= 73T5= 32972E-05

n= variabelp= 5

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean64L 00173 0002 4 -118 041 Fail 00173 00019 4 3 -0014L 00183 0002 4 -104 032 00183 00015 4 3 -001

12L 00227 0001 4 -038 022 00227 00010 4 3 00010L 00290 0001 3 055 021 00290 00010 3 2 00146L 00320 0002 4 100 039 00320 00018 4 3 00126L 00323 0011 2 105 234 - - 26L - - 001

Totgem 0025 0003 mgkg 1-level 187 (177) 5 00239 (26L) 5 4Totstd= 0007 0004 5-level 166 (154) 1

RESULTS Mean = 002385 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000153 --gt 643 r = 00043Between lab variance S2L = 000004Reproducibility var S2R = 000004Reproducibility std SR = 000666 --gt 2791 R = 00186Remarks 1 Lab rejected (26L)

000 050 100 150 200 250

k-values

64L

4L

12L

10L

46L

26L

Mandels k statistics(Sludge 1 - PBD 99)

00 00 00 00 00 00 00 00 00 00

Deviation from Mean

64L

4L

12L

10L

46L

26L

Labo

rato

ries

Sludge 1 - PBD 99 -- Mean PARM = 0024 [mgkg]

-200 -100 000 100 200

h-values

64L

4L

12L

10L

46L

26L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 99)

Sludge 1-PBD 99

Unit mgkg

Mandels k statistics(Soil 3 - PBD 99)Mandels h statistics(Soil 3 - PBD 99)

Sample Soil 3 NUM

Element PBD 99

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00017 0000 4 091 068 - - 10L - - NUM46L 00017 0001 4 100 211 - - 46L - - NUM64L 00005 0000 4 -106 023 NUM - 64L - - NUM12L 00012 0000 4 015 014 - - 12L - - NUM26L 00006 0000 2 -101 012 - - 26L - - NUM

Totgem 0001 0000 mgkg 1-level 172 (173) NUM (10L46L64L12L26L) -1Totstd= 0001 0000 5-level 157 (153) 5

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 5 Labs rejected (10L46L64L12L26L)

000 050 100 150 200 250

k-values

10L

46L

64L

12L

26L

Mandels k statistics(Soil 3 - PBD 99)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

10L

46L

64L

12L

26L

Labo

rato

ries

NUM

-200 -100 000 100 200

h-values

10L

46L

64L

12L

26L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 99)

Soil 3-PBD 99

Unit mgkg

Mandels k statistics(Compost 1 - PBD 100)Mandels h statistics(Compost 1 - PBD 100)

Sample Compost 1 Compost 1 - PBD 100 -- Mean PARM = 0001 [mgkg]

Element PBD 100

General calcparmT1= 124272E-02T2= 113129E-05T3= 14T4= 52T5= 46584E-07

n= variabelp= 4

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean26L 00006 0000 2 -131 037 Fail 00006 00001 2 1 00010L 00009 0000 4 003 083 00009 00002 4 3 00046L 00009 0000 4 016 115 00009 00002 4 3 00012L 00011 0000 4 112 136 Fail 00011 00003 4 3 000

Totgem 0001 0000 mgkg 1-level 149 (167) 4 00009 () 4 3Totstd= 0000 0000 5-level 142 (15)

RESULTS Mean = 000085 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000022 --gt 2531 r = 00006Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000025 --gt 2882 R = 00007Remarks none

000 050 100 150

k-values

26L

10L

46L

12L

Mandels k statistics(Compost 1 - PBD 100)

00 00 00 00 00 00 00 00 00 00 00

Deviation from Mean

26L

10L

46L

12L

Labo

rato

ries

Compost 1 - PBD 100 -- Mean PARM = 0001 [mgkg]

-200 -100 000 100 200

h-values

26L

10L

46L

12L

Labo

rato

ries

Mandels h statistics(Compost 1 - PBD 100)

Compost 1-PBD 100

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 100)Mandels h statistics(Sludge 1 - PBD 100)

Sample Sludge 1 Sludge 1 - PBD 100 -- Mean PARM = 0005 [mgkg]

Element PBD 100

General calcparmT1= 852065E-02T2= 412762E-04T3= 18T4= 68T5= 78914E-07

n= variabelp= 5

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00039 0000 4 -042 007 Fail 00039 00002 4 3 000

12L 00044 0000 4 -041 005 Fail 00044 00001 4 3 00010L 00046 0000 4 -041 013 Fail 00046 00003 4 3 00046L 00056 0000 4 -040 012 Fail 00056 00003 4 3 00026L 00059 0000 2 -040 013 Fail 00059 00003 2 1 00038L 02168 0006 4 204 244 Fail - - 38L - - 021

Totgem 0040 0001 mgkg 1-level 187 (177) 5 00049 (38L) 5 4Totstd= 0087 0002 5-level 166 (154) 1

RESULTS Mean = 000486 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000025 --gt 507 r = 00007Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000084 --gt 1731 R = 00024Remarks 1 Lab rejected (38L)

000 050 100 150 200 250

k-values

4L

12L

10L

46L

26L

38L

Mandels k statistics(Sludge 1 - PBD 100)

-01 00 01 01 02 02 03

Deviation from Mean

4L

12L

10L

46L

26L

38L

Labo

rato

ries

Sludge 1 - PBD 100 -- Mean PARM = 0005 [mgkg]

-100 000 100 200 300

h-values

4L

12L

10L

46L

26L

38L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 100)

Sludge 1-PBD 100

Unit mgkg

Mandels k statistics(Soil 3 - PBD 100)Mandels h statistics(Soil 3 - PBD 100)

Sample Soil 3 NUM

Element PBD 100

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00003 0000 4 -050 000 Fail - - 10L - - NUM46L 00003 0000 4 -050 000 Fail NUM - 46L - - NUM3L 305500 2051 2 150 200 Fail - - 3L - - NUM

26L 00005 0000 2 -050 000 Fail - - 26L - - NUM

Totgem 7638 0513 mgkg 1-level 149 (177) NUM (10L46L3L26L) -1Totstd= 15275 1025 5-level 142 (159) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (10L46L3L26L)

000 050 100 150 200

k-values

10L

46L

3L

26L

Mandels k statistics(Soil 3 - PBD 100)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

10L

46L

3L

26L

Labo

rato

ries

NUM

-100 000 100 200

h-values

10L

46L

3L

26L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 100)

Soil 3-PBD 100

Unit mgkg

Mandels k statistics(Compost 1 - PBD 153)Mandels h statistics(Compost 1 - PBD 153)

Sample Compost 1 NUM

Element PBD 153

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean44L 00053 0001 3 150 157 Fail - - 44L - - NUM46L 00007 0000 4 -044 111 Fail - - 46L - - NUM12L 00005 0000 4 -051 055 Fail - - 12L - - NUM26L 00005 0000 2 -054 001 Fail NUM - 26L - - NUM

Totgem 0002 0000 mgkg 1-level 149 (177) NUM (44L46L12L26L) -1Totstd= 0002 0000 5-level 142 (159) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (44L46L12L26L)

000 050 100 150 200

k-values

44L

46L

12L

26L

Mandels k statistics(Compost 1 - PBD 153)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

44L

46L

12L

26L

Labo

rato

ries

NUM

-100 000 100 200

h-values

44L

46L

12L

26L

Labo

rato

ries

Mandels h statistics(Compost 1 - PBD 153)

Compost 1-PBD 153

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 153)Mandels h statistics(Sludge 1 - PBD 153)

Sample Sludge 1 Sludge 1 - PBD 153 -- Mean PARM = 0004 [mgkg]

Element PBD 153

General calcparmT1= 676738E-02T2= 267609E-04T3= 18T4= 68T5= 19626E-05

n= variabelp= 5

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00024 0000 4 -157 017 00024 00002 4 3 000

12L 00038 0002 4 006 154 00038 00018 4 3 00046L 00039 0000 4 011 026 00039 00003 4 3 00026L 00039 0000 2 018 004 00039 00000 2 1 00064L 00049 0002 4 122 159 00049 00018 4 3 000

Totgem 0004 0001 mgkg 1-level 172 (173) 5 00038 () 5 4Totstd= 0001 0001 5-level 157 (153)

RESULTS Mean = 000378 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000123 --gt 3252 r = 00034Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000142 --gt 3754 R = 00040Remarks none

000 050 100 150 200

k-values

4L

12L

46L

26L

64L

Mandels k statistics(Sludge 1 - PBD 153)

00 00 00 00 00 00 00

Deviation from Mean

4L

12L

46L

26L

64L

Labo

rato

ries

Sludge 1 - PBD 153 -- Mean PARM = 0004 [mgkg]

-200 -100 000 100 200

h-values

4L

12L

46L

26L

64L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 153)

Sludge 1-PBD 153

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 154)Mandels h statistics(Sludge 1 - PBD 154)

Sample Sludge 1 NA

Element PBD 154

General calcparmT1= NAT2= NAT3=T4=T5=

n= variabelp=

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00021 0000 3 -100 021 NA - 4L - - NA

46L 00025 0000 4 115 018 NA - 46L - - NA64L 00021 0001 4 -066 179 - - 64L - - NA12L 00023 0000 4 050 085 - - 12L - - NA

Totgem 0002 0000 mgkg 1-level 149 (167) NA (4L46L64L12L) -1Totstd= 0000 0000 5-level 142 (15) 4

RESULTS Mean = NA mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NAReproducibility var S2R = NAReproducibility std SR = NA --gt NA R = NARemarks 4 Labs rejected (4L46L64L12L)

000 050 100 150 200

k-values

4L

46L

64L

12L

Mandels k statistics(Sludge 1 - PBD 154)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

4L

46L

64L

12L

Labo

rato

ries

NA

-100 000 100 200

h-values

4L

46L

64L

12L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 154)

Sludge 1-PBD 154

Unit mgkg

Mandels k statistics(Soil 3 - PBD 154)Mandels h statistics(Soil 3 - PBD 154)

Sample Soil 3 NUM

Element PBD 154

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

4L 00010 - 1 150 Fail - - 4L - - NUM46L 00001 0000 4 -053 096 Fail - - 46L - - NUM64L 00001 0000 4 -056 105 Fail NUM - 64L - - NUM12L 00002 0000 4 -040 099 Fail - - 12L - - NUM

Totgem 000037 0000 mgkg 1-level 149 (164) NUM (4L46L64L12L) -1Totstd= 000042 0000 5-level 142 (153) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (4L46L64L12L)

000 050 100 150

k-values

4L

46L

64L

12L

Mandels k statistics(Soil 3 - PBD 154)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

4L

46L

64L

12L

Labo

rato

ries

NUM

-100 000 100 200

h-values

4L

46L

64L

12L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 154)

Soil 3-PBD 154

Unit mgkg

Mandels k statistics(Compost 1 - PBD 209)Mandels h statistics(Compost 1 - PBD 209)

Sample Compost 1 NUM

Element PBD 209

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00065 0003 2 -049 032 - - 4L - - NUM

44L 00573 0021 4 150 197 Fail - - 44L - - NUM12L 00078 0001 4 -045 011 - - 12L - - NUM26L 00049 0000 2 -056 000 NUM - 26L - - NUM

Totgem 0019 0006 mgkg 1-level 149 (177) NUM (4L44L12L26L) -1Totstd= 0025 0010 5-level 142 (159) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (4L44L12L26L)

000 050 100 150 200

k-values

4L

44L

12L

26L

Mandels k statistics(Compost 1 - PBD 209)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

4L

44L

12L

26L

Labo

rato

ries

NUM

-100 000 100 200

h-values

4L

44L

12L

26L

Labo

rato

ries

Mandels h statistics(Compost 1 - PBD 209)

Compost 1-PBD 209

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 209)Mandels h statistics(Sludge 1 - PBD 209)

Sample Sludge 1 Sludge 1 - PBD 209 -- Mean PARM = 0249 [mgkg]

Element PBD 209

General calcparmT1= 394542E+00T2= 107296E+00T3= 16T4= 56T5= 19723E-02

n= variabelp= 5

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 01550 0055 4 -112 148 Fail 01550 00551 4 3 -009

46L 02050 0007 2 -053 019 02050 00071 2 1 -00412L 02137 0058 4 -042 155 02137 00576 4 3 -00426L 03149 0021 2 078 057 Fail 03149 00210 2 1 00764L 03577 0007 4 129 020 Fail 03577 00074 4 3 011

Totgem 0249 0030 mgkg 1-level 172 (185) 5 02493 () 5 4Totstd= 0084 0025 5-level 157 (162)

RESULTS Mean = 024926 mgkg

Repeatability variance S2r = 000179Repeatability std Sr = 004234 --gt 1699 r = 01186Between lab variance S2L = 000743Reproducibility var S2R = 000922Reproducibility std SR = 009604 --gt 3853 R = 02689Remarks none

000 050 100 150 200

k-values

4L

46L

12L

26L

64L

Mandels k statistics(Sludge 1 - PBD 209)

-01 -01 00 01 01 02

Deviation from Mean

4L

46L

12L

26L

64L

Labo

rato

ries

Sludge 1 - PBD 209 -- Mean PARM = 0249 [mgkg]

-200 -100 000 100 200

h-values

4L

46L

12L

26L

64L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 209)

Sludge 1-PBD 209

Unit mgkg

Mandels k statistics(Soil 3 - PBD 209)Mandels h statistics(Soil 3 - PBD 209)

Sample Soil 3 Soil 3 - PBD 209 -- Mean PARM = 0258 [mgkg]

Element PBD 209

General calcparmT1= 596398E+00T2= 191917E+00T3= 22T4= 84T5= 13249E-02

n= variabelp= 6

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean26L 01162 0021 2 -108 074 Fail 01162 00207 2 1 -0144L 01303 0031 4 -097 111 Fail 01303 00312 4 3 -013

46L 01975 0036 4 -046 128 Fail 01975 00359 4 3 -00644L 02898 0035 4 024 124 Fail 02898 00346 4 3 00312L 03895 0018 4 100 065 Fail 03895 00181 4 3 01364L 04260 0022 4 127 078 Fail 04260 00219 4 3 017

Totgem 0258 0027 mgkg 1-level 187 (177) 6 02582 () 6 5Totstd= 0132 0008 5-level 166 (154)

RESULTS Mean = 025818 mgkg

Repeatability variance S2r = 000083Repeatability std Sr = 002878 --gt 1115 r = 00806Between lab variance S2L = 001640Reproducibility var S2R = 001723Reproducibility std SR = 013127 --gt 5084 R = 03676Remarks none

000 050 100 150

k-values

26L

4L

46L

44L

12L

64L

Mandels k statistics(Soil 3 - PBD 209)

-02 -01 -01 00 01 01 02 02

Deviation from Mean

26L

4L

46L

44L

12L

64L

Labo

rato

ries

Soil 3 - PBD 209 -- Mean PARM = 0258 [mgkg]

-200 -100 000 100 200

h-values

26L

4L

46L

44L

12L

64L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 209)

Soil 3-PBD 209

Unit mgkg

Mandels k statistics(Compost 1 - Sum PBD)Mandels h statistics(Compost 1 - Sum PBD)

Sample Compost 1 Compost 1 - Sum PBD -- Mean PARM = 0009 [mgkg]

Element Sum PBD

General calcparmT1= 154064E-01T2= 169065E-03T3= 18T4= 68T5= 11354E-04

n= variabelp= 5

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00031 0002 4 -067 016 00031 00016 4 3 -0014L 00055 0005 4 -056 048 00055 00047 4 3 000

46L 00085 0003 4 -042 031 00085 00030 4 3 00026L 00123 0000 2 -024 003 00123 00002 2 1 00012L 00154 0002 4 -011 021 00154 00021 4 3 00144L 00613 0023 4 200 237 Fail - - 44L - - 005

Totgem 0018 0006 mgkg 1-level 187 (177) 5 00089 (44L) 5 4Totstd= 0022 0009 5-level 166 (154) 1

RESULTS Mean = 000893 mgkg

Repeatability variance S2r = 000001Repeatability std Sr = 000296 --gt 3308 r = 00083Between lab variance S2L = 000002Reproducibility var S2R = 000003Reproducibility std SR = 000570 --gt 6374 R = 00159Remarks 1 Lab rejected (44L)

000 050 100 150 200 250

k-values

10L

4L

46L

26L

12L

44L

Mandels k statistics(Compost 1 - Sum PBD)

00 00 00 00 00 00 01 01

Deviation from Mean

10L

4L

46L

26L

12L

44L

Labo

rato

ries

Compost 1 - Sum PBD -- Mean PARM = 0009 [mgkg]

-100 000 100 200

h-values

10L

4L

46L

26L

12L

44L

Labo

rato

ries

Mandels h statistics(Compost 1 - Sum PBD)

Compost 1-Sum PBD

Unit mgkg

Mandels k statistics(Sludge 1 - Sum PBD)Mandels h statistics(Sludge 1 - Sum PBD)

Sample Sludge 1 Sludge 1 - Sum PBD -- Mean PARM = 0256 [mgkg]

Element Sum PBD

General calcparmT1= 531806E+00T2= 162188E+00T3= 22T4= 84T5= 25223E-02

n= variabelp= 6

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00423 0025 4 -156 044 Fail 00423 00252 4 3 -02146L 01808 0118 4 -049 205 - - 46L - - -0074L 01810 0056 4 -049 097 01810 00558 4 3 -007

38L 02168 0006 4 -022 010 02168 00059 4 3 -00412L 02890 0065 4 034 113 02890 00647 4 3 00364L 03958 0008 4 116 014 Fail 03958 00079 4 3 01426L 04094 0034 2 126 059 Fail 04094 00337 2 1 015

Totgem 0245 0044 mgkg 1-level 198 (179) 6 02557 (46L) 6 5Totstd= 0130 0039 5-level 171 (155) 1

RESULTS Mean = 025570 mgkg

Repeatability variance S2r = 000158Repeatability std Sr = 003970 --gt 1553 r = 01112Between lab variance S2L = 001807Reproducibility var S2R = 001964Reproducibility std SR = 014015 --gt 5481 R = 03924Remarks 1 Lab rejected (46L)

000 050 100 150 200 250

k-values

10L

46L

4L

38L

12L

64L

26L

Mandels k statistics(Sludge 1 - Sum PBD)

-03 -02 -02 -01 -01 00 01 01 02 02

Deviation from Mean

10L

46L

4L

38L

12L

64L

26L

Labo

rato

ries

Sludge 1 - Sum PBD -- Mean PARM = 0256 [mgkg]

-200 -100 000 100 200

h-values

10L

46L

4L

38L

12L

64L

26L

Labo

rato

ries

Mandels h statistics(Sludge 1 - Sum PBD)

Sludge 1-Sum PBD

Unit mgkg

Mandels k statistics(Soil 3 - Sum PBD)Mandels h statistics(Soil 3 - Sum PBD)

Sample Soil 3 Soil 3 - Sum PBD -- Mean PARM = 0227 [mgkg]

Element Sum PBD

General calcparmT1= 610980E+00T2= 200876E+00T3= 26T4= 100T5= 13106E-02

n= variabelp= 7

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00028 0001 4 -037 000 Fail 00028 00005 4 3 -02226L 01179 0021 2 -036 003 Fail 01179 00208 2 1 -0114L 01305 0031 4 -036 004 Fail 01305 00308 4 3 -010

46L 02065 0035 4 -036 005 Fail 02065 00350 4 3 -00244L 02923 0037 4 -035 005 Fail 02923 00365 4 3 00712L 04051 0015 4 -034 002 Fail 04051 00149 4 3 01864L 04314 0022 4 -033 003 Fail 04314 00223 4 3 0203L 305500 2051 2 247 283 Fail - - 3L - - 3032

Totgem 4017 0276 mgkg 1-level 206 (181) 7 02266 (3L) 7 6Totstd= 10722 0717 5-level 175 (156) 1

RESULTS Mean = 022663 mgkg

Repeatability variance S2r = 000069Repeatability std Sr = 002626 --gt 1159 r = 00735Between lab variance S2L = 002568Reproducibility var S2R = 002637Reproducibility std SR = 016238 --gt 7165 R = 04547Remarks 1 Lab rejected (3L)

000 050 100 150 200 250 300

k-values

10L

26L

4L

46L

44L

12L

64L

3L

Mandels k statistics(Soil 3 - Sum PBD)

-50 00 50 100 150 200 250 300 350

Deviation from Mean

10L

26L

4L

46L

44L

12L

64L

3L

Labo

rato

ries

Soil 3 - Sum PBD -- Mean PARM = 0227 [mgkg]

-100 000 100 200 300

h-values

10L

26L

4L

46L

44L

12L

64L

3L

Labo

rato

ries

Mandels h statistics(Soil 3 - Sum PBD)

Soil 3-Sum PBD

19

Annex 4

Raw data submitted

Sample Compost1 Sample Compost 1 Sample Compost 1Element PBD 99 Element PBD 100 Element PBD 153

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]4L 00021 10L 00008 44L 000504L 00024 10L 00008 44L 000604L 00014 10L 00007 44L 000504L 00020 10L 00011 46L 00004

10L 00029 46L 00007 46L 0001210L 00027 46L 00012 46L 0000410L 00032 46L 00009 46L 0000946L 00025 46L 00007 12L 0000446L 00052 12L 00008 12L 0000846L 00029 12L 00012 12L 0000446L 00026 12L 00008 12L 0000712L 00026 12L 00014 26L 0000512L 00043 26L 00007 26L 0000512L 00026 26L 0000612L 0004726L 0002626L 00024

Sample Compost 1 Sample Compost 1 Sample Compost 1Element PBD 154 Element PBD 183 Element PBD 196

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]4L 00010 46L 00002 46L 00011

46L 00003 46L 00024 46L 0000846L 00007 46L 00021 12L 0000246L 00003 46L 00003 12L 0000346L 00004 12L 00003 12L 0000112L 00003 12L 00011 12L 0000212L 00005 12L 0000312L 00031 12L 0000312L 00006

Sample Compost 1 Sample Compost 1 Sample Compost 1Element PBD 197 Element PBD 203 Element PBD 209

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00002 46L 00010 4L 0004146L 00023 12L 00002 4L 0008946L 00022 12L 00003 44L 0041012L 00004 12L 00002 44L 0084012L 00006 12L 00002 44L 0064012L 00003 44L 0040012L 00004 12L 00079

12L 0007312L 0006512L 0009326L 0004926L 00049

Sample Compost 1Element PBD 47

LAB PARM [mgkg]26L 0003826L 00039

Element PBD 99 Element PBD 47 Element PBD 209LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]

4L 00170 10L 00210 4L 010004L 00200 10L 00220 4L 018004L 00170 10L 00210 4L 012004L 00190 46L 00300 4L 0220010L 00280 46L 00280 46L 0210010L 00300 46L 00250 46L 0200010L 00290 46L 00260 64L 0351846L 00340 64L 00059 64L 0363846L 00330 64L 00057 64L 0364546L 00300 64L 00062 64L 0350846L 00310 64L 00060 12L 0220964L 00194 12L 00191 12L 0177164L 00154 12L 00187 12L 0292264L 00185 12L 00190 12L 0164664L 00159 12L 00186 26L 0329712L 00242 26L 00666 26L 0300012L 00223 26L 0033212L 0022112L 0022226L 0024626L 00400

Element PBD 203 Element PBD 197 Element PBD 196LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00022 46L 00027 46L 0002446L 00014 46L 00024 46L 0002264L 00036 12L 00161 64L 0005864L 00058 12L 00060 64L 0006512L 00063 12L 00061 12L 0004812L 00034 12L 00036 12L 0002512L 00038 12L 0003212L 00027 12L 00022

Element PBD 183 Element PBD 154 Element PBD 153LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00049 4L 00020 4L 0002246L 00035 4L 00022 4L 0002446L 00036 4L 00020 4L 0002246L 00034 46L 00025 4L 0002664L 00027 46L 00025 46L 0004064L 00023 46L 00025 46L 0004264L 00024 46L 00023 46L 0003564L 00020 64L 00034 46L 0003812L 00230 64L 00023 64L 0007412L 00032 64L 00017 64L 0004712L 00031 64L 00011 64L 0004612L 00030 12L 00030 64L 0003026L 00007 12L 00021 12L 0006526L 00008 12L 00021 12L 00029

12L 00021 12L 0003226L 00015 12L 0002926L 00019 26L 00039

26L 00040

Element PBD 100LAB PARM [mgkg]

4L 000384L 000414L 000374L 00038

38L 0219038L 0220038L 0208038L 0220010L 0004410L 0005010L 0004310L 0004646L 0005746L 0005946L 0005346L 0005312L 0004312L 0004512L 0004312L 0004326L 0006226L 00057

Sample Soil 3 Sample Soil 3 Sample Soil 3Element PBD 99 Element PBD 47 Element PBD 100

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]10L 00016 10L 00011 10L 0000310L 00019 10L 00010 10L 0000410L 00013 10L 00012 10L 0000410L 00019 46L 00007 10L 0000246L 00025 46L 00022 46L 0000246L 00025 46L 00005 46L 0000646L 00008 46L 00007 46L 0000246L 00011 12L 00010 46L 0000264L 00005 12L 00017 3L 29100064L 00005 12L 00010 3L 32000064L 00006 12L 00009 26L 0000564L 00007 26L 00007 26L 0000512L 00012 26L 0000712L 0001312L 0001312L 0001226L 0000526L 00006

Sample Soil 3 Sample Soil 3 Sample Soil 3Element PBD 153 Element PBD 154 Element PBD 196

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]44L 00050 4L 00010 46L 0000744L 00050 46L 00001 46L 0001146L 00002 46L 00002 46L 0000846L 00003 46L 00001 46L 0001146L 00002 46L 00002 64L 0002646L 00002 64L 00001 64L 0002664L 00001 64L 00001 64L 0002964L 00001 64L 00001 64L 0003464L 00001 64L 00002 12L 0004564L 00002 12L 00003 12L 00032

12L 00002 12L 0002212L 00002 12L 0002112L 00002

Sample Soil 3 Sample Soil 3 Sample Soil 3Element PBD 197 Element PBD 203 Element PBD 209

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00006 46L 00011 4L 0091046L 00013 46L 00017 4L 0150046L 00011 46L 00015 4L 0120046L 00013 46L 00018 4L 0160012L 00090 64L 00013 44L 0337012L 00056 64L 00014 44L 0281012L 00033 64L 00016 44L 0287012L 00032 64L 00015 44L 02540

12L 00055 46L 0230012L 00041 46L 0220012L 00027 46L 0150012L 00026 46L 01900

64L 0438164L 0401664L 0414464L 0449812L 0367112L 0397812L 0409112L 03838

Sample Soil 3 26L 0102Element PBD 183 26L 0131

LAB PARM [mgkg]46L 0000746L 0000846L 0005846L 0000764L 0000264L 0000364L 0000364L 0000312L 0001512L 0001112L 0000712L 00007

European Commission EUR 23003 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on polybrominated diphenylethers Author(s) E Sobiecka H van der Sloot D Barcelo B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 68 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07403-5 Abstract Project HORIZONTAL is interdisciplinary aiming at a harmonisation and horizontal standardisation of test procedures in particular for sludge soils and biowastes In the context of this standardization project a series of draft technical specification were designed upon an extensive desk study fine-tuned after expert consultations and finally validated in international intercomparisons exercise This report summarises the work performed within the validation study of the draft standard for the determination of polybrominated diphenylethers (PBDE) in soils sludge and treated bio-waste using gas-chromatography method with mass selective detection (GC-MS) It further explains the underlying statistical concept for the calculation of reproducibility and repeatability from intercomparisons data In addition all single values results of the statistical evaluation as well as background information on the validation materials used are described and explained

The mission of the JRC is to provide customer-driven scientific and technical support for the conception development implementation and monitoring of EU policies As a service of the European Commission the JRC functions as a reference centre of science and technology for the Union Close to the policy-making process it serves the common interest of the Member States while being independent of special interests whether private or national

LB

-NA

-23003-EN

-C

11

23 Compost from Vienna Austria

The fresh compost material was obtained from the Austrian Federal Environment Agency (UBA Vienna) which had used a sub-batch of the raw material for national intercomparson The remainder of the material was stored at 4degC until shipment to IRMM for further processing The following analytical information was provided by UBA Austria and completed with various screenings

Table 14 ndash Analytical data on compost material received from UBA Austria Inorganic and sum parameters

Parameter Unit Sample fraction used Observed mean B CAT mgl FM Fresh sample lt10mm 61 K CAT mgl FM Fresh sample lt10mm 2624 Mg CAT mgl FM Fresh sample lt10mm 242 P CAT mgl FM Fresh sample lt10mm 49 B CAT DM Fresh sample lt10mm 00017 K CAT DM Fresh sample lt10mm 072 Mg CAT DM Fresh sample lt10mm 007 P CAT DM Fresh sample lt10mm 001 NO3-N mgkg FM Fresh sample lt10mm 35 NH4-N mgkg FM Fresh sample lt10mm 230 Ctotal DM lt45degdry milled 29 Corg DM lt45degdry milled 27 Ntotal DM lt45degdry milled 17 P mgkg DM lt45degdry milled 2596 K mgkg DM lt45degdry milled 11019 K DM lt45degdry milled 110 B mgkg DM lt45degdry milled 60 Cd mgkg DM lt45degdry milled 046 Cr mgkg DM lt45degdry milled 25 Cu mgkg DM lt45degdry milled 46 Hg mgkg DM lt45degdry milled 020 Ni mgkg DM lt45degdry milled 18 Pb mgkg DM lt45degdry milled 45 Zn mgkg DM lt45degdry milled 198 Ca mgkg DM lt45degdry milled 68776 Ca DM lt45degdry milled 69 Mo mgkg DM lt45degdry milled 08 S mgkg DM lt45degdry milled 2137 Fe mgkg DM lt45degdry milled 9959 Mn mgkg DM lt45degdry milled 418 Na mgkg DM lt45degdry milled 742 Co mgkg DM lt45degdry milled 41 AOX mgkg DM lt30deg dry milled 62

Table 15 ndash Analytical data on compost material received from UBA Austria Polycyclic aromatic hydrocarbons

PAH Unit Result Naphthaline microgkg DM 93 Acenaphthylene microgkg DM 86 Acenaphthene microgkg DM 5 Fluorene microgkg DM 80 Phenanthrene microgkg DM 89 Anthracene microgkg DM 27 Fluoranthene microgkg DM 487 Pyrene microgkg DM 380

12

PAH Unit Result Benzo(a)anthracene microgkg DM 278 Chrysene microgkg DM 317 Benzo(b)fluoranthene microgkg DM 365 Benzo(k)fluoranthene microgkg DM 193 Benz(a)pyrene microgkg DM 320 Indeno(123-cd)pyrene microgkg DM 233 Dibenz(ah)anthracene microgkg DM 67 Benzo(ghi)perylene microgkg DM 225 Sum EPA microgkg DM 3013 Sum EPA mgkg DM 30

Table 16 ndash Analytical data on compost material received from UBA Austria Sum PCDDs and PCBs

Parameter

Dioxine TEQ (ITEF) ngkg DM 73 TEQ (WHO) ngkg DM 35 PCB Σ Ballschmiter mgkg DM 005

Table 17 ndash Analytical data on compost material obtained by screening in IRMM

Parameter Result in ngg

PCB 28 2 52 2 101 4 118 3 153 10 105 1 138 8 156 1 180 5 170 lt1 PAH Naphtalene lt10 Acenaphtylene lt10 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene 26 Fluoranthene 611 Pyrene 510 Benz(a)anthracene 888 Chrysene 957 Benz(b)fluoranthene 1531 Benz(k)fluoranthene 547 Benz(a)pyrene 1101 Indeno(123-cd)pyrene 416 Dibenzo(ah)anthracene 81 Benzo(ghi)perylene 295

13

Table 18 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Compost 1

(Vienna)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

402

019

259

nq

023

004

nq

nq

144

174

259

Table 19 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Compost 1

(Vienna) 0058 1426 557

Table 20 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Compost 1 (Vienna) 039 736 319 410 365 127 495 004 079 013 208

Table 21 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Compost 1 (Vienna) 2063 431 617 426 199 249 1602 lt15 10521

Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Compost 1 (Vienna) 035 3496 81 375 79 55 653 60

Table 22 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Compost 1 (Vienna) 017

14

24 Agricultural soil sludge amended soil from Pavia Italy

This sludge-amended soil material was obtained during a monitoring campaign which aimed at a generic description of the over-all soil quality in Pavia Province Italy The material which was collected from the upper horizon originates from a small farm called ldquoCascina Novellordquo During the characterisation of the site the following analytical information was obtained on a pooled sample of a sub-area of the farm of 20 X 20 m2

Table 23 ndash Analytical data on Pavia soil

Parameter Result Al 713 Wgt As 224 mgkg Cd 079 mgkg Cr 59 mgkg Cu 308 mgkg Hg 008 mgkg Ni 344 mgkg Pb 246 mgkg Zn 95 mgkg C 091 Wgt 2378-TCDD 0047 pgg 12378-PeCDD 015 pgg 123478-HxCDD 019 pgg 123678-HxCDD 15 pgg 123789-HxCDD 074 pgg 1234678-HpCDD 26 pgg OCDD 382 pgg 2378-TCDF 068 pgg 12378-PeCDF 053 pgg 23478-PeCDF 071 pgg 123478-HxDF 100 pgg 123678-HxDF 066 pgg 234678-HxDF 16 pgg 123789-HxDF 027 pgg 1234678-HpDF 12 pgg 1234789-HpDF 068 pgg OCDF 33 pgg I-TEQ 20 pgg WHO-TEQ 17 pgg

In addition the screening performed at IRMM did not reveal significant quantities of PCBs and PAHs which were all below the LoDs (1 ngg for PCBs and 10 ngg for PAHs respectively)

Table 24 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 5 (Pavia) 0005 0011 154

15

Table 25 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 5

(Pavia)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

039

nq

nq

008

nq

nd

nd

670

671

Table 26 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 5 (Pavia) 033 184 573 225 426 305 206 200 lt 005 381 878

Table 27 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 5 (Pavia) 6939 129 145 224 425 116 6118 255 1789 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 5 (Pavia) 184 62 38 108 55 66 597 110

Table 28 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 5 (Pavia) 006

16

25 Sludge-amended-soil from Barcelona Spain

The sludge-amended soil material from Barcelona sampled upon indication from the Barcelorsquo- Group in Barcelona

Table 29 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 2 (Lleida T) 0015 0183 1138

Table 30 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 2

(Lleida T)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

159

045

nq

048

160

nq

nq

1000

1004

Table 31 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 2 (Lleida T) 059 141 327 536 405 186 184 224 lt 005 318 111

Table 32 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 2 (Lleida T) 4443 1067 1429 253 344 204 4116 780 3396 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 2 (Lleida T) 064 65 26 125 59 17 547 65

Table 33 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 2 (Lleida T) 010

17

26 Sludge amended soil from Essen Germany

The German sludge-amended soil from Essen which was provided as the three sludge materials by LUA NRW did not feature significant concentrations of the PCB congeners 28 52 101 118 153 105 138 156 180 170 but had detectable amounts of some PAHs

Table 34 ndash Analytical screening data on the German sludge-amended soil

Parameter Concentration(ngg)

Naphtalene lt10 Acenaphtylene lt10 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene lt10 Fluoranthene 28 Pyrene 20 Benz(a)anthracene 24 Chrysene 47 Benz(b)fluoranthene 76 Benz(k)fluoranthene 20 Benz(a)pyrene 35 Indeno(123-cd)pyrene 35 Dibenzo(ah)anthracene 10 Benzo(ghi)perylene 26

Table 35 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 4 (Essen) 0011 0302 055

Table 36 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 4

(Essen)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

nq

nq

nq

nq

nq

nq

128

191

203

18

Table 37 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 4 (Essen) 052 545 261 805 320 403 273 273 lt 005 295 781

Table 38 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 4 (Essen) 7947 442 085 06 086 007 2163 189 2019 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 4 (Essen) 045 19 42 87 683 60 462 61

Table 39 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 4 (Essen) 004

27 Long-term sludge exposed soil from Hohenheim-Stuttgart Germany

Similarly an additional sludge exposed soil was sampled at the University of Hohenheim Stuttgart were a test soil was long-term exposed to elevated concentrations of sewage sludge

Table 40 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 1 (Stuttgart) 0045 0263 1765

Table 41 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 1

(Stuttgart)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

230

006

004

004

nq

nd

nd

498

500

19

Table 42 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 1 (Stuttgart) 069 127 361 262 504 183 252 262 lt 005 266 142

Table 43 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 1 (Stuttgart) 7194 1006 133 186 366 088 7874 275 3571 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 1 (Stuttgart) 123 50 47 212 85 69 991 129

Table 44 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 1 (Stuttgart) 177

18

Annex 3

Statistical calculations

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 47)Mandels h statistics(Sludge 1 - PBD 47)

Sample Sludge 1 NUM

Element PBD 47

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00213 0001 3 -021 005 - - 10L - - NUM46L 00273 0002 4 016 021 - - 46L - - NUM64L 00059 0000 4 -116 002 NUM - 64L - - NUM12L 00188 0000 4 -036 002 - - 12L - - NUM26L 00499 0024 2 157 223 Fail - - 26L - - NUM

Totgem 0025 0005 mgkg 1-level 172 (185) NUM (10L46L64L12L26L) -1Totstd= 0016 0010 5-level 157 (162) 5

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 5 Labs rejected (10L46L64L12L26L)

000 050 100 150 200 250

k-values

10L

46L

64L

12L

26L

Mandels k statistics(Sludge 1 - PBD 47)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

10L

46L

64L

12L

26L

Labo

rato

ries

NUM

-200 -100 000 100 200

h-values

10L

46L

64L

12L

26L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 47)

Sludge 1-PBD 47

Unit mgkg

Mandels k statistics(Soil 3 - PBD 47)Mandels h statistics(Soil 3 - PBD 47)

Sample Soil 3 Soil 3 - PBD 47 -- Mean PARM = 0001 [mgkg]

Element PBD 47

General calcparmT1= 134814E-02T2= 142830E-05T3= 13T4= 45T5= 22767E-06

n= variabelp= 4

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean26L 00007 0000 2 -143 001 00007 00000 2 1 00046L 00010 0001 4 010 181 00010 00008 4 3 00010L 00011 0000 3 049 023 00011 00001 3 2 00012L 00012 0000 4 084 081 00012 00004 4 3 000

Totgem 0001 0000 mgkg 1-level 149 (177) 4 00010 () 4 3Totstd= 0000 0000 5-level 142 (159)

RESULTS Mean = 000100 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000050 --gt 5031 r = 00014Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000050 --gt 5031 R = 00014Remarks none

000 050 100 150 200

k-values

26L

46L

10L

12L

Mandels k statistics(Soil 3 - PBD 47)

00 00 00 00 00 00 00 00 00 00 00

Deviation from Mean

26L

46L

10L

12L

Labo

rato

ries

Soil 3 - PBD 47 -- Mean PARM = 0001 [mgkg]

-200 -100 000 100

h-values

26L

46L

10L

12L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 47)

Soil 3-PBD 47

Unit mgkg

Mandels k statistics(Compost 1 - PBD 99)Mandels h statistics(Compost 1 - PBD 99)

Sample Compost 1 Compost 1 - PBD 99 -- Mean PARM = 0003 [mgkg]

Element PBD 99

General calcparmT1= 492124E-02T2= 148747E-04T3= 17T4= 61T5= 93196E-06

n= variabelp= 5

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00020 0000 4 -137 053 00020 00004 4 3 000

26L 00025 0000 2 -058 024 00025 00002 2 1 00010L 00029 0000 3 012 032 00029 00003 3 2 00046L 00033 0001 4 069 161 00033 00013 4 3 00012L 00036 0001 4 114 140 00036 00011 4 3 000

Totgem 0003 0001 mgkg 1-level 172 (185) 5 00029 () 5 4Totstd= 0001 0001 5-level 157 (162)

RESULTS Mean = 000286 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000088 --gt 3086 r = 00025Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000101 --gt 3525 R = 00028Remarks none

000 050 100 150 200

k-values

4L

26L

10L

46L

12L

Mandels k statistics(Compost 1 - PBD 99)

00 00 00 00 00 00 00 00 00 00

Deviation from Mean

4L

26L

10L

46L

12L

Labo

rato

ries

Compost 1 - PBD 99 -- Mean PARM = 0003 [mgkg]

-200 -100 000 100 200

h-values

4L

26L

10L

46L

12L

Labo

rato

ries

Mandels h statistics(Compost 1 - PBD 99)

Compost 1-PBD 99

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 99)Mandels h statistics(Sludge 1 - PBD 99)

Sample Sludge 1 Sludge 1 - PBD 99 -- Mean PARM = 0024 [mgkg]

Element PBD 99

General calcparmT1= 448050E-01T2= 112113E-02T3= 19T4= 73T5= 32972E-05

n= variabelp= 5

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean64L 00173 0002 4 -118 041 Fail 00173 00019 4 3 -0014L 00183 0002 4 -104 032 00183 00015 4 3 -001

12L 00227 0001 4 -038 022 00227 00010 4 3 00010L 00290 0001 3 055 021 00290 00010 3 2 00146L 00320 0002 4 100 039 00320 00018 4 3 00126L 00323 0011 2 105 234 - - 26L - - 001

Totgem 0025 0003 mgkg 1-level 187 (177) 5 00239 (26L) 5 4Totstd= 0007 0004 5-level 166 (154) 1

RESULTS Mean = 002385 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000153 --gt 643 r = 00043Between lab variance S2L = 000004Reproducibility var S2R = 000004Reproducibility std SR = 000666 --gt 2791 R = 00186Remarks 1 Lab rejected (26L)

000 050 100 150 200 250

k-values

64L

4L

12L

10L

46L

26L

Mandels k statistics(Sludge 1 - PBD 99)

00 00 00 00 00 00 00 00 00 00

Deviation from Mean

64L

4L

12L

10L

46L

26L

Labo

rato

ries

Sludge 1 - PBD 99 -- Mean PARM = 0024 [mgkg]

-200 -100 000 100 200

h-values

64L

4L

12L

10L

46L

26L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 99)

Sludge 1-PBD 99

Unit mgkg

Mandels k statistics(Soil 3 - PBD 99)Mandels h statistics(Soil 3 - PBD 99)

Sample Soil 3 NUM

Element PBD 99

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00017 0000 4 091 068 - - 10L - - NUM46L 00017 0001 4 100 211 - - 46L - - NUM64L 00005 0000 4 -106 023 NUM - 64L - - NUM12L 00012 0000 4 015 014 - - 12L - - NUM26L 00006 0000 2 -101 012 - - 26L - - NUM

Totgem 0001 0000 mgkg 1-level 172 (173) NUM (10L46L64L12L26L) -1Totstd= 0001 0000 5-level 157 (153) 5

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 5 Labs rejected (10L46L64L12L26L)

000 050 100 150 200 250

k-values

10L

46L

64L

12L

26L

Mandels k statistics(Soil 3 - PBD 99)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

10L

46L

64L

12L

26L

Labo

rato

ries

NUM

-200 -100 000 100 200

h-values

10L

46L

64L

12L

26L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 99)

Soil 3-PBD 99

Unit mgkg

Mandels k statistics(Compost 1 - PBD 100)Mandels h statistics(Compost 1 - PBD 100)

Sample Compost 1 Compost 1 - PBD 100 -- Mean PARM = 0001 [mgkg]

Element PBD 100

General calcparmT1= 124272E-02T2= 113129E-05T3= 14T4= 52T5= 46584E-07

n= variabelp= 4

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean26L 00006 0000 2 -131 037 Fail 00006 00001 2 1 00010L 00009 0000 4 003 083 00009 00002 4 3 00046L 00009 0000 4 016 115 00009 00002 4 3 00012L 00011 0000 4 112 136 Fail 00011 00003 4 3 000

Totgem 0001 0000 mgkg 1-level 149 (167) 4 00009 () 4 3Totstd= 0000 0000 5-level 142 (15)

RESULTS Mean = 000085 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000022 --gt 2531 r = 00006Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000025 --gt 2882 R = 00007Remarks none

000 050 100 150

k-values

26L

10L

46L

12L

Mandels k statistics(Compost 1 - PBD 100)

00 00 00 00 00 00 00 00 00 00 00

Deviation from Mean

26L

10L

46L

12L

Labo

rato

ries

Compost 1 - PBD 100 -- Mean PARM = 0001 [mgkg]

-200 -100 000 100 200

h-values

26L

10L

46L

12L

Labo

rato

ries

Mandels h statistics(Compost 1 - PBD 100)

Compost 1-PBD 100

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 100)Mandels h statistics(Sludge 1 - PBD 100)

Sample Sludge 1 Sludge 1 - PBD 100 -- Mean PARM = 0005 [mgkg]

Element PBD 100

General calcparmT1= 852065E-02T2= 412762E-04T3= 18T4= 68T5= 78914E-07

n= variabelp= 5

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00039 0000 4 -042 007 Fail 00039 00002 4 3 000

12L 00044 0000 4 -041 005 Fail 00044 00001 4 3 00010L 00046 0000 4 -041 013 Fail 00046 00003 4 3 00046L 00056 0000 4 -040 012 Fail 00056 00003 4 3 00026L 00059 0000 2 -040 013 Fail 00059 00003 2 1 00038L 02168 0006 4 204 244 Fail - - 38L - - 021

Totgem 0040 0001 mgkg 1-level 187 (177) 5 00049 (38L) 5 4Totstd= 0087 0002 5-level 166 (154) 1

RESULTS Mean = 000486 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000025 --gt 507 r = 00007Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000084 --gt 1731 R = 00024Remarks 1 Lab rejected (38L)

000 050 100 150 200 250

k-values

4L

12L

10L

46L

26L

38L

Mandels k statistics(Sludge 1 - PBD 100)

-01 00 01 01 02 02 03

Deviation from Mean

4L

12L

10L

46L

26L

38L

Labo

rato

ries

Sludge 1 - PBD 100 -- Mean PARM = 0005 [mgkg]

-100 000 100 200 300

h-values

4L

12L

10L

46L

26L

38L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 100)

Sludge 1-PBD 100

Unit mgkg

Mandels k statistics(Soil 3 - PBD 100)Mandels h statistics(Soil 3 - PBD 100)

Sample Soil 3 NUM

Element PBD 100

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00003 0000 4 -050 000 Fail - - 10L - - NUM46L 00003 0000 4 -050 000 Fail NUM - 46L - - NUM3L 305500 2051 2 150 200 Fail - - 3L - - NUM

26L 00005 0000 2 -050 000 Fail - - 26L - - NUM

Totgem 7638 0513 mgkg 1-level 149 (177) NUM (10L46L3L26L) -1Totstd= 15275 1025 5-level 142 (159) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (10L46L3L26L)

000 050 100 150 200

k-values

10L

46L

3L

26L

Mandels k statistics(Soil 3 - PBD 100)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

10L

46L

3L

26L

Labo

rato

ries

NUM

-100 000 100 200

h-values

10L

46L

3L

26L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 100)

Soil 3-PBD 100

Unit mgkg

Mandels k statistics(Compost 1 - PBD 153)Mandels h statistics(Compost 1 - PBD 153)

Sample Compost 1 NUM

Element PBD 153

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean44L 00053 0001 3 150 157 Fail - - 44L - - NUM46L 00007 0000 4 -044 111 Fail - - 46L - - NUM12L 00005 0000 4 -051 055 Fail - - 12L - - NUM26L 00005 0000 2 -054 001 Fail NUM - 26L - - NUM

Totgem 0002 0000 mgkg 1-level 149 (177) NUM (44L46L12L26L) -1Totstd= 0002 0000 5-level 142 (159) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (44L46L12L26L)

000 050 100 150 200

k-values

44L

46L

12L

26L

Mandels k statistics(Compost 1 - PBD 153)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

44L

46L

12L

26L

Labo

rato

ries

NUM

-100 000 100 200

h-values

44L

46L

12L

26L

Labo

rato

ries

Mandels h statistics(Compost 1 - PBD 153)

Compost 1-PBD 153

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 153)Mandels h statistics(Sludge 1 - PBD 153)

Sample Sludge 1 Sludge 1 - PBD 153 -- Mean PARM = 0004 [mgkg]

Element PBD 153

General calcparmT1= 676738E-02T2= 267609E-04T3= 18T4= 68T5= 19626E-05

n= variabelp= 5

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00024 0000 4 -157 017 00024 00002 4 3 000

12L 00038 0002 4 006 154 00038 00018 4 3 00046L 00039 0000 4 011 026 00039 00003 4 3 00026L 00039 0000 2 018 004 00039 00000 2 1 00064L 00049 0002 4 122 159 00049 00018 4 3 000

Totgem 0004 0001 mgkg 1-level 172 (173) 5 00038 () 5 4Totstd= 0001 0001 5-level 157 (153)

RESULTS Mean = 000378 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000123 --gt 3252 r = 00034Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000142 --gt 3754 R = 00040Remarks none

000 050 100 150 200

k-values

4L

12L

46L

26L

64L

Mandels k statistics(Sludge 1 - PBD 153)

00 00 00 00 00 00 00

Deviation from Mean

4L

12L

46L

26L

64L

Labo

rato

ries

Sludge 1 - PBD 153 -- Mean PARM = 0004 [mgkg]

-200 -100 000 100 200

h-values

4L

12L

46L

26L

64L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 153)

Sludge 1-PBD 153

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 154)Mandels h statistics(Sludge 1 - PBD 154)

Sample Sludge 1 NA

Element PBD 154

General calcparmT1= NAT2= NAT3=T4=T5=

n= variabelp=

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00021 0000 3 -100 021 NA - 4L - - NA

46L 00025 0000 4 115 018 NA - 46L - - NA64L 00021 0001 4 -066 179 - - 64L - - NA12L 00023 0000 4 050 085 - - 12L - - NA

Totgem 0002 0000 mgkg 1-level 149 (167) NA (4L46L64L12L) -1Totstd= 0000 0000 5-level 142 (15) 4

RESULTS Mean = NA mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NAReproducibility var S2R = NAReproducibility std SR = NA --gt NA R = NARemarks 4 Labs rejected (4L46L64L12L)

000 050 100 150 200

k-values

4L

46L

64L

12L

Mandels k statistics(Sludge 1 - PBD 154)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

4L

46L

64L

12L

Labo

rato

ries

NA

-100 000 100 200

h-values

4L

46L

64L

12L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 154)

Sludge 1-PBD 154

Unit mgkg

Mandels k statistics(Soil 3 - PBD 154)Mandels h statistics(Soil 3 - PBD 154)

Sample Soil 3 NUM

Element PBD 154

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

4L 00010 - 1 150 Fail - - 4L - - NUM46L 00001 0000 4 -053 096 Fail - - 46L - - NUM64L 00001 0000 4 -056 105 Fail NUM - 64L - - NUM12L 00002 0000 4 -040 099 Fail - - 12L - - NUM

Totgem 000037 0000 mgkg 1-level 149 (164) NUM (4L46L64L12L) -1Totstd= 000042 0000 5-level 142 (153) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (4L46L64L12L)

000 050 100 150

k-values

4L

46L

64L

12L

Mandels k statistics(Soil 3 - PBD 154)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

4L

46L

64L

12L

Labo

rato

ries

NUM

-100 000 100 200

h-values

4L

46L

64L

12L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 154)

Soil 3-PBD 154

Unit mgkg

Mandels k statistics(Compost 1 - PBD 209)Mandels h statistics(Compost 1 - PBD 209)

Sample Compost 1 NUM

Element PBD 209

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00065 0003 2 -049 032 - - 4L - - NUM

44L 00573 0021 4 150 197 Fail - - 44L - - NUM12L 00078 0001 4 -045 011 - - 12L - - NUM26L 00049 0000 2 -056 000 NUM - 26L - - NUM

Totgem 0019 0006 mgkg 1-level 149 (177) NUM (4L44L12L26L) -1Totstd= 0025 0010 5-level 142 (159) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (4L44L12L26L)

000 050 100 150 200

k-values

4L

44L

12L

26L

Mandels k statistics(Compost 1 - PBD 209)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

4L

44L

12L

26L

Labo

rato

ries

NUM

-100 000 100 200

h-values

4L

44L

12L

26L

Labo

rato

ries

Mandels h statistics(Compost 1 - PBD 209)

Compost 1-PBD 209

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 209)Mandels h statistics(Sludge 1 - PBD 209)

Sample Sludge 1 Sludge 1 - PBD 209 -- Mean PARM = 0249 [mgkg]

Element PBD 209

General calcparmT1= 394542E+00T2= 107296E+00T3= 16T4= 56T5= 19723E-02

n= variabelp= 5

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 01550 0055 4 -112 148 Fail 01550 00551 4 3 -009

46L 02050 0007 2 -053 019 02050 00071 2 1 -00412L 02137 0058 4 -042 155 02137 00576 4 3 -00426L 03149 0021 2 078 057 Fail 03149 00210 2 1 00764L 03577 0007 4 129 020 Fail 03577 00074 4 3 011

Totgem 0249 0030 mgkg 1-level 172 (185) 5 02493 () 5 4Totstd= 0084 0025 5-level 157 (162)

RESULTS Mean = 024926 mgkg

Repeatability variance S2r = 000179Repeatability std Sr = 004234 --gt 1699 r = 01186Between lab variance S2L = 000743Reproducibility var S2R = 000922Reproducibility std SR = 009604 --gt 3853 R = 02689Remarks none

000 050 100 150 200

k-values

4L

46L

12L

26L

64L

Mandels k statistics(Sludge 1 - PBD 209)

-01 -01 00 01 01 02

Deviation from Mean

4L

46L

12L

26L

64L

Labo

rato

ries

Sludge 1 - PBD 209 -- Mean PARM = 0249 [mgkg]

-200 -100 000 100 200

h-values

4L

46L

12L

26L

64L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 209)

Sludge 1-PBD 209

Unit mgkg

Mandels k statistics(Soil 3 - PBD 209)Mandels h statistics(Soil 3 - PBD 209)

Sample Soil 3 Soil 3 - PBD 209 -- Mean PARM = 0258 [mgkg]

Element PBD 209

General calcparmT1= 596398E+00T2= 191917E+00T3= 22T4= 84T5= 13249E-02

n= variabelp= 6

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean26L 01162 0021 2 -108 074 Fail 01162 00207 2 1 -0144L 01303 0031 4 -097 111 Fail 01303 00312 4 3 -013

46L 01975 0036 4 -046 128 Fail 01975 00359 4 3 -00644L 02898 0035 4 024 124 Fail 02898 00346 4 3 00312L 03895 0018 4 100 065 Fail 03895 00181 4 3 01364L 04260 0022 4 127 078 Fail 04260 00219 4 3 017

Totgem 0258 0027 mgkg 1-level 187 (177) 6 02582 () 6 5Totstd= 0132 0008 5-level 166 (154)

RESULTS Mean = 025818 mgkg

Repeatability variance S2r = 000083Repeatability std Sr = 002878 --gt 1115 r = 00806Between lab variance S2L = 001640Reproducibility var S2R = 001723Reproducibility std SR = 013127 --gt 5084 R = 03676Remarks none

000 050 100 150

k-values

26L

4L

46L

44L

12L

64L

Mandels k statistics(Soil 3 - PBD 209)

-02 -01 -01 00 01 01 02 02

Deviation from Mean

26L

4L

46L

44L

12L

64L

Labo

rato

ries

Soil 3 - PBD 209 -- Mean PARM = 0258 [mgkg]

-200 -100 000 100 200

h-values

26L

4L

46L

44L

12L

64L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 209)

Soil 3-PBD 209

Unit mgkg

Mandels k statistics(Compost 1 - Sum PBD)Mandels h statistics(Compost 1 - Sum PBD)

Sample Compost 1 Compost 1 - Sum PBD -- Mean PARM = 0009 [mgkg]

Element Sum PBD

General calcparmT1= 154064E-01T2= 169065E-03T3= 18T4= 68T5= 11354E-04

n= variabelp= 5

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00031 0002 4 -067 016 00031 00016 4 3 -0014L 00055 0005 4 -056 048 00055 00047 4 3 000

46L 00085 0003 4 -042 031 00085 00030 4 3 00026L 00123 0000 2 -024 003 00123 00002 2 1 00012L 00154 0002 4 -011 021 00154 00021 4 3 00144L 00613 0023 4 200 237 Fail - - 44L - - 005

Totgem 0018 0006 mgkg 1-level 187 (177) 5 00089 (44L) 5 4Totstd= 0022 0009 5-level 166 (154) 1

RESULTS Mean = 000893 mgkg

Repeatability variance S2r = 000001Repeatability std Sr = 000296 --gt 3308 r = 00083Between lab variance S2L = 000002Reproducibility var S2R = 000003Reproducibility std SR = 000570 --gt 6374 R = 00159Remarks 1 Lab rejected (44L)

000 050 100 150 200 250

k-values

10L

4L

46L

26L

12L

44L

Mandels k statistics(Compost 1 - Sum PBD)

00 00 00 00 00 00 01 01

Deviation from Mean

10L

4L

46L

26L

12L

44L

Labo

rato

ries

Compost 1 - Sum PBD -- Mean PARM = 0009 [mgkg]

-100 000 100 200

h-values

10L

4L

46L

26L

12L

44L

Labo

rato

ries

Mandels h statistics(Compost 1 - Sum PBD)

Compost 1-Sum PBD

Unit mgkg

Mandels k statistics(Sludge 1 - Sum PBD)Mandels h statistics(Sludge 1 - Sum PBD)

Sample Sludge 1 Sludge 1 - Sum PBD -- Mean PARM = 0256 [mgkg]

Element Sum PBD

General calcparmT1= 531806E+00T2= 162188E+00T3= 22T4= 84T5= 25223E-02

n= variabelp= 6

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00423 0025 4 -156 044 Fail 00423 00252 4 3 -02146L 01808 0118 4 -049 205 - - 46L - - -0074L 01810 0056 4 -049 097 01810 00558 4 3 -007

38L 02168 0006 4 -022 010 02168 00059 4 3 -00412L 02890 0065 4 034 113 02890 00647 4 3 00364L 03958 0008 4 116 014 Fail 03958 00079 4 3 01426L 04094 0034 2 126 059 Fail 04094 00337 2 1 015

Totgem 0245 0044 mgkg 1-level 198 (179) 6 02557 (46L) 6 5Totstd= 0130 0039 5-level 171 (155) 1

RESULTS Mean = 025570 mgkg

Repeatability variance S2r = 000158Repeatability std Sr = 003970 --gt 1553 r = 01112Between lab variance S2L = 001807Reproducibility var S2R = 001964Reproducibility std SR = 014015 --gt 5481 R = 03924Remarks 1 Lab rejected (46L)

000 050 100 150 200 250

k-values

10L

46L

4L

38L

12L

64L

26L

Mandels k statistics(Sludge 1 - Sum PBD)

-03 -02 -02 -01 -01 00 01 01 02 02

Deviation from Mean

10L

46L

4L

38L

12L

64L

26L

Labo

rato

ries

Sludge 1 - Sum PBD -- Mean PARM = 0256 [mgkg]

-200 -100 000 100 200

h-values

10L

46L

4L

38L

12L

64L

26L

Labo

rato

ries

Mandels h statistics(Sludge 1 - Sum PBD)

Sludge 1-Sum PBD

Unit mgkg

Mandels k statistics(Soil 3 - Sum PBD)Mandels h statistics(Soil 3 - Sum PBD)

Sample Soil 3 Soil 3 - Sum PBD -- Mean PARM = 0227 [mgkg]

Element Sum PBD

General calcparmT1= 610980E+00T2= 200876E+00T3= 26T4= 100T5= 13106E-02

n= variabelp= 7

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00028 0001 4 -037 000 Fail 00028 00005 4 3 -02226L 01179 0021 2 -036 003 Fail 01179 00208 2 1 -0114L 01305 0031 4 -036 004 Fail 01305 00308 4 3 -010

46L 02065 0035 4 -036 005 Fail 02065 00350 4 3 -00244L 02923 0037 4 -035 005 Fail 02923 00365 4 3 00712L 04051 0015 4 -034 002 Fail 04051 00149 4 3 01864L 04314 0022 4 -033 003 Fail 04314 00223 4 3 0203L 305500 2051 2 247 283 Fail - - 3L - - 3032

Totgem 4017 0276 mgkg 1-level 206 (181) 7 02266 (3L) 7 6Totstd= 10722 0717 5-level 175 (156) 1

RESULTS Mean = 022663 mgkg

Repeatability variance S2r = 000069Repeatability std Sr = 002626 --gt 1159 r = 00735Between lab variance S2L = 002568Reproducibility var S2R = 002637Reproducibility std SR = 016238 --gt 7165 R = 04547Remarks 1 Lab rejected (3L)

000 050 100 150 200 250 300

k-values

10L

26L

4L

46L

44L

12L

64L

3L

Mandels k statistics(Soil 3 - Sum PBD)

-50 00 50 100 150 200 250 300 350

Deviation from Mean

10L

26L

4L

46L

44L

12L

64L

3L

Labo

rato

ries

Soil 3 - Sum PBD -- Mean PARM = 0227 [mgkg]

-100 000 100 200 300

h-values

10L

26L

4L

46L

44L

12L

64L

3L

Labo

rato

ries

Mandels h statistics(Soil 3 - Sum PBD)

Soil 3-Sum PBD

19

Annex 4

Raw data submitted

Sample Compost1 Sample Compost 1 Sample Compost 1Element PBD 99 Element PBD 100 Element PBD 153

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]4L 00021 10L 00008 44L 000504L 00024 10L 00008 44L 000604L 00014 10L 00007 44L 000504L 00020 10L 00011 46L 00004

10L 00029 46L 00007 46L 0001210L 00027 46L 00012 46L 0000410L 00032 46L 00009 46L 0000946L 00025 46L 00007 12L 0000446L 00052 12L 00008 12L 0000846L 00029 12L 00012 12L 0000446L 00026 12L 00008 12L 0000712L 00026 12L 00014 26L 0000512L 00043 26L 00007 26L 0000512L 00026 26L 0000612L 0004726L 0002626L 00024

Sample Compost 1 Sample Compost 1 Sample Compost 1Element PBD 154 Element PBD 183 Element PBD 196

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]4L 00010 46L 00002 46L 00011

46L 00003 46L 00024 46L 0000846L 00007 46L 00021 12L 0000246L 00003 46L 00003 12L 0000346L 00004 12L 00003 12L 0000112L 00003 12L 00011 12L 0000212L 00005 12L 0000312L 00031 12L 0000312L 00006

Sample Compost 1 Sample Compost 1 Sample Compost 1Element PBD 197 Element PBD 203 Element PBD 209

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00002 46L 00010 4L 0004146L 00023 12L 00002 4L 0008946L 00022 12L 00003 44L 0041012L 00004 12L 00002 44L 0084012L 00006 12L 00002 44L 0064012L 00003 44L 0040012L 00004 12L 00079

12L 0007312L 0006512L 0009326L 0004926L 00049

Sample Compost 1Element PBD 47

LAB PARM [mgkg]26L 0003826L 00039

Element PBD 99 Element PBD 47 Element PBD 209LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]

4L 00170 10L 00210 4L 010004L 00200 10L 00220 4L 018004L 00170 10L 00210 4L 012004L 00190 46L 00300 4L 0220010L 00280 46L 00280 46L 0210010L 00300 46L 00250 46L 0200010L 00290 46L 00260 64L 0351846L 00340 64L 00059 64L 0363846L 00330 64L 00057 64L 0364546L 00300 64L 00062 64L 0350846L 00310 64L 00060 12L 0220964L 00194 12L 00191 12L 0177164L 00154 12L 00187 12L 0292264L 00185 12L 00190 12L 0164664L 00159 12L 00186 26L 0329712L 00242 26L 00666 26L 0300012L 00223 26L 0033212L 0022112L 0022226L 0024626L 00400

Element PBD 203 Element PBD 197 Element PBD 196LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00022 46L 00027 46L 0002446L 00014 46L 00024 46L 0002264L 00036 12L 00161 64L 0005864L 00058 12L 00060 64L 0006512L 00063 12L 00061 12L 0004812L 00034 12L 00036 12L 0002512L 00038 12L 0003212L 00027 12L 00022

Element PBD 183 Element PBD 154 Element PBD 153LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00049 4L 00020 4L 0002246L 00035 4L 00022 4L 0002446L 00036 4L 00020 4L 0002246L 00034 46L 00025 4L 0002664L 00027 46L 00025 46L 0004064L 00023 46L 00025 46L 0004264L 00024 46L 00023 46L 0003564L 00020 64L 00034 46L 0003812L 00230 64L 00023 64L 0007412L 00032 64L 00017 64L 0004712L 00031 64L 00011 64L 0004612L 00030 12L 00030 64L 0003026L 00007 12L 00021 12L 0006526L 00008 12L 00021 12L 00029

12L 00021 12L 0003226L 00015 12L 0002926L 00019 26L 00039

26L 00040

Element PBD 100LAB PARM [mgkg]

4L 000384L 000414L 000374L 00038

38L 0219038L 0220038L 0208038L 0220010L 0004410L 0005010L 0004310L 0004646L 0005746L 0005946L 0005346L 0005312L 0004312L 0004512L 0004312L 0004326L 0006226L 00057

Sample Soil 3 Sample Soil 3 Sample Soil 3Element PBD 99 Element PBD 47 Element PBD 100

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]10L 00016 10L 00011 10L 0000310L 00019 10L 00010 10L 0000410L 00013 10L 00012 10L 0000410L 00019 46L 00007 10L 0000246L 00025 46L 00022 46L 0000246L 00025 46L 00005 46L 0000646L 00008 46L 00007 46L 0000246L 00011 12L 00010 46L 0000264L 00005 12L 00017 3L 29100064L 00005 12L 00010 3L 32000064L 00006 12L 00009 26L 0000564L 00007 26L 00007 26L 0000512L 00012 26L 0000712L 0001312L 0001312L 0001226L 0000526L 00006

Sample Soil 3 Sample Soil 3 Sample Soil 3Element PBD 153 Element PBD 154 Element PBD 196

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]44L 00050 4L 00010 46L 0000744L 00050 46L 00001 46L 0001146L 00002 46L 00002 46L 0000846L 00003 46L 00001 46L 0001146L 00002 46L 00002 64L 0002646L 00002 64L 00001 64L 0002664L 00001 64L 00001 64L 0002964L 00001 64L 00001 64L 0003464L 00001 64L 00002 12L 0004564L 00002 12L 00003 12L 00032

12L 00002 12L 0002212L 00002 12L 0002112L 00002

Sample Soil 3 Sample Soil 3 Sample Soil 3Element PBD 197 Element PBD 203 Element PBD 209

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00006 46L 00011 4L 0091046L 00013 46L 00017 4L 0150046L 00011 46L 00015 4L 0120046L 00013 46L 00018 4L 0160012L 00090 64L 00013 44L 0337012L 00056 64L 00014 44L 0281012L 00033 64L 00016 44L 0287012L 00032 64L 00015 44L 02540

12L 00055 46L 0230012L 00041 46L 0220012L 00027 46L 0150012L 00026 46L 01900

64L 0438164L 0401664L 0414464L 0449812L 0367112L 0397812L 0409112L 03838

Sample Soil 3 26L 0102Element PBD 183 26L 0131

LAB PARM [mgkg]46L 0000746L 0000846L 0005846L 0000764L 0000264L 0000364L 0000364L 0000312L 0001512L 0001112L 0000712L 00007

European Commission EUR 23003 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on polybrominated diphenylethers Author(s) E Sobiecka H van der Sloot D Barcelo B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 68 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07403-5 Abstract Project HORIZONTAL is interdisciplinary aiming at a harmonisation and horizontal standardisation of test procedures in particular for sludge soils and biowastes In the context of this standardization project a series of draft technical specification were designed upon an extensive desk study fine-tuned after expert consultations and finally validated in international intercomparisons exercise This report summarises the work performed within the validation study of the draft standard for the determination of polybrominated diphenylethers (PBDE) in soils sludge and treated bio-waste using gas-chromatography method with mass selective detection (GC-MS) It further explains the underlying statistical concept for the calculation of reproducibility and repeatability from intercomparisons data In addition all single values results of the statistical evaluation as well as background information on the validation materials used are described and explained

The mission of the JRC is to provide customer-driven scientific and technical support for the conception development implementation and monitoring of EU policies As a service of the European Commission the JRC functions as a reference centre of science and technology for the Union Close to the policy-making process it serves the common interest of the Member States while being independent of special interests whether private or national

LB

-NA

-23003-EN

-C

12

PAH Unit Result Benzo(a)anthracene microgkg DM 278 Chrysene microgkg DM 317 Benzo(b)fluoranthene microgkg DM 365 Benzo(k)fluoranthene microgkg DM 193 Benz(a)pyrene microgkg DM 320 Indeno(123-cd)pyrene microgkg DM 233 Dibenz(ah)anthracene microgkg DM 67 Benzo(ghi)perylene microgkg DM 225 Sum EPA microgkg DM 3013 Sum EPA mgkg DM 30

Table 16 ndash Analytical data on compost material received from UBA Austria Sum PCDDs and PCBs

Parameter

Dioxine TEQ (ITEF) ngkg DM 73 TEQ (WHO) ngkg DM 35 PCB Σ Ballschmiter mgkg DM 005

Table 17 ndash Analytical data on compost material obtained by screening in IRMM

Parameter Result in ngg

PCB 28 2 52 2 101 4 118 3 153 10 105 1 138 8 156 1 180 5 170 lt1 PAH Naphtalene lt10 Acenaphtylene lt10 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene 26 Fluoranthene 611 Pyrene 510 Benz(a)anthracene 888 Chrysene 957 Benz(b)fluoranthene 1531 Benz(k)fluoranthene 547 Benz(a)pyrene 1101 Indeno(123-cd)pyrene 416 Dibenzo(ah)anthracene 81 Benzo(ghi)perylene 295

13

Table 18 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Compost 1

(Vienna)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

402

019

259

nq

023

004

nq

nq

144

174

259

Table 19 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Compost 1

(Vienna) 0058 1426 557

Table 20 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Compost 1 (Vienna) 039 736 319 410 365 127 495 004 079 013 208

Table 21 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Compost 1 (Vienna) 2063 431 617 426 199 249 1602 lt15 10521

Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Compost 1 (Vienna) 035 3496 81 375 79 55 653 60

Table 22 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Compost 1 (Vienna) 017

14

24 Agricultural soil sludge amended soil from Pavia Italy

This sludge-amended soil material was obtained during a monitoring campaign which aimed at a generic description of the over-all soil quality in Pavia Province Italy The material which was collected from the upper horizon originates from a small farm called ldquoCascina Novellordquo During the characterisation of the site the following analytical information was obtained on a pooled sample of a sub-area of the farm of 20 X 20 m2

Table 23 ndash Analytical data on Pavia soil

Parameter Result Al 713 Wgt As 224 mgkg Cd 079 mgkg Cr 59 mgkg Cu 308 mgkg Hg 008 mgkg Ni 344 mgkg Pb 246 mgkg Zn 95 mgkg C 091 Wgt 2378-TCDD 0047 pgg 12378-PeCDD 015 pgg 123478-HxCDD 019 pgg 123678-HxCDD 15 pgg 123789-HxCDD 074 pgg 1234678-HpCDD 26 pgg OCDD 382 pgg 2378-TCDF 068 pgg 12378-PeCDF 053 pgg 23478-PeCDF 071 pgg 123478-HxDF 100 pgg 123678-HxDF 066 pgg 234678-HxDF 16 pgg 123789-HxDF 027 pgg 1234678-HpDF 12 pgg 1234789-HpDF 068 pgg OCDF 33 pgg I-TEQ 20 pgg WHO-TEQ 17 pgg

In addition the screening performed at IRMM did not reveal significant quantities of PCBs and PAHs which were all below the LoDs (1 ngg for PCBs and 10 ngg for PAHs respectively)

Table 24 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 5 (Pavia) 0005 0011 154

15

Table 25 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 5

(Pavia)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

039

nq

nq

008

nq

nd

nd

670

671

Table 26 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 5 (Pavia) 033 184 573 225 426 305 206 200 lt 005 381 878

Table 27 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 5 (Pavia) 6939 129 145 224 425 116 6118 255 1789 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 5 (Pavia) 184 62 38 108 55 66 597 110

Table 28 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 5 (Pavia) 006

16

25 Sludge-amended-soil from Barcelona Spain

The sludge-amended soil material from Barcelona sampled upon indication from the Barcelorsquo- Group in Barcelona

Table 29 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 2 (Lleida T) 0015 0183 1138

Table 30 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 2

(Lleida T)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

159

045

nq

048

160

nq

nq

1000

1004

Table 31 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 2 (Lleida T) 059 141 327 536 405 186 184 224 lt 005 318 111

Table 32 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 2 (Lleida T) 4443 1067 1429 253 344 204 4116 780 3396 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 2 (Lleida T) 064 65 26 125 59 17 547 65

Table 33 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 2 (Lleida T) 010

17

26 Sludge amended soil from Essen Germany

The German sludge-amended soil from Essen which was provided as the three sludge materials by LUA NRW did not feature significant concentrations of the PCB congeners 28 52 101 118 153 105 138 156 180 170 but had detectable amounts of some PAHs

Table 34 ndash Analytical screening data on the German sludge-amended soil

Parameter Concentration(ngg)

Naphtalene lt10 Acenaphtylene lt10 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene lt10 Fluoranthene 28 Pyrene 20 Benz(a)anthracene 24 Chrysene 47 Benz(b)fluoranthene 76 Benz(k)fluoranthene 20 Benz(a)pyrene 35 Indeno(123-cd)pyrene 35 Dibenzo(ah)anthracene 10 Benzo(ghi)perylene 26

Table 35 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 4 (Essen) 0011 0302 055

Table 36 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 4

(Essen)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

nq

nq

nq

nq

nq

nq

128

191

203

18

Table 37 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 4 (Essen) 052 545 261 805 320 403 273 273 lt 005 295 781

Table 38 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 4 (Essen) 7947 442 085 06 086 007 2163 189 2019 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 4 (Essen) 045 19 42 87 683 60 462 61

Table 39 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 4 (Essen) 004

27 Long-term sludge exposed soil from Hohenheim-Stuttgart Germany

Similarly an additional sludge exposed soil was sampled at the University of Hohenheim Stuttgart were a test soil was long-term exposed to elevated concentrations of sewage sludge

Table 40 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 1 (Stuttgart) 0045 0263 1765

Table 41 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 1

(Stuttgart)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

230

006

004

004

nq

nd

nd

498

500

19

Table 42 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 1 (Stuttgart) 069 127 361 262 504 183 252 262 lt 005 266 142

Table 43 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 1 (Stuttgart) 7194 1006 133 186 366 088 7874 275 3571 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 1 (Stuttgart) 123 50 47 212 85 69 991 129

Table 44 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 1 (Stuttgart) 177

18

Annex 3

Statistical calculations

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 47)Mandels h statistics(Sludge 1 - PBD 47)

Sample Sludge 1 NUM

Element PBD 47

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00213 0001 3 -021 005 - - 10L - - NUM46L 00273 0002 4 016 021 - - 46L - - NUM64L 00059 0000 4 -116 002 NUM - 64L - - NUM12L 00188 0000 4 -036 002 - - 12L - - NUM26L 00499 0024 2 157 223 Fail - - 26L - - NUM

Totgem 0025 0005 mgkg 1-level 172 (185) NUM (10L46L64L12L26L) -1Totstd= 0016 0010 5-level 157 (162) 5

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 5 Labs rejected (10L46L64L12L26L)

000 050 100 150 200 250

k-values

10L

46L

64L

12L

26L

Mandels k statistics(Sludge 1 - PBD 47)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

10L

46L

64L

12L

26L

Labo

rato

ries

NUM

-200 -100 000 100 200

h-values

10L

46L

64L

12L

26L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 47)

Sludge 1-PBD 47

Unit mgkg

Mandels k statistics(Soil 3 - PBD 47)Mandels h statistics(Soil 3 - PBD 47)

Sample Soil 3 Soil 3 - PBD 47 -- Mean PARM = 0001 [mgkg]

Element PBD 47

General calcparmT1= 134814E-02T2= 142830E-05T3= 13T4= 45T5= 22767E-06

n= variabelp= 4

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean26L 00007 0000 2 -143 001 00007 00000 2 1 00046L 00010 0001 4 010 181 00010 00008 4 3 00010L 00011 0000 3 049 023 00011 00001 3 2 00012L 00012 0000 4 084 081 00012 00004 4 3 000

Totgem 0001 0000 mgkg 1-level 149 (177) 4 00010 () 4 3Totstd= 0000 0000 5-level 142 (159)

RESULTS Mean = 000100 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000050 --gt 5031 r = 00014Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000050 --gt 5031 R = 00014Remarks none

000 050 100 150 200

k-values

26L

46L

10L

12L

Mandels k statistics(Soil 3 - PBD 47)

00 00 00 00 00 00 00 00 00 00 00

Deviation from Mean

26L

46L

10L

12L

Labo

rato

ries

Soil 3 - PBD 47 -- Mean PARM = 0001 [mgkg]

-200 -100 000 100

h-values

26L

46L

10L

12L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 47)

Soil 3-PBD 47

Unit mgkg

Mandels k statistics(Compost 1 - PBD 99)Mandels h statistics(Compost 1 - PBD 99)

Sample Compost 1 Compost 1 - PBD 99 -- Mean PARM = 0003 [mgkg]

Element PBD 99

General calcparmT1= 492124E-02T2= 148747E-04T3= 17T4= 61T5= 93196E-06

n= variabelp= 5

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00020 0000 4 -137 053 00020 00004 4 3 000

26L 00025 0000 2 -058 024 00025 00002 2 1 00010L 00029 0000 3 012 032 00029 00003 3 2 00046L 00033 0001 4 069 161 00033 00013 4 3 00012L 00036 0001 4 114 140 00036 00011 4 3 000

Totgem 0003 0001 mgkg 1-level 172 (185) 5 00029 () 5 4Totstd= 0001 0001 5-level 157 (162)

RESULTS Mean = 000286 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000088 --gt 3086 r = 00025Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000101 --gt 3525 R = 00028Remarks none

000 050 100 150 200

k-values

4L

26L

10L

46L

12L

Mandels k statistics(Compost 1 - PBD 99)

00 00 00 00 00 00 00 00 00 00

Deviation from Mean

4L

26L

10L

46L

12L

Labo

rato

ries

Compost 1 - PBD 99 -- Mean PARM = 0003 [mgkg]

-200 -100 000 100 200

h-values

4L

26L

10L

46L

12L

Labo

rato

ries

Mandels h statistics(Compost 1 - PBD 99)

Compost 1-PBD 99

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 99)Mandels h statistics(Sludge 1 - PBD 99)

Sample Sludge 1 Sludge 1 - PBD 99 -- Mean PARM = 0024 [mgkg]

Element PBD 99

General calcparmT1= 448050E-01T2= 112113E-02T3= 19T4= 73T5= 32972E-05

n= variabelp= 5

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean64L 00173 0002 4 -118 041 Fail 00173 00019 4 3 -0014L 00183 0002 4 -104 032 00183 00015 4 3 -001

12L 00227 0001 4 -038 022 00227 00010 4 3 00010L 00290 0001 3 055 021 00290 00010 3 2 00146L 00320 0002 4 100 039 00320 00018 4 3 00126L 00323 0011 2 105 234 - - 26L - - 001

Totgem 0025 0003 mgkg 1-level 187 (177) 5 00239 (26L) 5 4Totstd= 0007 0004 5-level 166 (154) 1

RESULTS Mean = 002385 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000153 --gt 643 r = 00043Between lab variance S2L = 000004Reproducibility var S2R = 000004Reproducibility std SR = 000666 --gt 2791 R = 00186Remarks 1 Lab rejected (26L)

000 050 100 150 200 250

k-values

64L

4L

12L

10L

46L

26L

Mandels k statistics(Sludge 1 - PBD 99)

00 00 00 00 00 00 00 00 00 00

Deviation from Mean

64L

4L

12L

10L

46L

26L

Labo

rato

ries

Sludge 1 - PBD 99 -- Mean PARM = 0024 [mgkg]

-200 -100 000 100 200

h-values

64L

4L

12L

10L

46L

26L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 99)

Sludge 1-PBD 99

Unit mgkg

Mandels k statistics(Soil 3 - PBD 99)Mandels h statistics(Soil 3 - PBD 99)

Sample Soil 3 NUM

Element PBD 99

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00017 0000 4 091 068 - - 10L - - NUM46L 00017 0001 4 100 211 - - 46L - - NUM64L 00005 0000 4 -106 023 NUM - 64L - - NUM12L 00012 0000 4 015 014 - - 12L - - NUM26L 00006 0000 2 -101 012 - - 26L - - NUM

Totgem 0001 0000 mgkg 1-level 172 (173) NUM (10L46L64L12L26L) -1Totstd= 0001 0000 5-level 157 (153) 5

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 5 Labs rejected (10L46L64L12L26L)

000 050 100 150 200 250

k-values

10L

46L

64L

12L

26L

Mandels k statistics(Soil 3 - PBD 99)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

10L

46L

64L

12L

26L

Labo

rato

ries

NUM

-200 -100 000 100 200

h-values

10L

46L

64L

12L

26L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 99)

Soil 3-PBD 99

Unit mgkg

Mandels k statistics(Compost 1 - PBD 100)Mandels h statistics(Compost 1 - PBD 100)

Sample Compost 1 Compost 1 - PBD 100 -- Mean PARM = 0001 [mgkg]

Element PBD 100

General calcparmT1= 124272E-02T2= 113129E-05T3= 14T4= 52T5= 46584E-07

n= variabelp= 4

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean26L 00006 0000 2 -131 037 Fail 00006 00001 2 1 00010L 00009 0000 4 003 083 00009 00002 4 3 00046L 00009 0000 4 016 115 00009 00002 4 3 00012L 00011 0000 4 112 136 Fail 00011 00003 4 3 000

Totgem 0001 0000 mgkg 1-level 149 (167) 4 00009 () 4 3Totstd= 0000 0000 5-level 142 (15)

RESULTS Mean = 000085 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000022 --gt 2531 r = 00006Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000025 --gt 2882 R = 00007Remarks none

000 050 100 150

k-values

26L

10L

46L

12L

Mandels k statistics(Compost 1 - PBD 100)

00 00 00 00 00 00 00 00 00 00 00

Deviation from Mean

26L

10L

46L

12L

Labo

rato

ries

Compost 1 - PBD 100 -- Mean PARM = 0001 [mgkg]

-200 -100 000 100 200

h-values

26L

10L

46L

12L

Labo

rato

ries

Mandels h statistics(Compost 1 - PBD 100)

Compost 1-PBD 100

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 100)Mandels h statistics(Sludge 1 - PBD 100)

Sample Sludge 1 Sludge 1 - PBD 100 -- Mean PARM = 0005 [mgkg]

Element PBD 100

General calcparmT1= 852065E-02T2= 412762E-04T3= 18T4= 68T5= 78914E-07

n= variabelp= 5

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00039 0000 4 -042 007 Fail 00039 00002 4 3 000

12L 00044 0000 4 -041 005 Fail 00044 00001 4 3 00010L 00046 0000 4 -041 013 Fail 00046 00003 4 3 00046L 00056 0000 4 -040 012 Fail 00056 00003 4 3 00026L 00059 0000 2 -040 013 Fail 00059 00003 2 1 00038L 02168 0006 4 204 244 Fail - - 38L - - 021

Totgem 0040 0001 mgkg 1-level 187 (177) 5 00049 (38L) 5 4Totstd= 0087 0002 5-level 166 (154) 1

RESULTS Mean = 000486 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000025 --gt 507 r = 00007Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000084 --gt 1731 R = 00024Remarks 1 Lab rejected (38L)

000 050 100 150 200 250

k-values

4L

12L

10L

46L

26L

38L

Mandels k statistics(Sludge 1 - PBD 100)

-01 00 01 01 02 02 03

Deviation from Mean

4L

12L

10L

46L

26L

38L

Labo

rato

ries

Sludge 1 - PBD 100 -- Mean PARM = 0005 [mgkg]

-100 000 100 200 300

h-values

4L

12L

10L

46L

26L

38L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 100)

Sludge 1-PBD 100

Unit mgkg

Mandels k statistics(Soil 3 - PBD 100)Mandels h statistics(Soil 3 - PBD 100)

Sample Soil 3 NUM

Element PBD 100

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00003 0000 4 -050 000 Fail - - 10L - - NUM46L 00003 0000 4 -050 000 Fail NUM - 46L - - NUM3L 305500 2051 2 150 200 Fail - - 3L - - NUM

26L 00005 0000 2 -050 000 Fail - - 26L - - NUM

Totgem 7638 0513 mgkg 1-level 149 (177) NUM (10L46L3L26L) -1Totstd= 15275 1025 5-level 142 (159) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (10L46L3L26L)

000 050 100 150 200

k-values

10L

46L

3L

26L

Mandels k statistics(Soil 3 - PBD 100)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

10L

46L

3L

26L

Labo

rato

ries

NUM

-100 000 100 200

h-values

10L

46L

3L

26L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 100)

Soil 3-PBD 100

Unit mgkg

Mandels k statistics(Compost 1 - PBD 153)Mandels h statistics(Compost 1 - PBD 153)

Sample Compost 1 NUM

Element PBD 153

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean44L 00053 0001 3 150 157 Fail - - 44L - - NUM46L 00007 0000 4 -044 111 Fail - - 46L - - NUM12L 00005 0000 4 -051 055 Fail - - 12L - - NUM26L 00005 0000 2 -054 001 Fail NUM - 26L - - NUM

Totgem 0002 0000 mgkg 1-level 149 (177) NUM (44L46L12L26L) -1Totstd= 0002 0000 5-level 142 (159) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (44L46L12L26L)

000 050 100 150 200

k-values

44L

46L

12L

26L

Mandels k statistics(Compost 1 - PBD 153)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

44L

46L

12L

26L

Labo

rato

ries

NUM

-100 000 100 200

h-values

44L

46L

12L

26L

Labo

rato

ries

Mandels h statistics(Compost 1 - PBD 153)

Compost 1-PBD 153

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 153)Mandels h statistics(Sludge 1 - PBD 153)

Sample Sludge 1 Sludge 1 - PBD 153 -- Mean PARM = 0004 [mgkg]

Element PBD 153

General calcparmT1= 676738E-02T2= 267609E-04T3= 18T4= 68T5= 19626E-05

n= variabelp= 5

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00024 0000 4 -157 017 00024 00002 4 3 000

12L 00038 0002 4 006 154 00038 00018 4 3 00046L 00039 0000 4 011 026 00039 00003 4 3 00026L 00039 0000 2 018 004 00039 00000 2 1 00064L 00049 0002 4 122 159 00049 00018 4 3 000

Totgem 0004 0001 mgkg 1-level 172 (173) 5 00038 () 5 4Totstd= 0001 0001 5-level 157 (153)

RESULTS Mean = 000378 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000123 --gt 3252 r = 00034Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000142 --gt 3754 R = 00040Remarks none

000 050 100 150 200

k-values

4L

12L

46L

26L

64L

Mandels k statistics(Sludge 1 - PBD 153)

00 00 00 00 00 00 00

Deviation from Mean

4L

12L

46L

26L

64L

Labo

rato

ries

Sludge 1 - PBD 153 -- Mean PARM = 0004 [mgkg]

-200 -100 000 100 200

h-values

4L

12L

46L

26L

64L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 153)

Sludge 1-PBD 153

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 154)Mandels h statistics(Sludge 1 - PBD 154)

Sample Sludge 1 NA

Element PBD 154

General calcparmT1= NAT2= NAT3=T4=T5=

n= variabelp=

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00021 0000 3 -100 021 NA - 4L - - NA

46L 00025 0000 4 115 018 NA - 46L - - NA64L 00021 0001 4 -066 179 - - 64L - - NA12L 00023 0000 4 050 085 - - 12L - - NA

Totgem 0002 0000 mgkg 1-level 149 (167) NA (4L46L64L12L) -1Totstd= 0000 0000 5-level 142 (15) 4

RESULTS Mean = NA mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NAReproducibility var S2R = NAReproducibility std SR = NA --gt NA R = NARemarks 4 Labs rejected (4L46L64L12L)

000 050 100 150 200

k-values

4L

46L

64L

12L

Mandels k statistics(Sludge 1 - PBD 154)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

4L

46L

64L

12L

Labo

rato

ries

NA

-100 000 100 200

h-values

4L

46L

64L

12L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 154)

Sludge 1-PBD 154

Unit mgkg

Mandels k statistics(Soil 3 - PBD 154)Mandels h statistics(Soil 3 - PBD 154)

Sample Soil 3 NUM

Element PBD 154

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

4L 00010 - 1 150 Fail - - 4L - - NUM46L 00001 0000 4 -053 096 Fail - - 46L - - NUM64L 00001 0000 4 -056 105 Fail NUM - 64L - - NUM12L 00002 0000 4 -040 099 Fail - - 12L - - NUM

Totgem 000037 0000 mgkg 1-level 149 (164) NUM (4L46L64L12L) -1Totstd= 000042 0000 5-level 142 (153) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (4L46L64L12L)

000 050 100 150

k-values

4L

46L

64L

12L

Mandels k statistics(Soil 3 - PBD 154)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

4L

46L

64L

12L

Labo

rato

ries

NUM

-100 000 100 200

h-values

4L

46L

64L

12L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 154)

Soil 3-PBD 154

Unit mgkg

Mandels k statistics(Compost 1 - PBD 209)Mandels h statistics(Compost 1 - PBD 209)

Sample Compost 1 NUM

Element PBD 209

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00065 0003 2 -049 032 - - 4L - - NUM

44L 00573 0021 4 150 197 Fail - - 44L - - NUM12L 00078 0001 4 -045 011 - - 12L - - NUM26L 00049 0000 2 -056 000 NUM - 26L - - NUM

Totgem 0019 0006 mgkg 1-level 149 (177) NUM (4L44L12L26L) -1Totstd= 0025 0010 5-level 142 (159) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (4L44L12L26L)

000 050 100 150 200

k-values

4L

44L

12L

26L

Mandels k statistics(Compost 1 - PBD 209)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

4L

44L

12L

26L

Labo

rato

ries

NUM

-100 000 100 200

h-values

4L

44L

12L

26L

Labo

rato

ries

Mandels h statistics(Compost 1 - PBD 209)

Compost 1-PBD 209

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 209)Mandels h statistics(Sludge 1 - PBD 209)

Sample Sludge 1 Sludge 1 - PBD 209 -- Mean PARM = 0249 [mgkg]

Element PBD 209

General calcparmT1= 394542E+00T2= 107296E+00T3= 16T4= 56T5= 19723E-02

n= variabelp= 5

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 01550 0055 4 -112 148 Fail 01550 00551 4 3 -009

46L 02050 0007 2 -053 019 02050 00071 2 1 -00412L 02137 0058 4 -042 155 02137 00576 4 3 -00426L 03149 0021 2 078 057 Fail 03149 00210 2 1 00764L 03577 0007 4 129 020 Fail 03577 00074 4 3 011

Totgem 0249 0030 mgkg 1-level 172 (185) 5 02493 () 5 4Totstd= 0084 0025 5-level 157 (162)

RESULTS Mean = 024926 mgkg

Repeatability variance S2r = 000179Repeatability std Sr = 004234 --gt 1699 r = 01186Between lab variance S2L = 000743Reproducibility var S2R = 000922Reproducibility std SR = 009604 --gt 3853 R = 02689Remarks none

000 050 100 150 200

k-values

4L

46L

12L

26L

64L

Mandels k statistics(Sludge 1 - PBD 209)

-01 -01 00 01 01 02

Deviation from Mean

4L

46L

12L

26L

64L

Labo

rato

ries

Sludge 1 - PBD 209 -- Mean PARM = 0249 [mgkg]

-200 -100 000 100 200

h-values

4L

46L

12L

26L

64L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 209)

Sludge 1-PBD 209

Unit mgkg

Mandels k statistics(Soil 3 - PBD 209)Mandels h statistics(Soil 3 - PBD 209)

Sample Soil 3 Soil 3 - PBD 209 -- Mean PARM = 0258 [mgkg]

Element PBD 209

General calcparmT1= 596398E+00T2= 191917E+00T3= 22T4= 84T5= 13249E-02

n= variabelp= 6

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean26L 01162 0021 2 -108 074 Fail 01162 00207 2 1 -0144L 01303 0031 4 -097 111 Fail 01303 00312 4 3 -013

46L 01975 0036 4 -046 128 Fail 01975 00359 4 3 -00644L 02898 0035 4 024 124 Fail 02898 00346 4 3 00312L 03895 0018 4 100 065 Fail 03895 00181 4 3 01364L 04260 0022 4 127 078 Fail 04260 00219 4 3 017

Totgem 0258 0027 mgkg 1-level 187 (177) 6 02582 () 6 5Totstd= 0132 0008 5-level 166 (154)

RESULTS Mean = 025818 mgkg

Repeatability variance S2r = 000083Repeatability std Sr = 002878 --gt 1115 r = 00806Between lab variance S2L = 001640Reproducibility var S2R = 001723Reproducibility std SR = 013127 --gt 5084 R = 03676Remarks none

000 050 100 150

k-values

26L

4L

46L

44L

12L

64L

Mandels k statistics(Soil 3 - PBD 209)

-02 -01 -01 00 01 01 02 02

Deviation from Mean

26L

4L

46L

44L

12L

64L

Labo

rato

ries

Soil 3 - PBD 209 -- Mean PARM = 0258 [mgkg]

-200 -100 000 100 200

h-values

26L

4L

46L

44L

12L

64L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 209)

Soil 3-PBD 209

Unit mgkg

Mandels k statistics(Compost 1 - Sum PBD)Mandels h statistics(Compost 1 - Sum PBD)

Sample Compost 1 Compost 1 - Sum PBD -- Mean PARM = 0009 [mgkg]

Element Sum PBD

General calcparmT1= 154064E-01T2= 169065E-03T3= 18T4= 68T5= 11354E-04

n= variabelp= 5

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00031 0002 4 -067 016 00031 00016 4 3 -0014L 00055 0005 4 -056 048 00055 00047 4 3 000

46L 00085 0003 4 -042 031 00085 00030 4 3 00026L 00123 0000 2 -024 003 00123 00002 2 1 00012L 00154 0002 4 -011 021 00154 00021 4 3 00144L 00613 0023 4 200 237 Fail - - 44L - - 005

Totgem 0018 0006 mgkg 1-level 187 (177) 5 00089 (44L) 5 4Totstd= 0022 0009 5-level 166 (154) 1

RESULTS Mean = 000893 mgkg

Repeatability variance S2r = 000001Repeatability std Sr = 000296 --gt 3308 r = 00083Between lab variance S2L = 000002Reproducibility var S2R = 000003Reproducibility std SR = 000570 --gt 6374 R = 00159Remarks 1 Lab rejected (44L)

000 050 100 150 200 250

k-values

10L

4L

46L

26L

12L

44L

Mandels k statistics(Compost 1 - Sum PBD)

00 00 00 00 00 00 01 01

Deviation from Mean

10L

4L

46L

26L

12L

44L

Labo

rato

ries

Compost 1 - Sum PBD -- Mean PARM = 0009 [mgkg]

-100 000 100 200

h-values

10L

4L

46L

26L

12L

44L

Labo

rato

ries

Mandels h statistics(Compost 1 - Sum PBD)

Compost 1-Sum PBD

Unit mgkg

Mandels k statistics(Sludge 1 - Sum PBD)Mandels h statistics(Sludge 1 - Sum PBD)

Sample Sludge 1 Sludge 1 - Sum PBD -- Mean PARM = 0256 [mgkg]

Element Sum PBD

General calcparmT1= 531806E+00T2= 162188E+00T3= 22T4= 84T5= 25223E-02

n= variabelp= 6

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00423 0025 4 -156 044 Fail 00423 00252 4 3 -02146L 01808 0118 4 -049 205 - - 46L - - -0074L 01810 0056 4 -049 097 01810 00558 4 3 -007

38L 02168 0006 4 -022 010 02168 00059 4 3 -00412L 02890 0065 4 034 113 02890 00647 4 3 00364L 03958 0008 4 116 014 Fail 03958 00079 4 3 01426L 04094 0034 2 126 059 Fail 04094 00337 2 1 015

Totgem 0245 0044 mgkg 1-level 198 (179) 6 02557 (46L) 6 5Totstd= 0130 0039 5-level 171 (155) 1

RESULTS Mean = 025570 mgkg

Repeatability variance S2r = 000158Repeatability std Sr = 003970 --gt 1553 r = 01112Between lab variance S2L = 001807Reproducibility var S2R = 001964Reproducibility std SR = 014015 --gt 5481 R = 03924Remarks 1 Lab rejected (46L)

000 050 100 150 200 250

k-values

10L

46L

4L

38L

12L

64L

26L

Mandels k statistics(Sludge 1 - Sum PBD)

-03 -02 -02 -01 -01 00 01 01 02 02

Deviation from Mean

10L

46L

4L

38L

12L

64L

26L

Labo

rato

ries

Sludge 1 - Sum PBD -- Mean PARM = 0256 [mgkg]

-200 -100 000 100 200

h-values

10L

46L

4L

38L

12L

64L

26L

Labo

rato

ries

Mandels h statistics(Sludge 1 - Sum PBD)

Sludge 1-Sum PBD

Unit mgkg

Mandels k statistics(Soil 3 - Sum PBD)Mandels h statistics(Soil 3 - Sum PBD)

Sample Soil 3 Soil 3 - Sum PBD -- Mean PARM = 0227 [mgkg]

Element Sum PBD

General calcparmT1= 610980E+00T2= 200876E+00T3= 26T4= 100T5= 13106E-02

n= variabelp= 7

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00028 0001 4 -037 000 Fail 00028 00005 4 3 -02226L 01179 0021 2 -036 003 Fail 01179 00208 2 1 -0114L 01305 0031 4 -036 004 Fail 01305 00308 4 3 -010

46L 02065 0035 4 -036 005 Fail 02065 00350 4 3 -00244L 02923 0037 4 -035 005 Fail 02923 00365 4 3 00712L 04051 0015 4 -034 002 Fail 04051 00149 4 3 01864L 04314 0022 4 -033 003 Fail 04314 00223 4 3 0203L 305500 2051 2 247 283 Fail - - 3L - - 3032

Totgem 4017 0276 mgkg 1-level 206 (181) 7 02266 (3L) 7 6Totstd= 10722 0717 5-level 175 (156) 1

RESULTS Mean = 022663 mgkg

Repeatability variance S2r = 000069Repeatability std Sr = 002626 --gt 1159 r = 00735Between lab variance S2L = 002568Reproducibility var S2R = 002637Reproducibility std SR = 016238 --gt 7165 R = 04547Remarks 1 Lab rejected (3L)

000 050 100 150 200 250 300

k-values

10L

26L

4L

46L

44L

12L

64L

3L

Mandels k statistics(Soil 3 - Sum PBD)

-50 00 50 100 150 200 250 300 350

Deviation from Mean

10L

26L

4L

46L

44L

12L

64L

3L

Labo

rato

ries

Soil 3 - Sum PBD -- Mean PARM = 0227 [mgkg]

-100 000 100 200 300

h-values

10L

26L

4L

46L

44L

12L

64L

3L

Labo

rato

ries

Mandels h statistics(Soil 3 - Sum PBD)

Soil 3-Sum PBD

19

Annex 4

Raw data submitted

Sample Compost1 Sample Compost 1 Sample Compost 1Element PBD 99 Element PBD 100 Element PBD 153

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]4L 00021 10L 00008 44L 000504L 00024 10L 00008 44L 000604L 00014 10L 00007 44L 000504L 00020 10L 00011 46L 00004

10L 00029 46L 00007 46L 0001210L 00027 46L 00012 46L 0000410L 00032 46L 00009 46L 0000946L 00025 46L 00007 12L 0000446L 00052 12L 00008 12L 0000846L 00029 12L 00012 12L 0000446L 00026 12L 00008 12L 0000712L 00026 12L 00014 26L 0000512L 00043 26L 00007 26L 0000512L 00026 26L 0000612L 0004726L 0002626L 00024

Sample Compost 1 Sample Compost 1 Sample Compost 1Element PBD 154 Element PBD 183 Element PBD 196

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]4L 00010 46L 00002 46L 00011

46L 00003 46L 00024 46L 0000846L 00007 46L 00021 12L 0000246L 00003 46L 00003 12L 0000346L 00004 12L 00003 12L 0000112L 00003 12L 00011 12L 0000212L 00005 12L 0000312L 00031 12L 0000312L 00006

Sample Compost 1 Sample Compost 1 Sample Compost 1Element PBD 197 Element PBD 203 Element PBD 209

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00002 46L 00010 4L 0004146L 00023 12L 00002 4L 0008946L 00022 12L 00003 44L 0041012L 00004 12L 00002 44L 0084012L 00006 12L 00002 44L 0064012L 00003 44L 0040012L 00004 12L 00079

12L 0007312L 0006512L 0009326L 0004926L 00049

Sample Compost 1Element PBD 47

LAB PARM [mgkg]26L 0003826L 00039

Element PBD 99 Element PBD 47 Element PBD 209LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]

4L 00170 10L 00210 4L 010004L 00200 10L 00220 4L 018004L 00170 10L 00210 4L 012004L 00190 46L 00300 4L 0220010L 00280 46L 00280 46L 0210010L 00300 46L 00250 46L 0200010L 00290 46L 00260 64L 0351846L 00340 64L 00059 64L 0363846L 00330 64L 00057 64L 0364546L 00300 64L 00062 64L 0350846L 00310 64L 00060 12L 0220964L 00194 12L 00191 12L 0177164L 00154 12L 00187 12L 0292264L 00185 12L 00190 12L 0164664L 00159 12L 00186 26L 0329712L 00242 26L 00666 26L 0300012L 00223 26L 0033212L 0022112L 0022226L 0024626L 00400

Element PBD 203 Element PBD 197 Element PBD 196LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00022 46L 00027 46L 0002446L 00014 46L 00024 46L 0002264L 00036 12L 00161 64L 0005864L 00058 12L 00060 64L 0006512L 00063 12L 00061 12L 0004812L 00034 12L 00036 12L 0002512L 00038 12L 0003212L 00027 12L 00022

Element PBD 183 Element PBD 154 Element PBD 153LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00049 4L 00020 4L 0002246L 00035 4L 00022 4L 0002446L 00036 4L 00020 4L 0002246L 00034 46L 00025 4L 0002664L 00027 46L 00025 46L 0004064L 00023 46L 00025 46L 0004264L 00024 46L 00023 46L 0003564L 00020 64L 00034 46L 0003812L 00230 64L 00023 64L 0007412L 00032 64L 00017 64L 0004712L 00031 64L 00011 64L 0004612L 00030 12L 00030 64L 0003026L 00007 12L 00021 12L 0006526L 00008 12L 00021 12L 00029

12L 00021 12L 0003226L 00015 12L 0002926L 00019 26L 00039

26L 00040

Element PBD 100LAB PARM [mgkg]

4L 000384L 000414L 000374L 00038

38L 0219038L 0220038L 0208038L 0220010L 0004410L 0005010L 0004310L 0004646L 0005746L 0005946L 0005346L 0005312L 0004312L 0004512L 0004312L 0004326L 0006226L 00057

Sample Soil 3 Sample Soil 3 Sample Soil 3Element PBD 99 Element PBD 47 Element PBD 100

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]10L 00016 10L 00011 10L 0000310L 00019 10L 00010 10L 0000410L 00013 10L 00012 10L 0000410L 00019 46L 00007 10L 0000246L 00025 46L 00022 46L 0000246L 00025 46L 00005 46L 0000646L 00008 46L 00007 46L 0000246L 00011 12L 00010 46L 0000264L 00005 12L 00017 3L 29100064L 00005 12L 00010 3L 32000064L 00006 12L 00009 26L 0000564L 00007 26L 00007 26L 0000512L 00012 26L 0000712L 0001312L 0001312L 0001226L 0000526L 00006

Sample Soil 3 Sample Soil 3 Sample Soil 3Element PBD 153 Element PBD 154 Element PBD 196

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]44L 00050 4L 00010 46L 0000744L 00050 46L 00001 46L 0001146L 00002 46L 00002 46L 0000846L 00003 46L 00001 46L 0001146L 00002 46L 00002 64L 0002646L 00002 64L 00001 64L 0002664L 00001 64L 00001 64L 0002964L 00001 64L 00001 64L 0003464L 00001 64L 00002 12L 0004564L 00002 12L 00003 12L 00032

12L 00002 12L 0002212L 00002 12L 0002112L 00002

Sample Soil 3 Sample Soil 3 Sample Soil 3Element PBD 197 Element PBD 203 Element PBD 209

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00006 46L 00011 4L 0091046L 00013 46L 00017 4L 0150046L 00011 46L 00015 4L 0120046L 00013 46L 00018 4L 0160012L 00090 64L 00013 44L 0337012L 00056 64L 00014 44L 0281012L 00033 64L 00016 44L 0287012L 00032 64L 00015 44L 02540

12L 00055 46L 0230012L 00041 46L 0220012L 00027 46L 0150012L 00026 46L 01900

64L 0438164L 0401664L 0414464L 0449812L 0367112L 0397812L 0409112L 03838

Sample Soil 3 26L 0102Element PBD 183 26L 0131

LAB PARM [mgkg]46L 0000746L 0000846L 0005846L 0000764L 0000264L 0000364L 0000364L 0000312L 0001512L 0001112L 0000712L 00007

European Commission EUR 23003 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on polybrominated diphenylethers Author(s) E Sobiecka H van der Sloot D Barcelo B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 68 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07403-5 Abstract Project HORIZONTAL is interdisciplinary aiming at a harmonisation and horizontal standardisation of test procedures in particular for sludge soils and biowastes In the context of this standardization project a series of draft technical specification were designed upon an extensive desk study fine-tuned after expert consultations and finally validated in international intercomparisons exercise This report summarises the work performed within the validation study of the draft standard for the determination of polybrominated diphenylethers (PBDE) in soils sludge and treated bio-waste using gas-chromatography method with mass selective detection (GC-MS) It further explains the underlying statistical concept for the calculation of reproducibility and repeatability from intercomparisons data In addition all single values results of the statistical evaluation as well as background information on the validation materials used are described and explained

The mission of the JRC is to provide customer-driven scientific and technical support for the conception development implementation and monitoring of EU policies As a service of the European Commission the JRC functions as a reference centre of science and technology for the Union Close to the policy-making process it serves the common interest of the Member States while being independent of special interests whether private or national

LB

-NA

-23003-EN

-C

13

Table 18 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Compost 1

(Vienna)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

402

019

259

nq

023

004

nq

nq

144

174

259

Table 19 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Compost 1

(Vienna) 0058 1426 557

Table 20 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Compost 1 (Vienna) 039 736 319 410 365 127 495 004 079 013 208

Table 21 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Compost 1 (Vienna) 2063 431 617 426 199 249 1602 lt15 10521

Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Compost 1 (Vienna) 035 3496 81 375 79 55 653 60

Table 22 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Compost 1 (Vienna) 017

14

24 Agricultural soil sludge amended soil from Pavia Italy

This sludge-amended soil material was obtained during a monitoring campaign which aimed at a generic description of the over-all soil quality in Pavia Province Italy The material which was collected from the upper horizon originates from a small farm called ldquoCascina Novellordquo During the characterisation of the site the following analytical information was obtained on a pooled sample of a sub-area of the farm of 20 X 20 m2

Table 23 ndash Analytical data on Pavia soil

Parameter Result Al 713 Wgt As 224 mgkg Cd 079 mgkg Cr 59 mgkg Cu 308 mgkg Hg 008 mgkg Ni 344 mgkg Pb 246 mgkg Zn 95 mgkg C 091 Wgt 2378-TCDD 0047 pgg 12378-PeCDD 015 pgg 123478-HxCDD 019 pgg 123678-HxCDD 15 pgg 123789-HxCDD 074 pgg 1234678-HpCDD 26 pgg OCDD 382 pgg 2378-TCDF 068 pgg 12378-PeCDF 053 pgg 23478-PeCDF 071 pgg 123478-HxDF 100 pgg 123678-HxDF 066 pgg 234678-HxDF 16 pgg 123789-HxDF 027 pgg 1234678-HpDF 12 pgg 1234789-HpDF 068 pgg OCDF 33 pgg I-TEQ 20 pgg WHO-TEQ 17 pgg

In addition the screening performed at IRMM did not reveal significant quantities of PCBs and PAHs which were all below the LoDs (1 ngg for PCBs and 10 ngg for PAHs respectively)

Table 24 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 5 (Pavia) 0005 0011 154

15

Table 25 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 5

(Pavia)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

039

nq

nq

008

nq

nd

nd

670

671

Table 26 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 5 (Pavia) 033 184 573 225 426 305 206 200 lt 005 381 878

Table 27 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 5 (Pavia) 6939 129 145 224 425 116 6118 255 1789 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 5 (Pavia) 184 62 38 108 55 66 597 110

Table 28 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 5 (Pavia) 006

16

25 Sludge-amended-soil from Barcelona Spain

The sludge-amended soil material from Barcelona sampled upon indication from the Barcelorsquo- Group in Barcelona

Table 29 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 2 (Lleida T) 0015 0183 1138

Table 30 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 2

(Lleida T)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

159

045

nq

048

160

nq

nq

1000

1004

Table 31 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 2 (Lleida T) 059 141 327 536 405 186 184 224 lt 005 318 111

Table 32 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 2 (Lleida T) 4443 1067 1429 253 344 204 4116 780 3396 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 2 (Lleida T) 064 65 26 125 59 17 547 65

Table 33 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 2 (Lleida T) 010

17

26 Sludge amended soil from Essen Germany

The German sludge-amended soil from Essen which was provided as the three sludge materials by LUA NRW did not feature significant concentrations of the PCB congeners 28 52 101 118 153 105 138 156 180 170 but had detectable amounts of some PAHs

Table 34 ndash Analytical screening data on the German sludge-amended soil

Parameter Concentration(ngg)

Naphtalene lt10 Acenaphtylene lt10 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene lt10 Fluoranthene 28 Pyrene 20 Benz(a)anthracene 24 Chrysene 47 Benz(b)fluoranthene 76 Benz(k)fluoranthene 20 Benz(a)pyrene 35 Indeno(123-cd)pyrene 35 Dibenzo(ah)anthracene 10 Benzo(ghi)perylene 26

Table 35 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 4 (Essen) 0011 0302 055

Table 36 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 4

(Essen)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

nq

nq

nq

nq

nq

nq

128

191

203

18

Table 37 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 4 (Essen) 052 545 261 805 320 403 273 273 lt 005 295 781

Table 38 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 4 (Essen) 7947 442 085 06 086 007 2163 189 2019 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 4 (Essen) 045 19 42 87 683 60 462 61

Table 39 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 4 (Essen) 004

27 Long-term sludge exposed soil from Hohenheim-Stuttgart Germany

Similarly an additional sludge exposed soil was sampled at the University of Hohenheim Stuttgart were a test soil was long-term exposed to elevated concentrations of sewage sludge

Table 40 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 1 (Stuttgart) 0045 0263 1765

Table 41 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 1

(Stuttgart)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

230

006

004

004

nq

nd

nd

498

500

19

Table 42 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 1 (Stuttgart) 069 127 361 262 504 183 252 262 lt 005 266 142

Table 43 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 1 (Stuttgart) 7194 1006 133 186 366 088 7874 275 3571 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 1 (Stuttgart) 123 50 47 212 85 69 991 129

Table 44 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 1 (Stuttgart) 177

18

Annex 3

Statistical calculations

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 47)Mandels h statistics(Sludge 1 - PBD 47)

Sample Sludge 1 NUM

Element PBD 47

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00213 0001 3 -021 005 - - 10L - - NUM46L 00273 0002 4 016 021 - - 46L - - NUM64L 00059 0000 4 -116 002 NUM - 64L - - NUM12L 00188 0000 4 -036 002 - - 12L - - NUM26L 00499 0024 2 157 223 Fail - - 26L - - NUM

Totgem 0025 0005 mgkg 1-level 172 (185) NUM (10L46L64L12L26L) -1Totstd= 0016 0010 5-level 157 (162) 5

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 5 Labs rejected (10L46L64L12L26L)

000 050 100 150 200 250

k-values

10L

46L

64L

12L

26L

Mandels k statistics(Sludge 1 - PBD 47)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

10L

46L

64L

12L

26L

Labo

rato

ries

NUM

-200 -100 000 100 200

h-values

10L

46L

64L

12L

26L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 47)

Sludge 1-PBD 47

Unit mgkg

Mandels k statistics(Soil 3 - PBD 47)Mandels h statistics(Soil 3 - PBD 47)

Sample Soil 3 Soil 3 - PBD 47 -- Mean PARM = 0001 [mgkg]

Element PBD 47

General calcparmT1= 134814E-02T2= 142830E-05T3= 13T4= 45T5= 22767E-06

n= variabelp= 4

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean26L 00007 0000 2 -143 001 00007 00000 2 1 00046L 00010 0001 4 010 181 00010 00008 4 3 00010L 00011 0000 3 049 023 00011 00001 3 2 00012L 00012 0000 4 084 081 00012 00004 4 3 000

Totgem 0001 0000 mgkg 1-level 149 (177) 4 00010 () 4 3Totstd= 0000 0000 5-level 142 (159)

RESULTS Mean = 000100 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000050 --gt 5031 r = 00014Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000050 --gt 5031 R = 00014Remarks none

000 050 100 150 200

k-values

26L

46L

10L

12L

Mandels k statistics(Soil 3 - PBD 47)

00 00 00 00 00 00 00 00 00 00 00

Deviation from Mean

26L

46L

10L

12L

Labo

rato

ries

Soil 3 - PBD 47 -- Mean PARM = 0001 [mgkg]

-200 -100 000 100

h-values

26L

46L

10L

12L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 47)

Soil 3-PBD 47

Unit mgkg

Mandels k statistics(Compost 1 - PBD 99)Mandels h statistics(Compost 1 - PBD 99)

Sample Compost 1 Compost 1 - PBD 99 -- Mean PARM = 0003 [mgkg]

Element PBD 99

General calcparmT1= 492124E-02T2= 148747E-04T3= 17T4= 61T5= 93196E-06

n= variabelp= 5

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00020 0000 4 -137 053 00020 00004 4 3 000

26L 00025 0000 2 -058 024 00025 00002 2 1 00010L 00029 0000 3 012 032 00029 00003 3 2 00046L 00033 0001 4 069 161 00033 00013 4 3 00012L 00036 0001 4 114 140 00036 00011 4 3 000

Totgem 0003 0001 mgkg 1-level 172 (185) 5 00029 () 5 4Totstd= 0001 0001 5-level 157 (162)

RESULTS Mean = 000286 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000088 --gt 3086 r = 00025Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000101 --gt 3525 R = 00028Remarks none

000 050 100 150 200

k-values

4L

26L

10L

46L

12L

Mandels k statistics(Compost 1 - PBD 99)

00 00 00 00 00 00 00 00 00 00

Deviation from Mean

4L

26L

10L

46L

12L

Labo

rato

ries

Compost 1 - PBD 99 -- Mean PARM = 0003 [mgkg]

-200 -100 000 100 200

h-values

4L

26L

10L

46L

12L

Labo

rato

ries

Mandels h statistics(Compost 1 - PBD 99)

Compost 1-PBD 99

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 99)Mandels h statistics(Sludge 1 - PBD 99)

Sample Sludge 1 Sludge 1 - PBD 99 -- Mean PARM = 0024 [mgkg]

Element PBD 99

General calcparmT1= 448050E-01T2= 112113E-02T3= 19T4= 73T5= 32972E-05

n= variabelp= 5

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean64L 00173 0002 4 -118 041 Fail 00173 00019 4 3 -0014L 00183 0002 4 -104 032 00183 00015 4 3 -001

12L 00227 0001 4 -038 022 00227 00010 4 3 00010L 00290 0001 3 055 021 00290 00010 3 2 00146L 00320 0002 4 100 039 00320 00018 4 3 00126L 00323 0011 2 105 234 - - 26L - - 001

Totgem 0025 0003 mgkg 1-level 187 (177) 5 00239 (26L) 5 4Totstd= 0007 0004 5-level 166 (154) 1

RESULTS Mean = 002385 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000153 --gt 643 r = 00043Between lab variance S2L = 000004Reproducibility var S2R = 000004Reproducibility std SR = 000666 --gt 2791 R = 00186Remarks 1 Lab rejected (26L)

000 050 100 150 200 250

k-values

64L

4L

12L

10L

46L

26L

Mandels k statistics(Sludge 1 - PBD 99)

00 00 00 00 00 00 00 00 00 00

Deviation from Mean

64L

4L

12L

10L

46L

26L

Labo

rato

ries

Sludge 1 - PBD 99 -- Mean PARM = 0024 [mgkg]

-200 -100 000 100 200

h-values

64L

4L

12L

10L

46L

26L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 99)

Sludge 1-PBD 99

Unit mgkg

Mandels k statistics(Soil 3 - PBD 99)Mandels h statistics(Soil 3 - PBD 99)

Sample Soil 3 NUM

Element PBD 99

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00017 0000 4 091 068 - - 10L - - NUM46L 00017 0001 4 100 211 - - 46L - - NUM64L 00005 0000 4 -106 023 NUM - 64L - - NUM12L 00012 0000 4 015 014 - - 12L - - NUM26L 00006 0000 2 -101 012 - - 26L - - NUM

Totgem 0001 0000 mgkg 1-level 172 (173) NUM (10L46L64L12L26L) -1Totstd= 0001 0000 5-level 157 (153) 5

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 5 Labs rejected (10L46L64L12L26L)

000 050 100 150 200 250

k-values

10L

46L

64L

12L

26L

Mandels k statistics(Soil 3 - PBD 99)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

10L

46L

64L

12L

26L

Labo

rato

ries

NUM

-200 -100 000 100 200

h-values

10L

46L

64L

12L

26L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 99)

Soil 3-PBD 99

Unit mgkg

Mandels k statistics(Compost 1 - PBD 100)Mandels h statistics(Compost 1 - PBD 100)

Sample Compost 1 Compost 1 - PBD 100 -- Mean PARM = 0001 [mgkg]

Element PBD 100

General calcparmT1= 124272E-02T2= 113129E-05T3= 14T4= 52T5= 46584E-07

n= variabelp= 4

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean26L 00006 0000 2 -131 037 Fail 00006 00001 2 1 00010L 00009 0000 4 003 083 00009 00002 4 3 00046L 00009 0000 4 016 115 00009 00002 4 3 00012L 00011 0000 4 112 136 Fail 00011 00003 4 3 000

Totgem 0001 0000 mgkg 1-level 149 (167) 4 00009 () 4 3Totstd= 0000 0000 5-level 142 (15)

RESULTS Mean = 000085 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000022 --gt 2531 r = 00006Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000025 --gt 2882 R = 00007Remarks none

000 050 100 150

k-values

26L

10L

46L

12L

Mandels k statistics(Compost 1 - PBD 100)

00 00 00 00 00 00 00 00 00 00 00

Deviation from Mean

26L

10L

46L

12L

Labo

rato

ries

Compost 1 - PBD 100 -- Mean PARM = 0001 [mgkg]

-200 -100 000 100 200

h-values

26L

10L

46L

12L

Labo

rato

ries

Mandels h statistics(Compost 1 - PBD 100)

Compost 1-PBD 100

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 100)Mandels h statistics(Sludge 1 - PBD 100)

Sample Sludge 1 Sludge 1 - PBD 100 -- Mean PARM = 0005 [mgkg]

Element PBD 100

General calcparmT1= 852065E-02T2= 412762E-04T3= 18T4= 68T5= 78914E-07

n= variabelp= 5

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00039 0000 4 -042 007 Fail 00039 00002 4 3 000

12L 00044 0000 4 -041 005 Fail 00044 00001 4 3 00010L 00046 0000 4 -041 013 Fail 00046 00003 4 3 00046L 00056 0000 4 -040 012 Fail 00056 00003 4 3 00026L 00059 0000 2 -040 013 Fail 00059 00003 2 1 00038L 02168 0006 4 204 244 Fail - - 38L - - 021

Totgem 0040 0001 mgkg 1-level 187 (177) 5 00049 (38L) 5 4Totstd= 0087 0002 5-level 166 (154) 1

RESULTS Mean = 000486 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000025 --gt 507 r = 00007Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000084 --gt 1731 R = 00024Remarks 1 Lab rejected (38L)

000 050 100 150 200 250

k-values

4L

12L

10L

46L

26L

38L

Mandels k statistics(Sludge 1 - PBD 100)

-01 00 01 01 02 02 03

Deviation from Mean

4L

12L

10L

46L

26L

38L

Labo

rato

ries

Sludge 1 - PBD 100 -- Mean PARM = 0005 [mgkg]

-100 000 100 200 300

h-values

4L

12L

10L

46L

26L

38L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 100)

Sludge 1-PBD 100

Unit mgkg

Mandels k statistics(Soil 3 - PBD 100)Mandels h statistics(Soil 3 - PBD 100)

Sample Soil 3 NUM

Element PBD 100

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00003 0000 4 -050 000 Fail - - 10L - - NUM46L 00003 0000 4 -050 000 Fail NUM - 46L - - NUM3L 305500 2051 2 150 200 Fail - - 3L - - NUM

26L 00005 0000 2 -050 000 Fail - - 26L - - NUM

Totgem 7638 0513 mgkg 1-level 149 (177) NUM (10L46L3L26L) -1Totstd= 15275 1025 5-level 142 (159) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (10L46L3L26L)

000 050 100 150 200

k-values

10L

46L

3L

26L

Mandels k statistics(Soil 3 - PBD 100)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

10L

46L

3L

26L

Labo

rato

ries

NUM

-100 000 100 200

h-values

10L

46L

3L

26L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 100)

Soil 3-PBD 100

Unit mgkg

Mandels k statistics(Compost 1 - PBD 153)Mandels h statistics(Compost 1 - PBD 153)

Sample Compost 1 NUM

Element PBD 153

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean44L 00053 0001 3 150 157 Fail - - 44L - - NUM46L 00007 0000 4 -044 111 Fail - - 46L - - NUM12L 00005 0000 4 -051 055 Fail - - 12L - - NUM26L 00005 0000 2 -054 001 Fail NUM - 26L - - NUM

Totgem 0002 0000 mgkg 1-level 149 (177) NUM (44L46L12L26L) -1Totstd= 0002 0000 5-level 142 (159) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (44L46L12L26L)

000 050 100 150 200

k-values

44L

46L

12L

26L

Mandels k statistics(Compost 1 - PBD 153)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

44L

46L

12L

26L

Labo

rato

ries

NUM

-100 000 100 200

h-values

44L

46L

12L

26L

Labo

rato

ries

Mandels h statistics(Compost 1 - PBD 153)

Compost 1-PBD 153

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 153)Mandels h statistics(Sludge 1 - PBD 153)

Sample Sludge 1 Sludge 1 - PBD 153 -- Mean PARM = 0004 [mgkg]

Element PBD 153

General calcparmT1= 676738E-02T2= 267609E-04T3= 18T4= 68T5= 19626E-05

n= variabelp= 5

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00024 0000 4 -157 017 00024 00002 4 3 000

12L 00038 0002 4 006 154 00038 00018 4 3 00046L 00039 0000 4 011 026 00039 00003 4 3 00026L 00039 0000 2 018 004 00039 00000 2 1 00064L 00049 0002 4 122 159 00049 00018 4 3 000

Totgem 0004 0001 mgkg 1-level 172 (173) 5 00038 () 5 4Totstd= 0001 0001 5-level 157 (153)

RESULTS Mean = 000378 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000123 --gt 3252 r = 00034Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000142 --gt 3754 R = 00040Remarks none

000 050 100 150 200

k-values

4L

12L

46L

26L

64L

Mandels k statistics(Sludge 1 - PBD 153)

00 00 00 00 00 00 00

Deviation from Mean

4L

12L

46L

26L

64L

Labo

rato

ries

Sludge 1 - PBD 153 -- Mean PARM = 0004 [mgkg]

-200 -100 000 100 200

h-values

4L

12L

46L

26L

64L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 153)

Sludge 1-PBD 153

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 154)Mandels h statistics(Sludge 1 - PBD 154)

Sample Sludge 1 NA

Element PBD 154

General calcparmT1= NAT2= NAT3=T4=T5=

n= variabelp=

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00021 0000 3 -100 021 NA - 4L - - NA

46L 00025 0000 4 115 018 NA - 46L - - NA64L 00021 0001 4 -066 179 - - 64L - - NA12L 00023 0000 4 050 085 - - 12L - - NA

Totgem 0002 0000 mgkg 1-level 149 (167) NA (4L46L64L12L) -1Totstd= 0000 0000 5-level 142 (15) 4

RESULTS Mean = NA mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NAReproducibility var S2R = NAReproducibility std SR = NA --gt NA R = NARemarks 4 Labs rejected (4L46L64L12L)

000 050 100 150 200

k-values

4L

46L

64L

12L

Mandels k statistics(Sludge 1 - PBD 154)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

4L

46L

64L

12L

Labo

rato

ries

NA

-100 000 100 200

h-values

4L

46L

64L

12L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 154)

Sludge 1-PBD 154

Unit mgkg

Mandels k statistics(Soil 3 - PBD 154)Mandels h statistics(Soil 3 - PBD 154)

Sample Soil 3 NUM

Element PBD 154

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

4L 00010 - 1 150 Fail - - 4L - - NUM46L 00001 0000 4 -053 096 Fail - - 46L - - NUM64L 00001 0000 4 -056 105 Fail NUM - 64L - - NUM12L 00002 0000 4 -040 099 Fail - - 12L - - NUM

Totgem 000037 0000 mgkg 1-level 149 (164) NUM (4L46L64L12L) -1Totstd= 000042 0000 5-level 142 (153) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (4L46L64L12L)

000 050 100 150

k-values

4L

46L

64L

12L

Mandels k statistics(Soil 3 - PBD 154)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

4L

46L

64L

12L

Labo

rato

ries

NUM

-100 000 100 200

h-values

4L

46L

64L

12L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 154)

Soil 3-PBD 154

Unit mgkg

Mandels k statistics(Compost 1 - PBD 209)Mandels h statistics(Compost 1 - PBD 209)

Sample Compost 1 NUM

Element PBD 209

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00065 0003 2 -049 032 - - 4L - - NUM

44L 00573 0021 4 150 197 Fail - - 44L - - NUM12L 00078 0001 4 -045 011 - - 12L - - NUM26L 00049 0000 2 -056 000 NUM - 26L - - NUM

Totgem 0019 0006 mgkg 1-level 149 (177) NUM (4L44L12L26L) -1Totstd= 0025 0010 5-level 142 (159) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (4L44L12L26L)

000 050 100 150 200

k-values

4L

44L

12L

26L

Mandels k statistics(Compost 1 - PBD 209)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

4L

44L

12L

26L

Labo

rato

ries

NUM

-100 000 100 200

h-values

4L

44L

12L

26L

Labo

rato

ries

Mandels h statistics(Compost 1 - PBD 209)

Compost 1-PBD 209

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 209)Mandels h statistics(Sludge 1 - PBD 209)

Sample Sludge 1 Sludge 1 - PBD 209 -- Mean PARM = 0249 [mgkg]

Element PBD 209

General calcparmT1= 394542E+00T2= 107296E+00T3= 16T4= 56T5= 19723E-02

n= variabelp= 5

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 01550 0055 4 -112 148 Fail 01550 00551 4 3 -009

46L 02050 0007 2 -053 019 02050 00071 2 1 -00412L 02137 0058 4 -042 155 02137 00576 4 3 -00426L 03149 0021 2 078 057 Fail 03149 00210 2 1 00764L 03577 0007 4 129 020 Fail 03577 00074 4 3 011

Totgem 0249 0030 mgkg 1-level 172 (185) 5 02493 () 5 4Totstd= 0084 0025 5-level 157 (162)

RESULTS Mean = 024926 mgkg

Repeatability variance S2r = 000179Repeatability std Sr = 004234 --gt 1699 r = 01186Between lab variance S2L = 000743Reproducibility var S2R = 000922Reproducibility std SR = 009604 --gt 3853 R = 02689Remarks none

000 050 100 150 200

k-values

4L

46L

12L

26L

64L

Mandels k statistics(Sludge 1 - PBD 209)

-01 -01 00 01 01 02

Deviation from Mean

4L

46L

12L

26L

64L

Labo

rato

ries

Sludge 1 - PBD 209 -- Mean PARM = 0249 [mgkg]

-200 -100 000 100 200

h-values

4L

46L

12L

26L

64L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 209)

Sludge 1-PBD 209

Unit mgkg

Mandels k statistics(Soil 3 - PBD 209)Mandels h statistics(Soil 3 - PBD 209)

Sample Soil 3 Soil 3 - PBD 209 -- Mean PARM = 0258 [mgkg]

Element PBD 209

General calcparmT1= 596398E+00T2= 191917E+00T3= 22T4= 84T5= 13249E-02

n= variabelp= 6

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean26L 01162 0021 2 -108 074 Fail 01162 00207 2 1 -0144L 01303 0031 4 -097 111 Fail 01303 00312 4 3 -013

46L 01975 0036 4 -046 128 Fail 01975 00359 4 3 -00644L 02898 0035 4 024 124 Fail 02898 00346 4 3 00312L 03895 0018 4 100 065 Fail 03895 00181 4 3 01364L 04260 0022 4 127 078 Fail 04260 00219 4 3 017

Totgem 0258 0027 mgkg 1-level 187 (177) 6 02582 () 6 5Totstd= 0132 0008 5-level 166 (154)

RESULTS Mean = 025818 mgkg

Repeatability variance S2r = 000083Repeatability std Sr = 002878 --gt 1115 r = 00806Between lab variance S2L = 001640Reproducibility var S2R = 001723Reproducibility std SR = 013127 --gt 5084 R = 03676Remarks none

000 050 100 150

k-values

26L

4L

46L

44L

12L

64L

Mandels k statistics(Soil 3 - PBD 209)

-02 -01 -01 00 01 01 02 02

Deviation from Mean

26L

4L

46L

44L

12L

64L

Labo

rato

ries

Soil 3 - PBD 209 -- Mean PARM = 0258 [mgkg]

-200 -100 000 100 200

h-values

26L

4L

46L

44L

12L

64L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 209)

Soil 3-PBD 209

Unit mgkg

Mandels k statistics(Compost 1 - Sum PBD)Mandels h statistics(Compost 1 - Sum PBD)

Sample Compost 1 Compost 1 - Sum PBD -- Mean PARM = 0009 [mgkg]

Element Sum PBD

General calcparmT1= 154064E-01T2= 169065E-03T3= 18T4= 68T5= 11354E-04

n= variabelp= 5

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00031 0002 4 -067 016 00031 00016 4 3 -0014L 00055 0005 4 -056 048 00055 00047 4 3 000

46L 00085 0003 4 -042 031 00085 00030 4 3 00026L 00123 0000 2 -024 003 00123 00002 2 1 00012L 00154 0002 4 -011 021 00154 00021 4 3 00144L 00613 0023 4 200 237 Fail - - 44L - - 005

Totgem 0018 0006 mgkg 1-level 187 (177) 5 00089 (44L) 5 4Totstd= 0022 0009 5-level 166 (154) 1

RESULTS Mean = 000893 mgkg

Repeatability variance S2r = 000001Repeatability std Sr = 000296 --gt 3308 r = 00083Between lab variance S2L = 000002Reproducibility var S2R = 000003Reproducibility std SR = 000570 --gt 6374 R = 00159Remarks 1 Lab rejected (44L)

000 050 100 150 200 250

k-values

10L

4L

46L

26L

12L

44L

Mandels k statistics(Compost 1 - Sum PBD)

00 00 00 00 00 00 01 01

Deviation from Mean

10L

4L

46L

26L

12L

44L

Labo

rato

ries

Compost 1 - Sum PBD -- Mean PARM = 0009 [mgkg]

-100 000 100 200

h-values

10L

4L

46L

26L

12L

44L

Labo

rato

ries

Mandels h statistics(Compost 1 - Sum PBD)

Compost 1-Sum PBD

Unit mgkg

Mandels k statistics(Sludge 1 - Sum PBD)Mandels h statistics(Sludge 1 - Sum PBD)

Sample Sludge 1 Sludge 1 - Sum PBD -- Mean PARM = 0256 [mgkg]

Element Sum PBD

General calcparmT1= 531806E+00T2= 162188E+00T3= 22T4= 84T5= 25223E-02

n= variabelp= 6

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00423 0025 4 -156 044 Fail 00423 00252 4 3 -02146L 01808 0118 4 -049 205 - - 46L - - -0074L 01810 0056 4 -049 097 01810 00558 4 3 -007

38L 02168 0006 4 -022 010 02168 00059 4 3 -00412L 02890 0065 4 034 113 02890 00647 4 3 00364L 03958 0008 4 116 014 Fail 03958 00079 4 3 01426L 04094 0034 2 126 059 Fail 04094 00337 2 1 015

Totgem 0245 0044 mgkg 1-level 198 (179) 6 02557 (46L) 6 5Totstd= 0130 0039 5-level 171 (155) 1

RESULTS Mean = 025570 mgkg

Repeatability variance S2r = 000158Repeatability std Sr = 003970 --gt 1553 r = 01112Between lab variance S2L = 001807Reproducibility var S2R = 001964Reproducibility std SR = 014015 --gt 5481 R = 03924Remarks 1 Lab rejected (46L)

000 050 100 150 200 250

k-values

10L

46L

4L

38L

12L

64L

26L

Mandels k statistics(Sludge 1 - Sum PBD)

-03 -02 -02 -01 -01 00 01 01 02 02

Deviation from Mean

10L

46L

4L

38L

12L

64L

26L

Labo

rato

ries

Sludge 1 - Sum PBD -- Mean PARM = 0256 [mgkg]

-200 -100 000 100 200

h-values

10L

46L

4L

38L

12L

64L

26L

Labo

rato

ries

Mandels h statistics(Sludge 1 - Sum PBD)

Sludge 1-Sum PBD

Unit mgkg

Mandels k statistics(Soil 3 - Sum PBD)Mandels h statistics(Soil 3 - Sum PBD)

Sample Soil 3 Soil 3 - Sum PBD -- Mean PARM = 0227 [mgkg]

Element Sum PBD

General calcparmT1= 610980E+00T2= 200876E+00T3= 26T4= 100T5= 13106E-02

n= variabelp= 7

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00028 0001 4 -037 000 Fail 00028 00005 4 3 -02226L 01179 0021 2 -036 003 Fail 01179 00208 2 1 -0114L 01305 0031 4 -036 004 Fail 01305 00308 4 3 -010

46L 02065 0035 4 -036 005 Fail 02065 00350 4 3 -00244L 02923 0037 4 -035 005 Fail 02923 00365 4 3 00712L 04051 0015 4 -034 002 Fail 04051 00149 4 3 01864L 04314 0022 4 -033 003 Fail 04314 00223 4 3 0203L 305500 2051 2 247 283 Fail - - 3L - - 3032

Totgem 4017 0276 mgkg 1-level 206 (181) 7 02266 (3L) 7 6Totstd= 10722 0717 5-level 175 (156) 1

RESULTS Mean = 022663 mgkg

Repeatability variance S2r = 000069Repeatability std Sr = 002626 --gt 1159 r = 00735Between lab variance S2L = 002568Reproducibility var S2R = 002637Reproducibility std SR = 016238 --gt 7165 R = 04547Remarks 1 Lab rejected (3L)

000 050 100 150 200 250 300

k-values

10L

26L

4L

46L

44L

12L

64L

3L

Mandels k statistics(Soil 3 - Sum PBD)

-50 00 50 100 150 200 250 300 350

Deviation from Mean

10L

26L

4L

46L

44L

12L

64L

3L

Labo

rato

ries

Soil 3 - Sum PBD -- Mean PARM = 0227 [mgkg]

-100 000 100 200 300

h-values

10L

26L

4L

46L

44L

12L

64L

3L

Labo

rato

ries

Mandels h statistics(Soil 3 - Sum PBD)

Soil 3-Sum PBD

19

Annex 4

Raw data submitted

Sample Compost1 Sample Compost 1 Sample Compost 1Element PBD 99 Element PBD 100 Element PBD 153

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]4L 00021 10L 00008 44L 000504L 00024 10L 00008 44L 000604L 00014 10L 00007 44L 000504L 00020 10L 00011 46L 00004

10L 00029 46L 00007 46L 0001210L 00027 46L 00012 46L 0000410L 00032 46L 00009 46L 0000946L 00025 46L 00007 12L 0000446L 00052 12L 00008 12L 0000846L 00029 12L 00012 12L 0000446L 00026 12L 00008 12L 0000712L 00026 12L 00014 26L 0000512L 00043 26L 00007 26L 0000512L 00026 26L 0000612L 0004726L 0002626L 00024

Sample Compost 1 Sample Compost 1 Sample Compost 1Element PBD 154 Element PBD 183 Element PBD 196

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]4L 00010 46L 00002 46L 00011

46L 00003 46L 00024 46L 0000846L 00007 46L 00021 12L 0000246L 00003 46L 00003 12L 0000346L 00004 12L 00003 12L 0000112L 00003 12L 00011 12L 0000212L 00005 12L 0000312L 00031 12L 0000312L 00006

Sample Compost 1 Sample Compost 1 Sample Compost 1Element PBD 197 Element PBD 203 Element PBD 209

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00002 46L 00010 4L 0004146L 00023 12L 00002 4L 0008946L 00022 12L 00003 44L 0041012L 00004 12L 00002 44L 0084012L 00006 12L 00002 44L 0064012L 00003 44L 0040012L 00004 12L 00079

12L 0007312L 0006512L 0009326L 0004926L 00049

Sample Compost 1Element PBD 47

LAB PARM [mgkg]26L 0003826L 00039

Element PBD 99 Element PBD 47 Element PBD 209LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]

4L 00170 10L 00210 4L 010004L 00200 10L 00220 4L 018004L 00170 10L 00210 4L 012004L 00190 46L 00300 4L 0220010L 00280 46L 00280 46L 0210010L 00300 46L 00250 46L 0200010L 00290 46L 00260 64L 0351846L 00340 64L 00059 64L 0363846L 00330 64L 00057 64L 0364546L 00300 64L 00062 64L 0350846L 00310 64L 00060 12L 0220964L 00194 12L 00191 12L 0177164L 00154 12L 00187 12L 0292264L 00185 12L 00190 12L 0164664L 00159 12L 00186 26L 0329712L 00242 26L 00666 26L 0300012L 00223 26L 0033212L 0022112L 0022226L 0024626L 00400

Element PBD 203 Element PBD 197 Element PBD 196LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00022 46L 00027 46L 0002446L 00014 46L 00024 46L 0002264L 00036 12L 00161 64L 0005864L 00058 12L 00060 64L 0006512L 00063 12L 00061 12L 0004812L 00034 12L 00036 12L 0002512L 00038 12L 0003212L 00027 12L 00022

Element PBD 183 Element PBD 154 Element PBD 153LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00049 4L 00020 4L 0002246L 00035 4L 00022 4L 0002446L 00036 4L 00020 4L 0002246L 00034 46L 00025 4L 0002664L 00027 46L 00025 46L 0004064L 00023 46L 00025 46L 0004264L 00024 46L 00023 46L 0003564L 00020 64L 00034 46L 0003812L 00230 64L 00023 64L 0007412L 00032 64L 00017 64L 0004712L 00031 64L 00011 64L 0004612L 00030 12L 00030 64L 0003026L 00007 12L 00021 12L 0006526L 00008 12L 00021 12L 00029

12L 00021 12L 0003226L 00015 12L 0002926L 00019 26L 00039

26L 00040

Element PBD 100LAB PARM [mgkg]

4L 000384L 000414L 000374L 00038

38L 0219038L 0220038L 0208038L 0220010L 0004410L 0005010L 0004310L 0004646L 0005746L 0005946L 0005346L 0005312L 0004312L 0004512L 0004312L 0004326L 0006226L 00057

Sample Soil 3 Sample Soil 3 Sample Soil 3Element PBD 99 Element PBD 47 Element PBD 100

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]10L 00016 10L 00011 10L 0000310L 00019 10L 00010 10L 0000410L 00013 10L 00012 10L 0000410L 00019 46L 00007 10L 0000246L 00025 46L 00022 46L 0000246L 00025 46L 00005 46L 0000646L 00008 46L 00007 46L 0000246L 00011 12L 00010 46L 0000264L 00005 12L 00017 3L 29100064L 00005 12L 00010 3L 32000064L 00006 12L 00009 26L 0000564L 00007 26L 00007 26L 0000512L 00012 26L 0000712L 0001312L 0001312L 0001226L 0000526L 00006

Sample Soil 3 Sample Soil 3 Sample Soil 3Element PBD 153 Element PBD 154 Element PBD 196

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]44L 00050 4L 00010 46L 0000744L 00050 46L 00001 46L 0001146L 00002 46L 00002 46L 0000846L 00003 46L 00001 46L 0001146L 00002 46L 00002 64L 0002646L 00002 64L 00001 64L 0002664L 00001 64L 00001 64L 0002964L 00001 64L 00001 64L 0003464L 00001 64L 00002 12L 0004564L 00002 12L 00003 12L 00032

12L 00002 12L 0002212L 00002 12L 0002112L 00002

Sample Soil 3 Sample Soil 3 Sample Soil 3Element PBD 197 Element PBD 203 Element PBD 209

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00006 46L 00011 4L 0091046L 00013 46L 00017 4L 0150046L 00011 46L 00015 4L 0120046L 00013 46L 00018 4L 0160012L 00090 64L 00013 44L 0337012L 00056 64L 00014 44L 0281012L 00033 64L 00016 44L 0287012L 00032 64L 00015 44L 02540

12L 00055 46L 0230012L 00041 46L 0220012L 00027 46L 0150012L 00026 46L 01900

64L 0438164L 0401664L 0414464L 0449812L 0367112L 0397812L 0409112L 03838

Sample Soil 3 26L 0102Element PBD 183 26L 0131

LAB PARM [mgkg]46L 0000746L 0000846L 0005846L 0000764L 0000264L 0000364L 0000364L 0000312L 0001512L 0001112L 0000712L 00007

European Commission EUR 23003 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on polybrominated diphenylethers Author(s) E Sobiecka H van der Sloot D Barcelo B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 68 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07403-5 Abstract Project HORIZONTAL is interdisciplinary aiming at a harmonisation and horizontal standardisation of test procedures in particular for sludge soils and biowastes In the context of this standardization project a series of draft technical specification were designed upon an extensive desk study fine-tuned after expert consultations and finally validated in international intercomparisons exercise This report summarises the work performed within the validation study of the draft standard for the determination of polybrominated diphenylethers (PBDE) in soils sludge and treated bio-waste using gas-chromatography method with mass selective detection (GC-MS) It further explains the underlying statistical concept for the calculation of reproducibility and repeatability from intercomparisons data In addition all single values results of the statistical evaluation as well as background information on the validation materials used are described and explained

The mission of the JRC is to provide customer-driven scientific and technical support for the conception development implementation and monitoring of EU policies As a service of the European Commission the JRC functions as a reference centre of science and technology for the Union Close to the policy-making process it serves the common interest of the Member States while being independent of special interests whether private or national

LB

-NA

-23003-EN

-C

14

24 Agricultural soil sludge amended soil from Pavia Italy

This sludge-amended soil material was obtained during a monitoring campaign which aimed at a generic description of the over-all soil quality in Pavia Province Italy The material which was collected from the upper horizon originates from a small farm called ldquoCascina Novellordquo During the characterisation of the site the following analytical information was obtained on a pooled sample of a sub-area of the farm of 20 X 20 m2

Table 23 ndash Analytical data on Pavia soil

Parameter Result Al 713 Wgt As 224 mgkg Cd 079 mgkg Cr 59 mgkg Cu 308 mgkg Hg 008 mgkg Ni 344 mgkg Pb 246 mgkg Zn 95 mgkg C 091 Wgt 2378-TCDD 0047 pgg 12378-PeCDD 015 pgg 123478-HxCDD 019 pgg 123678-HxCDD 15 pgg 123789-HxCDD 074 pgg 1234678-HpCDD 26 pgg OCDD 382 pgg 2378-TCDF 068 pgg 12378-PeCDF 053 pgg 23478-PeCDF 071 pgg 123478-HxDF 100 pgg 123678-HxDF 066 pgg 234678-HxDF 16 pgg 123789-HxDF 027 pgg 1234678-HpDF 12 pgg 1234789-HpDF 068 pgg OCDF 33 pgg I-TEQ 20 pgg WHO-TEQ 17 pgg

In addition the screening performed at IRMM did not reveal significant quantities of PCBs and PAHs which were all below the LoDs (1 ngg for PCBs and 10 ngg for PAHs respectively)

Table 24 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 5 (Pavia) 0005 0011 154

15

Table 25 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 5

(Pavia)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

039

nq

nq

008

nq

nd

nd

670

671

Table 26 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 5 (Pavia) 033 184 573 225 426 305 206 200 lt 005 381 878

Table 27 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 5 (Pavia) 6939 129 145 224 425 116 6118 255 1789 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 5 (Pavia) 184 62 38 108 55 66 597 110

Table 28 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 5 (Pavia) 006

16

25 Sludge-amended-soil from Barcelona Spain

The sludge-amended soil material from Barcelona sampled upon indication from the Barcelorsquo- Group in Barcelona

Table 29 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 2 (Lleida T) 0015 0183 1138

Table 30 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 2

(Lleida T)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

159

045

nq

048

160

nq

nq

1000

1004

Table 31 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 2 (Lleida T) 059 141 327 536 405 186 184 224 lt 005 318 111

Table 32 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 2 (Lleida T) 4443 1067 1429 253 344 204 4116 780 3396 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 2 (Lleida T) 064 65 26 125 59 17 547 65

Table 33 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 2 (Lleida T) 010

17

26 Sludge amended soil from Essen Germany

The German sludge-amended soil from Essen which was provided as the three sludge materials by LUA NRW did not feature significant concentrations of the PCB congeners 28 52 101 118 153 105 138 156 180 170 but had detectable amounts of some PAHs

Table 34 ndash Analytical screening data on the German sludge-amended soil

Parameter Concentration(ngg)

Naphtalene lt10 Acenaphtylene lt10 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene lt10 Fluoranthene 28 Pyrene 20 Benz(a)anthracene 24 Chrysene 47 Benz(b)fluoranthene 76 Benz(k)fluoranthene 20 Benz(a)pyrene 35 Indeno(123-cd)pyrene 35 Dibenzo(ah)anthracene 10 Benzo(ghi)perylene 26

Table 35 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 4 (Essen) 0011 0302 055

Table 36 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 4

(Essen)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

nq

nq

nq

nq

nq

nq

128

191

203

18

Table 37 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 4 (Essen) 052 545 261 805 320 403 273 273 lt 005 295 781

Table 38 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 4 (Essen) 7947 442 085 06 086 007 2163 189 2019 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 4 (Essen) 045 19 42 87 683 60 462 61

Table 39 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 4 (Essen) 004

27 Long-term sludge exposed soil from Hohenheim-Stuttgart Germany

Similarly an additional sludge exposed soil was sampled at the University of Hohenheim Stuttgart were a test soil was long-term exposed to elevated concentrations of sewage sludge

Table 40 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 1 (Stuttgart) 0045 0263 1765

Table 41 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 1

(Stuttgart)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

230

006

004

004

nq

nd

nd

498

500

19

Table 42 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 1 (Stuttgart) 069 127 361 262 504 183 252 262 lt 005 266 142

Table 43 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 1 (Stuttgart) 7194 1006 133 186 366 088 7874 275 3571 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 1 (Stuttgart) 123 50 47 212 85 69 991 129

Table 44 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 1 (Stuttgart) 177

18

Annex 3

Statistical calculations

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 47)Mandels h statistics(Sludge 1 - PBD 47)

Sample Sludge 1 NUM

Element PBD 47

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00213 0001 3 -021 005 - - 10L - - NUM46L 00273 0002 4 016 021 - - 46L - - NUM64L 00059 0000 4 -116 002 NUM - 64L - - NUM12L 00188 0000 4 -036 002 - - 12L - - NUM26L 00499 0024 2 157 223 Fail - - 26L - - NUM

Totgem 0025 0005 mgkg 1-level 172 (185) NUM (10L46L64L12L26L) -1Totstd= 0016 0010 5-level 157 (162) 5

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 5 Labs rejected (10L46L64L12L26L)

000 050 100 150 200 250

k-values

10L

46L

64L

12L

26L

Mandels k statistics(Sludge 1 - PBD 47)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

10L

46L

64L

12L

26L

Labo

rato

ries

NUM

-200 -100 000 100 200

h-values

10L

46L

64L

12L

26L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 47)

Sludge 1-PBD 47

Unit mgkg

Mandels k statistics(Soil 3 - PBD 47)Mandels h statistics(Soil 3 - PBD 47)

Sample Soil 3 Soil 3 - PBD 47 -- Mean PARM = 0001 [mgkg]

Element PBD 47

General calcparmT1= 134814E-02T2= 142830E-05T3= 13T4= 45T5= 22767E-06

n= variabelp= 4

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean26L 00007 0000 2 -143 001 00007 00000 2 1 00046L 00010 0001 4 010 181 00010 00008 4 3 00010L 00011 0000 3 049 023 00011 00001 3 2 00012L 00012 0000 4 084 081 00012 00004 4 3 000

Totgem 0001 0000 mgkg 1-level 149 (177) 4 00010 () 4 3Totstd= 0000 0000 5-level 142 (159)

RESULTS Mean = 000100 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000050 --gt 5031 r = 00014Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000050 --gt 5031 R = 00014Remarks none

000 050 100 150 200

k-values

26L

46L

10L

12L

Mandels k statistics(Soil 3 - PBD 47)

00 00 00 00 00 00 00 00 00 00 00

Deviation from Mean

26L

46L

10L

12L

Labo

rato

ries

Soil 3 - PBD 47 -- Mean PARM = 0001 [mgkg]

-200 -100 000 100

h-values

26L

46L

10L

12L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 47)

Soil 3-PBD 47

Unit mgkg

Mandels k statistics(Compost 1 - PBD 99)Mandels h statistics(Compost 1 - PBD 99)

Sample Compost 1 Compost 1 - PBD 99 -- Mean PARM = 0003 [mgkg]

Element PBD 99

General calcparmT1= 492124E-02T2= 148747E-04T3= 17T4= 61T5= 93196E-06

n= variabelp= 5

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00020 0000 4 -137 053 00020 00004 4 3 000

26L 00025 0000 2 -058 024 00025 00002 2 1 00010L 00029 0000 3 012 032 00029 00003 3 2 00046L 00033 0001 4 069 161 00033 00013 4 3 00012L 00036 0001 4 114 140 00036 00011 4 3 000

Totgem 0003 0001 mgkg 1-level 172 (185) 5 00029 () 5 4Totstd= 0001 0001 5-level 157 (162)

RESULTS Mean = 000286 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000088 --gt 3086 r = 00025Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000101 --gt 3525 R = 00028Remarks none

000 050 100 150 200

k-values

4L

26L

10L

46L

12L

Mandels k statistics(Compost 1 - PBD 99)

00 00 00 00 00 00 00 00 00 00

Deviation from Mean

4L

26L

10L

46L

12L

Labo

rato

ries

Compost 1 - PBD 99 -- Mean PARM = 0003 [mgkg]

-200 -100 000 100 200

h-values

4L

26L

10L

46L

12L

Labo

rato

ries

Mandels h statistics(Compost 1 - PBD 99)

Compost 1-PBD 99

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 99)Mandels h statistics(Sludge 1 - PBD 99)

Sample Sludge 1 Sludge 1 - PBD 99 -- Mean PARM = 0024 [mgkg]

Element PBD 99

General calcparmT1= 448050E-01T2= 112113E-02T3= 19T4= 73T5= 32972E-05

n= variabelp= 5

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean64L 00173 0002 4 -118 041 Fail 00173 00019 4 3 -0014L 00183 0002 4 -104 032 00183 00015 4 3 -001

12L 00227 0001 4 -038 022 00227 00010 4 3 00010L 00290 0001 3 055 021 00290 00010 3 2 00146L 00320 0002 4 100 039 00320 00018 4 3 00126L 00323 0011 2 105 234 - - 26L - - 001

Totgem 0025 0003 mgkg 1-level 187 (177) 5 00239 (26L) 5 4Totstd= 0007 0004 5-level 166 (154) 1

RESULTS Mean = 002385 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000153 --gt 643 r = 00043Between lab variance S2L = 000004Reproducibility var S2R = 000004Reproducibility std SR = 000666 --gt 2791 R = 00186Remarks 1 Lab rejected (26L)

000 050 100 150 200 250

k-values

64L

4L

12L

10L

46L

26L

Mandels k statistics(Sludge 1 - PBD 99)

00 00 00 00 00 00 00 00 00 00

Deviation from Mean

64L

4L

12L

10L

46L

26L

Labo

rato

ries

Sludge 1 - PBD 99 -- Mean PARM = 0024 [mgkg]

-200 -100 000 100 200

h-values

64L

4L

12L

10L

46L

26L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 99)

Sludge 1-PBD 99

Unit mgkg

Mandels k statistics(Soil 3 - PBD 99)Mandels h statistics(Soil 3 - PBD 99)

Sample Soil 3 NUM

Element PBD 99

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00017 0000 4 091 068 - - 10L - - NUM46L 00017 0001 4 100 211 - - 46L - - NUM64L 00005 0000 4 -106 023 NUM - 64L - - NUM12L 00012 0000 4 015 014 - - 12L - - NUM26L 00006 0000 2 -101 012 - - 26L - - NUM

Totgem 0001 0000 mgkg 1-level 172 (173) NUM (10L46L64L12L26L) -1Totstd= 0001 0000 5-level 157 (153) 5

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 5 Labs rejected (10L46L64L12L26L)

000 050 100 150 200 250

k-values

10L

46L

64L

12L

26L

Mandels k statistics(Soil 3 - PBD 99)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

10L

46L

64L

12L

26L

Labo

rato

ries

NUM

-200 -100 000 100 200

h-values

10L

46L

64L

12L

26L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 99)

Soil 3-PBD 99

Unit mgkg

Mandels k statistics(Compost 1 - PBD 100)Mandels h statistics(Compost 1 - PBD 100)

Sample Compost 1 Compost 1 - PBD 100 -- Mean PARM = 0001 [mgkg]

Element PBD 100

General calcparmT1= 124272E-02T2= 113129E-05T3= 14T4= 52T5= 46584E-07

n= variabelp= 4

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean26L 00006 0000 2 -131 037 Fail 00006 00001 2 1 00010L 00009 0000 4 003 083 00009 00002 4 3 00046L 00009 0000 4 016 115 00009 00002 4 3 00012L 00011 0000 4 112 136 Fail 00011 00003 4 3 000

Totgem 0001 0000 mgkg 1-level 149 (167) 4 00009 () 4 3Totstd= 0000 0000 5-level 142 (15)

RESULTS Mean = 000085 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000022 --gt 2531 r = 00006Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000025 --gt 2882 R = 00007Remarks none

000 050 100 150

k-values

26L

10L

46L

12L

Mandels k statistics(Compost 1 - PBD 100)

00 00 00 00 00 00 00 00 00 00 00

Deviation from Mean

26L

10L

46L

12L

Labo

rato

ries

Compost 1 - PBD 100 -- Mean PARM = 0001 [mgkg]

-200 -100 000 100 200

h-values

26L

10L

46L

12L

Labo

rato

ries

Mandels h statistics(Compost 1 - PBD 100)

Compost 1-PBD 100

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 100)Mandels h statistics(Sludge 1 - PBD 100)

Sample Sludge 1 Sludge 1 - PBD 100 -- Mean PARM = 0005 [mgkg]

Element PBD 100

General calcparmT1= 852065E-02T2= 412762E-04T3= 18T4= 68T5= 78914E-07

n= variabelp= 5

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00039 0000 4 -042 007 Fail 00039 00002 4 3 000

12L 00044 0000 4 -041 005 Fail 00044 00001 4 3 00010L 00046 0000 4 -041 013 Fail 00046 00003 4 3 00046L 00056 0000 4 -040 012 Fail 00056 00003 4 3 00026L 00059 0000 2 -040 013 Fail 00059 00003 2 1 00038L 02168 0006 4 204 244 Fail - - 38L - - 021

Totgem 0040 0001 mgkg 1-level 187 (177) 5 00049 (38L) 5 4Totstd= 0087 0002 5-level 166 (154) 1

RESULTS Mean = 000486 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000025 --gt 507 r = 00007Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000084 --gt 1731 R = 00024Remarks 1 Lab rejected (38L)

000 050 100 150 200 250

k-values

4L

12L

10L

46L

26L

38L

Mandels k statistics(Sludge 1 - PBD 100)

-01 00 01 01 02 02 03

Deviation from Mean

4L

12L

10L

46L

26L

38L

Labo

rato

ries

Sludge 1 - PBD 100 -- Mean PARM = 0005 [mgkg]

-100 000 100 200 300

h-values

4L

12L

10L

46L

26L

38L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 100)

Sludge 1-PBD 100

Unit mgkg

Mandels k statistics(Soil 3 - PBD 100)Mandels h statistics(Soil 3 - PBD 100)

Sample Soil 3 NUM

Element PBD 100

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00003 0000 4 -050 000 Fail - - 10L - - NUM46L 00003 0000 4 -050 000 Fail NUM - 46L - - NUM3L 305500 2051 2 150 200 Fail - - 3L - - NUM

26L 00005 0000 2 -050 000 Fail - - 26L - - NUM

Totgem 7638 0513 mgkg 1-level 149 (177) NUM (10L46L3L26L) -1Totstd= 15275 1025 5-level 142 (159) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (10L46L3L26L)

000 050 100 150 200

k-values

10L

46L

3L

26L

Mandels k statistics(Soil 3 - PBD 100)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

10L

46L

3L

26L

Labo

rato

ries

NUM

-100 000 100 200

h-values

10L

46L

3L

26L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 100)

Soil 3-PBD 100

Unit mgkg

Mandels k statistics(Compost 1 - PBD 153)Mandels h statistics(Compost 1 - PBD 153)

Sample Compost 1 NUM

Element PBD 153

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean44L 00053 0001 3 150 157 Fail - - 44L - - NUM46L 00007 0000 4 -044 111 Fail - - 46L - - NUM12L 00005 0000 4 -051 055 Fail - - 12L - - NUM26L 00005 0000 2 -054 001 Fail NUM - 26L - - NUM

Totgem 0002 0000 mgkg 1-level 149 (177) NUM (44L46L12L26L) -1Totstd= 0002 0000 5-level 142 (159) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (44L46L12L26L)

000 050 100 150 200

k-values

44L

46L

12L

26L

Mandels k statistics(Compost 1 - PBD 153)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

44L

46L

12L

26L

Labo

rato

ries

NUM

-100 000 100 200

h-values

44L

46L

12L

26L

Labo

rato

ries

Mandels h statistics(Compost 1 - PBD 153)

Compost 1-PBD 153

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 153)Mandels h statistics(Sludge 1 - PBD 153)

Sample Sludge 1 Sludge 1 - PBD 153 -- Mean PARM = 0004 [mgkg]

Element PBD 153

General calcparmT1= 676738E-02T2= 267609E-04T3= 18T4= 68T5= 19626E-05

n= variabelp= 5

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00024 0000 4 -157 017 00024 00002 4 3 000

12L 00038 0002 4 006 154 00038 00018 4 3 00046L 00039 0000 4 011 026 00039 00003 4 3 00026L 00039 0000 2 018 004 00039 00000 2 1 00064L 00049 0002 4 122 159 00049 00018 4 3 000

Totgem 0004 0001 mgkg 1-level 172 (173) 5 00038 () 5 4Totstd= 0001 0001 5-level 157 (153)

RESULTS Mean = 000378 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000123 --gt 3252 r = 00034Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000142 --gt 3754 R = 00040Remarks none

000 050 100 150 200

k-values

4L

12L

46L

26L

64L

Mandels k statistics(Sludge 1 - PBD 153)

00 00 00 00 00 00 00

Deviation from Mean

4L

12L

46L

26L

64L

Labo

rato

ries

Sludge 1 - PBD 153 -- Mean PARM = 0004 [mgkg]

-200 -100 000 100 200

h-values

4L

12L

46L

26L

64L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 153)

Sludge 1-PBD 153

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 154)Mandels h statistics(Sludge 1 - PBD 154)

Sample Sludge 1 NA

Element PBD 154

General calcparmT1= NAT2= NAT3=T4=T5=

n= variabelp=

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00021 0000 3 -100 021 NA - 4L - - NA

46L 00025 0000 4 115 018 NA - 46L - - NA64L 00021 0001 4 -066 179 - - 64L - - NA12L 00023 0000 4 050 085 - - 12L - - NA

Totgem 0002 0000 mgkg 1-level 149 (167) NA (4L46L64L12L) -1Totstd= 0000 0000 5-level 142 (15) 4

RESULTS Mean = NA mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NAReproducibility var S2R = NAReproducibility std SR = NA --gt NA R = NARemarks 4 Labs rejected (4L46L64L12L)

000 050 100 150 200

k-values

4L

46L

64L

12L

Mandels k statistics(Sludge 1 - PBD 154)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

4L

46L

64L

12L

Labo

rato

ries

NA

-100 000 100 200

h-values

4L

46L

64L

12L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 154)

Sludge 1-PBD 154

Unit mgkg

Mandels k statistics(Soil 3 - PBD 154)Mandels h statistics(Soil 3 - PBD 154)

Sample Soil 3 NUM

Element PBD 154

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

4L 00010 - 1 150 Fail - - 4L - - NUM46L 00001 0000 4 -053 096 Fail - - 46L - - NUM64L 00001 0000 4 -056 105 Fail NUM - 64L - - NUM12L 00002 0000 4 -040 099 Fail - - 12L - - NUM

Totgem 000037 0000 mgkg 1-level 149 (164) NUM (4L46L64L12L) -1Totstd= 000042 0000 5-level 142 (153) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (4L46L64L12L)

000 050 100 150

k-values

4L

46L

64L

12L

Mandels k statistics(Soil 3 - PBD 154)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

4L

46L

64L

12L

Labo

rato

ries

NUM

-100 000 100 200

h-values

4L

46L

64L

12L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 154)

Soil 3-PBD 154

Unit mgkg

Mandels k statistics(Compost 1 - PBD 209)Mandels h statistics(Compost 1 - PBD 209)

Sample Compost 1 NUM

Element PBD 209

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00065 0003 2 -049 032 - - 4L - - NUM

44L 00573 0021 4 150 197 Fail - - 44L - - NUM12L 00078 0001 4 -045 011 - - 12L - - NUM26L 00049 0000 2 -056 000 NUM - 26L - - NUM

Totgem 0019 0006 mgkg 1-level 149 (177) NUM (4L44L12L26L) -1Totstd= 0025 0010 5-level 142 (159) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (4L44L12L26L)

000 050 100 150 200

k-values

4L

44L

12L

26L

Mandels k statistics(Compost 1 - PBD 209)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

4L

44L

12L

26L

Labo

rato

ries

NUM

-100 000 100 200

h-values

4L

44L

12L

26L

Labo

rato

ries

Mandels h statistics(Compost 1 - PBD 209)

Compost 1-PBD 209

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 209)Mandels h statistics(Sludge 1 - PBD 209)

Sample Sludge 1 Sludge 1 - PBD 209 -- Mean PARM = 0249 [mgkg]

Element PBD 209

General calcparmT1= 394542E+00T2= 107296E+00T3= 16T4= 56T5= 19723E-02

n= variabelp= 5

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 01550 0055 4 -112 148 Fail 01550 00551 4 3 -009

46L 02050 0007 2 -053 019 02050 00071 2 1 -00412L 02137 0058 4 -042 155 02137 00576 4 3 -00426L 03149 0021 2 078 057 Fail 03149 00210 2 1 00764L 03577 0007 4 129 020 Fail 03577 00074 4 3 011

Totgem 0249 0030 mgkg 1-level 172 (185) 5 02493 () 5 4Totstd= 0084 0025 5-level 157 (162)

RESULTS Mean = 024926 mgkg

Repeatability variance S2r = 000179Repeatability std Sr = 004234 --gt 1699 r = 01186Between lab variance S2L = 000743Reproducibility var S2R = 000922Reproducibility std SR = 009604 --gt 3853 R = 02689Remarks none

000 050 100 150 200

k-values

4L

46L

12L

26L

64L

Mandels k statistics(Sludge 1 - PBD 209)

-01 -01 00 01 01 02

Deviation from Mean

4L

46L

12L

26L

64L

Labo

rato

ries

Sludge 1 - PBD 209 -- Mean PARM = 0249 [mgkg]

-200 -100 000 100 200

h-values

4L

46L

12L

26L

64L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 209)

Sludge 1-PBD 209

Unit mgkg

Mandels k statistics(Soil 3 - PBD 209)Mandels h statistics(Soil 3 - PBD 209)

Sample Soil 3 Soil 3 - PBD 209 -- Mean PARM = 0258 [mgkg]

Element PBD 209

General calcparmT1= 596398E+00T2= 191917E+00T3= 22T4= 84T5= 13249E-02

n= variabelp= 6

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean26L 01162 0021 2 -108 074 Fail 01162 00207 2 1 -0144L 01303 0031 4 -097 111 Fail 01303 00312 4 3 -013

46L 01975 0036 4 -046 128 Fail 01975 00359 4 3 -00644L 02898 0035 4 024 124 Fail 02898 00346 4 3 00312L 03895 0018 4 100 065 Fail 03895 00181 4 3 01364L 04260 0022 4 127 078 Fail 04260 00219 4 3 017

Totgem 0258 0027 mgkg 1-level 187 (177) 6 02582 () 6 5Totstd= 0132 0008 5-level 166 (154)

RESULTS Mean = 025818 mgkg

Repeatability variance S2r = 000083Repeatability std Sr = 002878 --gt 1115 r = 00806Between lab variance S2L = 001640Reproducibility var S2R = 001723Reproducibility std SR = 013127 --gt 5084 R = 03676Remarks none

000 050 100 150

k-values

26L

4L

46L

44L

12L

64L

Mandels k statistics(Soil 3 - PBD 209)

-02 -01 -01 00 01 01 02 02

Deviation from Mean

26L

4L

46L

44L

12L

64L

Labo

rato

ries

Soil 3 - PBD 209 -- Mean PARM = 0258 [mgkg]

-200 -100 000 100 200

h-values

26L

4L

46L

44L

12L

64L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 209)

Soil 3-PBD 209

Unit mgkg

Mandels k statistics(Compost 1 - Sum PBD)Mandels h statistics(Compost 1 - Sum PBD)

Sample Compost 1 Compost 1 - Sum PBD -- Mean PARM = 0009 [mgkg]

Element Sum PBD

General calcparmT1= 154064E-01T2= 169065E-03T3= 18T4= 68T5= 11354E-04

n= variabelp= 5

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00031 0002 4 -067 016 00031 00016 4 3 -0014L 00055 0005 4 -056 048 00055 00047 4 3 000

46L 00085 0003 4 -042 031 00085 00030 4 3 00026L 00123 0000 2 -024 003 00123 00002 2 1 00012L 00154 0002 4 -011 021 00154 00021 4 3 00144L 00613 0023 4 200 237 Fail - - 44L - - 005

Totgem 0018 0006 mgkg 1-level 187 (177) 5 00089 (44L) 5 4Totstd= 0022 0009 5-level 166 (154) 1

RESULTS Mean = 000893 mgkg

Repeatability variance S2r = 000001Repeatability std Sr = 000296 --gt 3308 r = 00083Between lab variance S2L = 000002Reproducibility var S2R = 000003Reproducibility std SR = 000570 --gt 6374 R = 00159Remarks 1 Lab rejected (44L)

000 050 100 150 200 250

k-values

10L

4L

46L

26L

12L

44L

Mandels k statistics(Compost 1 - Sum PBD)

00 00 00 00 00 00 01 01

Deviation from Mean

10L

4L

46L

26L

12L

44L

Labo

rato

ries

Compost 1 - Sum PBD -- Mean PARM = 0009 [mgkg]

-100 000 100 200

h-values

10L

4L

46L

26L

12L

44L

Labo

rato

ries

Mandels h statistics(Compost 1 - Sum PBD)

Compost 1-Sum PBD

Unit mgkg

Mandels k statistics(Sludge 1 - Sum PBD)Mandels h statistics(Sludge 1 - Sum PBD)

Sample Sludge 1 Sludge 1 - Sum PBD -- Mean PARM = 0256 [mgkg]

Element Sum PBD

General calcparmT1= 531806E+00T2= 162188E+00T3= 22T4= 84T5= 25223E-02

n= variabelp= 6

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00423 0025 4 -156 044 Fail 00423 00252 4 3 -02146L 01808 0118 4 -049 205 - - 46L - - -0074L 01810 0056 4 -049 097 01810 00558 4 3 -007

38L 02168 0006 4 -022 010 02168 00059 4 3 -00412L 02890 0065 4 034 113 02890 00647 4 3 00364L 03958 0008 4 116 014 Fail 03958 00079 4 3 01426L 04094 0034 2 126 059 Fail 04094 00337 2 1 015

Totgem 0245 0044 mgkg 1-level 198 (179) 6 02557 (46L) 6 5Totstd= 0130 0039 5-level 171 (155) 1

RESULTS Mean = 025570 mgkg

Repeatability variance S2r = 000158Repeatability std Sr = 003970 --gt 1553 r = 01112Between lab variance S2L = 001807Reproducibility var S2R = 001964Reproducibility std SR = 014015 --gt 5481 R = 03924Remarks 1 Lab rejected (46L)

000 050 100 150 200 250

k-values

10L

46L

4L

38L

12L

64L

26L

Mandels k statistics(Sludge 1 - Sum PBD)

-03 -02 -02 -01 -01 00 01 01 02 02

Deviation from Mean

10L

46L

4L

38L

12L

64L

26L

Labo

rato

ries

Sludge 1 - Sum PBD -- Mean PARM = 0256 [mgkg]

-200 -100 000 100 200

h-values

10L

46L

4L

38L

12L

64L

26L

Labo

rato

ries

Mandels h statistics(Sludge 1 - Sum PBD)

Sludge 1-Sum PBD

Unit mgkg

Mandels k statistics(Soil 3 - Sum PBD)Mandels h statistics(Soil 3 - Sum PBD)

Sample Soil 3 Soil 3 - Sum PBD -- Mean PARM = 0227 [mgkg]

Element Sum PBD

General calcparmT1= 610980E+00T2= 200876E+00T3= 26T4= 100T5= 13106E-02

n= variabelp= 7

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00028 0001 4 -037 000 Fail 00028 00005 4 3 -02226L 01179 0021 2 -036 003 Fail 01179 00208 2 1 -0114L 01305 0031 4 -036 004 Fail 01305 00308 4 3 -010

46L 02065 0035 4 -036 005 Fail 02065 00350 4 3 -00244L 02923 0037 4 -035 005 Fail 02923 00365 4 3 00712L 04051 0015 4 -034 002 Fail 04051 00149 4 3 01864L 04314 0022 4 -033 003 Fail 04314 00223 4 3 0203L 305500 2051 2 247 283 Fail - - 3L - - 3032

Totgem 4017 0276 mgkg 1-level 206 (181) 7 02266 (3L) 7 6Totstd= 10722 0717 5-level 175 (156) 1

RESULTS Mean = 022663 mgkg

Repeatability variance S2r = 000069Repeatability std Sr = 002626 --gt 1159 r = 00735Between lab variance S2L = 002568Reproducibility var S2R = 002637Reproducibility std SR = 016238 --gt 7165 R = 04547Remarks 1 Lab rejected (3L)

000 050 100 150 200 250 300

k-values

10L

26L

4L

46L

44L

12L

64L

3L

Mandels k statistics(Soil 3 - Sum PBD)

-50 00 50 100 150 200 250 300 350

Deviation from Mean

10L

26L

4L

46L

44L

12L

64L

3L

Labo

rato

ries

Soil 3 - Sum PBD -- Mean PARM = 0227 [mgkg]

-100 000 100 200 300

h-values

10L

26L

4L

46L

44L

12L

64L

3L

Labo

rato

ries

Mandels h statistics(Soil 3 - Sum PBD)

Soil 3-Sum PBD

19

Annex 4

Raw data submitted

Sample Compost1 Sample Compost 1 Sample Compost 1Element PBD 99 Element PBD 100 Element PBD 153

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]4L 00021 10L 00008 44L 000504L 00024 10L 00008 44L 000604L 00014 10L 00007 44L 000504L 00020 10L 00011 46L 00004

10L 00029 46L 00007 46L 0001210L 00027 46L 00012 46L 0000410L 00032 46L 00009 46L 0000946L 00025 46L 00007 12L 0000446L 00052 12L 00008 12L 0000846L 00029 12L 00012 12L 0000446L 00026 12L 00008 12L 0000712L 00026 12L 00014 26L 0000512L 00043 26L 00007 26L 0000512L 00026 26L 0000612L 0004726L 0002626L 00024

Sample Compost 1 Sample Compost 1 Sample Compost 1Element PBD 154 Element PBD 183 Element PBD 196

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]4L 00010 46L 00002 46L 00011

46L 00003 46L 00024 46L 0000846L 00007 46L 00021 12L 0000246L 00003 46L 00003 12L 0000346L 00004 12L 00003 12L 0000112L 00003 12L 00011 12L 0000212L 00005 12L 0000312L 00031 12L 0000312L 00006

Sample Compost 1 Sample Compost 1 Sample Compost 1Element PBD 197 Element PBD 203 Element PBD 209

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00002 46L 00010 4L 0004146L 00023 12L 00002 4L 0008946L 00022 12L 00003 44L 0041012L 00004 12L 00002 44L 0084012L 00006 12L 00002 44L 0064012L 00003 44L 0040012L 00004 12L 00079

12L 0007312L 0006512L 0009326L 0004926L 00049

Sample Compost 1Element PBD 47

LAB PARM [mgkg]26L 0003826L 00039

Element PBD 99 Element PBD 47 Element PBD 209LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]

4L 00170 10L 00210 4L 010004L 00200 10L 00220 4L 018004L 00170 10L 00210 4L 012004L 00190 46L 00300 4L 0220010L 00280 46L 00280 46L 0210010L 00300 46L 00250 46L 0200010L 00290 46L 00260 64L 0351846L 00340 64L 00059 64L 0363846L 00330 64L 00057 64L 0364546L 00300 64L 00062 64L 0350846L 00310 64L 00060 12L 0220964L 00194 12L 00191 12L 0177164L 00154 12L 00187 12L 0292264L 00185 12L 00190 12L 0164664L 00159 12L 00186 26L 0329712L 00242 26L 00666 26L 0300012L 00223 26L 0033212L 0022112L 0022226L 0024626L 00400

Element PBD 203 Element PBD 197 Element PBD 196LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00022 46L 00027 46L 0002446L 00014 46L 00024 46L 0002264L 00036 12L 00161 64L 0005864L 00058 12L 00060 64L 0006512L 00063 12L 00061 12L 0004812L 00034 12L 00036 12L 0002512L 00038 12L 0003212L 00027 12L 00022

Element PBD 183 Element PBD 154 Element PBD 153LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00049 4L 00020 4L 0002246L 00035 4L 00022 4L 0002446L 00036 4L 00020 4L 0002246L 00034 46L 00025 4L 0002664L 00027 46L 00025 46L 0004064L 00023 46L 00025 46L 0004264L 00024 46L 00023 46L 0003564L 00020 64L 00034 46L 0003812L 00230 64L 00023 64L 0007412L 00032 64L 00017 64L 0004712L 00031 64L 00011 64L 0004612L 00030 12L 00030 64L 0003026L 00007 12L 00021 12L 0006526L 00008 12L 00021 12L 00029

12L 00021 12L 0003226L 00015 12L 0002926L 00019 26L 00039

26L 00040

Element PBD 100LAB PARM [mgkg]

4L 000384L 000414L 000374L 00038

38L 0219038L 0220038L 0208038L 0220010L 0004410L 0005010L 0004310L 0004646L 0005746L 0005946L 0005346L 0005312L 0004312L 0004512L 0004312L 0004326L 0006226L 00057

Sample Soil 3 Sample Soil 3 Sample Soil 3Element PBD 99 Element PBD 47 Element PBD 100

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]10L 00016 10L 00011 10L 0000310L 00019 10L 00010 10L 0000410L 00013 10L 00012 10L 0000410L 00019 46L 00007 10L 0000246L 00025 46L 00022 46L 0000246L 00025 46L 00005 46L 0000646L 00008 46L 00007 46L 0000246L 00011 12L 00010 46L 0000264L 00005 12L 00017 3L 29100064L 00005 12L 00010 3L 32000064L 00006 12L 00009 26L 0000564L 00007 26L 00007 26L 0000512L 00012 26L 0000712L 0001312L 0001312L 0001226L 0000526L 00006

Sample Soil 3 Sample Soil 3 Sample Soil 3Element PBD 153 Element PBD 154 Element PBD 196

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]44L 00050 4L 00010 46L 0000744L 00050 46L 00001 46L 0001146L 00002 46L 00002 46L 0000846L 00003 46L 00001 46L 0001146L 00002 46L 00002 64L 0002646L 00002 64L 00001 64L 0002664L 00001 64L 00001 64L 0002964L 00001 64L 00001 64L 0003464L 00001 64L 00002 12L 0004564L 00002 12L 00003 12L 00032

12L 00002 12L 0002212L 00002 12L 0002112L 00002

Sample Soil 3 Sample Soil 3 Sample Soil 3Element PBD 197 Element PBD 203 Element PBD 209

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00006 46L 00011 4L 0091046L 00013 46L 00017 4L 0150046L 00011 46L 00015 4L 0120046L 00013 46L 00018 4L 0160012L 00090 64L 00013 44L 0337012L 00056 64L 00014 44L 0281012L 00033 64L 00016 44L 0287012L 00032 64L 00015 44L 02540

12L 00055 46L 0230012L 00041 46L 0220012L 00027 46L 0150012L 00026 46L 01900

64L 0438164L 0401664L 0414464L 0449812L 0367112L 0397812L 0409112L 03838

Sample Soil 3 26L 0102Element PBD 183 26L 0131

LAB PARM [mgkg]46L 0000746L 0000846L 0005846L 0000764L 0000264L 0000364L 0000364L 0000312L 0001512L 0001112L 0000712L 00007

European Commission EUR 23003 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on polybrominated diphenylethers Author(s) E Sobiecka H van der Sloot D Barcelo B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 68 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07403-5 Abstract Project HORIZONTAL is interdisciplinary aiming at a harmonisation and horizontal standardisation of test procedures in particular for sludge soils and biowastes In the context of this standardization project a series of draft technical specification were designed upon an extensive desk study fine-tuned after expert consultations and finally validated in international intercomparisons exercise This report summarises the work performed within the validation study of the draft standard for the determination of polybrominated diphenylethers (PBDE) in soils sludge and treated bio-waste using gas-chromatography method with mass selective detection (GC-MS) It further explains the underlying statistical concept for the calculation of reproducibility and repeatability from intercomparisons data In addition all single values results of the statistical evaluation as well as background information on the validation materials used are described and explained

The mission of the JRC is to provide customer-driven scientific and technical support for the conception development implementation and monitoring of EU policies As a service of the European Commission the JRC functions as a reference centre of science and technology for the Union Close to the policy-making process it serves the common interest of the Member States while being independent of special interests whether private or national

LB

-NA

-23003-EN

-C

15

Table 25 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 5

(Pavia)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

039

nq

nq

008

nq

nd

nd

670

671

Table 26 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 5 (Pavia) 033 184 573 225 426 305 206 200 lt 005 381 878

Table 27 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 5 (Pavia) 6939 129 145 224 425 116 6118 255 1789 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 5 (Pavia) 184 62 38 108 55 66 597 110

Table 28 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 5 (Pavia) 006

16

25 Sludge-amended-soil from Barcelona Spain

The sludge-amended soil material from Barcelona sampled upon indication from the Barcelorsquo- Group in Barcelona

Table 29 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 2 (Lleida T) 0015 0183 1138

Table 30 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 2

(Lleida T)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

159

045

nq

048

160

nq

nq

1000

1004

Table 31 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 2 (Lleida T) 059 141 327 536 405 186 184 224 lt 005 318 111

Table 32 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 2 (Lleida T) 4443 1067 1429 253 344 204 4116 780 3396 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 2 (Lleida T) 064 65 26 125 59 17 547 65

Table 33 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 2 (Lleida T) 010

17

26 Sludge amended soil from Essen Germany

The German sludge-amended soil from Essen which was provided as the three sludge materials by LUA NRW did not feature significant concentrations of the PCB congeners 28 52 101 118 153 105 138 156 180 170 but had detectable amounts of some PAHs

Table 34 ndash Analytical screening data on the German sludge-amended soil

Parameter Concentration(ngg)

Naphtalene lt10 Acenaphtylene lt10 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene lt10 Fluoranthene 28 Pyrene 20 Benz(a)anthracene 24 Chrysene 47 Benz(b)fluoranthene 76 Benz(k)fluoranthene 20 Benz(a)pyrene 35 Indeno(123-cd)pyrene 35 Dibenzo(ah)anthracene 10 Benzo(ghi)perylene 26

Table 35 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 4 (Essen) 0011 0302 055

Table 36 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 4

(Essen)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

nq

nq

nq

nq

nq

nq

128

191

203

18

Table 37 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 4 (Essen) 052 545 261 805 320 403 273 273 lt 005 295 781

Table 38 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 4 (Essen) 7947 442 085 06 086 007 2163 189 2019 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 4 (Essen) 045 19 42 87 683 60 462 61

Table 39 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 4 (Essen) 004

27 Long-term sludge exposed soil from Hohenheim-Stuttgart Germany

Similarly an additional sludge exposed soil was sampled at the University of Hohenheim Stuttgart were a test soil was long-term exposed to elevated concentrations of sewage sludge

Table 40 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 1 (Stuttgart) 0045 0263 1765

Table 41 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 1

(Stuttgart)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

230

006

004

004

nq

nd

nd

498

500

19

Table 42 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 1 (Stuttgart) 069 127 361 262 504 183 252 262 lt 005 266 142

Table 43 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 1 (Stuttgart) 7194 1006 133 186 366 088 7874 275 3571 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 1 (Stuttgart) 123 50 47 212 85 69 991 129

Table 44 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 1 (Stuttgart) 177

18

Annex 3

Statistical calculations

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 47)Mandels h statistics(Sludge 1 - PBD 47)

Sample Sludge 1 NUM

Element PBD 47

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00213 0001 3 -021 005 - - 10L - - NUM46L 00273 0002 4 016 021 - - 46L - - NUM64L 00059 0000 4 -116 002 NUM - 64L - - NUM12L 00188 0000 4 -036 002 - - 12L - - NUM26L 00499 0024 2 157 223 Fail - - 26L - - NUM

Totgem 0025 0005 mgkg 1-level 172 (185) NUM (10L46L64L12L26L) -1Totstd= 0016 0010 5-level 157 (162) 5

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 5 Labs rejected (10L46L64L12L26L)

000 050 100 150 200 250

k-values

10L

46L

64L

12L

26L

Mandels k statistics(Sludge 1 - PBD 47)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

10L

46L

64L

12L

26L

Labo

rato

ries

NUM

-200 -100 000 100 200

h-values

10L

46L

64L

12L

26L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 47)

Sludge 1-PBD 47

Unit mgkg

Mandels k statistics(Soil 3 - PBD 47)Mandels h statistics(Soil 3 - PBD 47)

Sample Soil 3 Soil 3 - PBD 47 -- Mean PARM = 0001 [mgkg]

Element PBD 47

General calcparmT1= 134814E-02T2= 142830E-05T3= 13T4= 45T5= 22767E-06

n= variabelp= 4

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean26L 00007 0000 2 -143 001 00007 00000 2 1 00046L 00010 0001 4 010 181 00010 00008 4 3 00010L 00011 0000 3 049 023 00011 00001 3 2 00012L 00012 0000 4 084 081 00012 00004 4 3 000

Totgem 0001 0000 mgkg 1-level 149 (177) 4 00010 () 4 3Totstd= 0000 0000 5-level 142 (159)

RESULTS Mean = 000100 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000050 --gt 5031 r = 00014Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000050 --gt 5031 R = 00014Remarks none

000 050 100 150 200

k-values

26L

46L

10L

12L

Mandels k statistics(Soil 3 - PBD 47)

00 00 00 00 00 00 00 00 00 00 00

Deviation from Mean

26L

46L

10L

12L

Labo

rato

ries

Soil 3 - PBD 47 -- Mean PARM = 0001 [mgkg]

-200 -100 000 100

h-values

26L

46L

10L

12L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 47)

Soil 3-PBD 47

Unit mgkg

Mandels k statistics(Compost 1 - PBD 99)Mandels h statistics(Compost 1 - PBD 99)

Sample Compost 1 Compost 1 - PBD 99 -- Mean PARM = 0003 [mgkg]

Element PBD 99

General calcparmT1= 492124E-02T2= 148747E-04T3= 17T4= 61T5= 93196E-06

n= variabelp= 5

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00020 0000 4 -137 053 00020 00004 4 3 000

26L 00025 0000 2 -058 024 00025 00002 2 1 00010L 00029 0000 3 012 032 00029 00003 3 2 00046L 00033 0001 4 069 161 00033 00013 4 3 00012L 00036 0001 4 114 140 00036 00011 4 3 000

Totgem 0003 0001 mgkg 1-level 172 (185) 5 00029 () 5 4Totstd= 0001 0001 5-level 157 (162)

RESULTS Mean = 000286 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000088 --gt 3086 r = 00025Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000101 --gt 3525 R = 00028Remarks none

000 050 100 150 200

k-values

4L

26L

10L

46L

12L

Mandels k statistics(Compost 1 - PBD 99)

00 00 00 00 00 00 00 00 00 00

Deviation from Mean

4L

26L

10L

46L

12L

Labo

rato

ries

Compost 1 - PBD 99 -- Mean PARM = 0003 [mgkg]

-200 -100 000 100 200

h-values

4L

26L

10L

46L

12L

Labo

rato

ries

Mandels h statistics(Compost 1 - PBD 99)

Compost 1-PBD 99

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 99)Mandels h statistics(Sludge 1 - PBD 99)

Sample Sludge 1 Sludge 1 - PBD 99 -- Mean PARM = 0024 [mgkg]

Element PBD 99

General calcparmT1= 448050E-01T2= 112113E-02T3= 19T4= 73T5= 32972E-05

n= variabelp= 5

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean64L 00173 0002 4 -118 041 Fail 00173 00019 4 3 -0014L 00183 0002 4 -104 032 00183 00015 4 3 -001

12L 00227 0001 4 -038 022 00227 00010 4 3 00010L 00290 0001 3 055 021 00290 00010 3 2 00146L 00320 0002 4 100 039 00320 00018 4 3 00126L 00323 0011 2 105 234 - - 26L - - 001

Totgem 0025 0003 mgkg 1-level 187 (177) 5 00239 (26L) 5 4Totstd= 0007 0004 5-level 166 (154) 1

RESULTS Mean = 002385 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000153 --gt 643 r = 00043Between lab variance S2L = 000004Reproducibility var S2R = 000004Reproducibility std SR = 000666 --gt 2791 R = 00186Remarks 1 Lab rejected (26L)

000 050 100 150 200 250

k-values

64L

4L

12L

10L

46L

26L

Mandels k statistics(Sludge 1 - PBD 99)

00 00 00 00 00 00 00 00 00 00

Deviation from Mean

64L

4L

12L

10L

46L

26L

Labo

rato

ries

Sludge 1 - PBD 99 -- Mean PARM = 0024 [mgkg]

-200 -100 000 100 200

h-values

64L

4L

12L

10L

46L

26L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 99)

Sludge 1-PBD 99

Unit mgkg

Mandels k statistics(Soil 3 - PBD 99)Mandels h statistics(Soil 3 - PBD 99)

Sample Soil 3 NUM

Element PBD 99

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00017 0000 4 091 068 - - 10L - - NUM46L 00017 0001 4 100 211 - - 46L - - NUM64L 00005 0000 4 -106 023 NUM - 64L - - NUM12L 00012 0000 4 015 014 - - 12L - - NUM26L 00006 0000 2 -101 012 - - 26L - - NUM

Totgem 0001 0000 mgkg 1-level 172 (173) NUM (10L46L64L12L26L) -1Totstd= 0001 0000 5-level 157 (153) 5

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 5 Labs rejected (10L46L64L12L26L)

000 050 100 150 200 250

k-values

10L

46L

64L

12L

26L

Mandels k statistics(Soil 3 - PBD 99)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

10L

46L

64L

12L

26L

Labo

rato

ries

NUM

-200 -100 000 100 200

h-values

10L

46L

64L

12L

26L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 99)

Soil 3-PBD 99

Unit mgkg

Mandels k statistics(Compost 1 - PBD 100)Mandels h statistics(Compost 1 - PBD 100)

Sample Compost 1 Compost 1 - PBD 100 -- Mean PARM = 0001 [mgkg]

Element PBD 100

General calcparmT1= 124272E-02T2= 113129E-05T3= 14T4= 52T5= 46584E-07

n= variabelp= 4

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean26L 00006 0000 2 -131 037 Fail 00006 00001 2 1 00010L 00009 0000 4 003 083 00009 00002 4 3 00046L 00009 0000 4 016 115 00009 00002 4 3 00012L 00011 0000 4 112 136 Fail 00011 00003 4 3 000

Totgem 0001 0000 mgkg 1-level 149 (167) 4 00009 () 4 3Totstd= 0000 0000 5-level 142 (15)

RESULTS Mean = 000085 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000022 --gt 2531 r = 00006Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000025 --gt 2882 R = 00007Remarks none

000 050 100 150

k-values

26L

10L

46L

12L

Mandels k statistics(Compost 1 - PBD 100)

00 00 00 00 00 00 00 00 00 00 00

Deviation from Mean

26L

10L

46L

12L

Labo

rato

ries

Compost 1 - PBD 100 -- Mean PARM = 0001 [mgkg]

-200 -100 000 100 200

h-values

26L

10L

46L

12L

Labo

rato

ries

Mandels h statistics(Compost 1 - PBD 100)

Compost 1-PBD 100

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 100)Mandels h statistics(Sludge 1 - PBD 100)

Sample Sludge 1 Sludge 1 - PBD 100 -- Mean PARM = 0005 [mgkg]

Element PBD 100

General calcparmT1= 852065E-02T2= 412762E-04T3= 18T4= 68T5= 78914E-07

n= variabelp= 5

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00039 0000 4 -042 007 Fail 00039 00002 4 3 000

12L 00044 0000 4 -041 005 Fail 00044 00001 4 3 00010L 00046 0000 4 -041 013 Fail 00046 00003 4 3 00046L 00056 0000 4 -040 012 Fail 00056 00003 4 3 00026L 00059 0000 2 -040 013 Fail 00059 00003 2 1 00038L 02168 0006 4 204 244 Fail - - 38L - - 021

Totgem 0040 0001 mgkg 1-level 187 (177) 5 00049 (38L) 5 4Totstd= 0087 0002 5-level 166 (154) 1

RESULTS Mean = 000486 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000025 --gt 507 r = 00007Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000084 --gt 1731 R = 00024Remarks 1 Lab rejected (38L)

000 050 100 150 200 250

k-values

4L

12L

10L

46L

26L

38L

Mandels k statistics(Sludge 1 - PBD 100)

-01 00 01 01 02 02 03

Deviation from Mean

4L

12L

10L

46L

26L

38L

Labo

rato

ries

Sludge 1 - PBD 100 -- Mean PARM = 0005 [mgkg]

-100 000 100 200 300

h-values

4L

12L

10L

46L

26L

38L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 100)

Sludge 1-PBD 100

Unit mgkg

Mandels k statistics(Soil 3 - PBD 100)Mandels h statistics(Soil 3 - PBD 100)

Sample Soil 3 NUM

Element PBD 100

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00003 0000 4 -050 000 Fail - - 10L - - NUM46L 00003 0000 4 -050 000 Fail NUM - 46L - - NUM3L 305500 2051 2 150 200 Fail - - 3L - - NUM

26L 00005 0000 2 -050 000 Fail - - 26L - - NUM

Totgem 7638 0513 mgkg 1-level 149 (177) NUM (10L46L3L26L) -1Totstd= 15275 1025 5-level 142 (159) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (10L46L3L26L)

000 050 100 150 200

k-values

10L

46L

3L

26L

Mandels k statistics(Soil 3 - PBD 100)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

10L

46L

3L

26L

Labo

rato

ries

NUM

-100 000 100 200

h-values

10L

46L

3L

26L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 100)

Soil 3-PBD 100

Unit mgkg

Mandels k statistics(Compost 1 - PBD 153)Mandels h statistics(Compost 1 - PBD 153)

Sample Compost 1 NUM

Element PBD 153

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean44L 00053 0001 3 150 157 Fail - - 44L - - NUM46L 00007 0000 4 -044 111 Fail - - 46L - - NUM12L 00005 0000 4 -051 055 Fail - - 12L - - NUM26L 00005 0000 2 -054 001 Fail NUM - 26L - - NUM

Totgem 0002 0000 mgkg 1-level 149 (177) NUM (44L46L12L26L) -1Totstd= 0002 0000 5-level 142 (159) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (44L46L12L26L)

000 050 100 150 200

k-values

44L

46L

12L

26L

Mandels k statistics(Compost 1 - PBD 153)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

44L

46L

12L

26L

Labo

rato

ries

NUM

-100 000 100 200

h-values

44L

46L

12L

26L

Labo

rato

ries

Mandels h statistics(Compost 1 - PBD 153)

Compost 1-PBD 153

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 153)Mandels h statistics(Sludge 1 - PBD 153)

Sample Sludge 1 Sludge 1 - PBD 153 -- Mean PARM = 0004 [mgkg]

Element PBD 153

General calcparmT1= 676738E-02T2= 267609E-04T3= 18T4= 68T5= 19626E-05

n= variabelp= 5

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00024 0000 4 -157 017 00024 00002 4 3 000

12L 00038 0002 4 006 154 00038 00018 4 3 00046L 00039 0000 4 011 026 00039 00003 4 3 00026L 00039 0000 2 018 004 00039 00000 2 1 00064L 00049 0002 4 122 159 00049 00018 4 3 000

Totgem 0004 0001 mgkg 1-level 172 (173) 5 00038 () 5 4Totstd= 0001 0001 5-level 157 (153)

RESULTS Mean = 000378 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000123 --gt 3252 r = 00034Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000142 --gt 3754 R = 00040Remarks none

000 050 100 150 200

k-values

4L

12L

46L

26L

64L

Mandels k statistics(Sludge 1 - PBD 153)

00 00 00 00 00 00 00

Deviation from Mean

4L

12L

46L

26L

64L

Labo

rato

ries

Sludge 1 - PBD 153 -- Mean PARM = 0004 [mgkg]

-200 -100 000 100 200

h-values

4L

12L

46L

26L

64L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 153)

Sludge 1-PBD 153

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 154)Mandels h statistics(Sludge 1 - PBD 154)

Sample Sludge 1 NA

Element PBD 154

General calcparmT1= NAT2= NAT3=T4=T5=

n= variabelp=

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00021 0000 3 -100 021 NA - 4L - - NA

46L 00025 0000 4 115 018 NA - 46L - - NA64L 00021 0001 4 -066 179 - - 64L - - NA12L 00023 0000 4 050 085 - - 12L - - NA

Totgem 0002 0000 mgkg 1-level 149 (167) NA (4L46L64L12L) -1Totstd= 0000 0000 5-level 142 (15) 4

RESULTS Mean = NA mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NAReproducibility var S2R = NAReproducibility std SR = NA --gt NA R = NARemarks 4 Labs rejected (4L46L64L12L)

000 050 100 150 200

k-values

4L

46L

64L

12L

Mandels k statistics(Sludge 1 - PBD 154)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

4L

46L

64L

12L

Labo

rato

ries

NA

-100 000 100 200

h-values

4L

46L

64L

12L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 154)

Sludge 1-PBD 154

Unit mgkg

Mandels k statistics(Soil 3 - PBD 154)Mandels h statistics(Soil 3 - PBD 154)

Sample Soil 3 NUM

Element PBD 154

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

4L 00010 - 1 150 Fail - - 4L - - NUM46L 00001 0000 4 -053 096 Fail - - 46L - - NUM64L 00001 0000 4 -056 105 Fail NUM - 64L - - NUM12L 00002 0000 4 -040 099 Fail - - 12L - - NUM

Totgem 000037 0000 mgkg 1-level 149 (164) NUM (4L46L64L12L) -1Totstd= 000042 0000 5-level 142 (153) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (4L46L64L12L)

000 050 100 150

k-values

4L

46L

64L

12L

Mandels k statistics(Soil 3 - PBD 154)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

4L

46L

64L

12L

Labo

rato

ries

NUM

-100 000 100 200

h-values

4L

46L

64L

12L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 154)

Soil 3-PBD 154

Unit mgkg

Mandels k statistics(Compost 1 - PBD 209)Mandels h statistics(Compost 1 - PBD 209)

Sample Compost 1 NUM

Element PBD 209

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00065 0003 2 -049 032 - - 4L - - NUM

44L 00573 0021 4 150 197 Fail - - 44L - - NUM12L 00078 0001 4 -045 011 - - 12L - - NUM26L 00049 0000 2 -056 000 NUM - 26L - - NUM

Totgem 0019 0006 mgkg 1-level 149 (177) NUM (4L44L12L26L) -1Totstd= 0025 0010 5-level 142 (159) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (4L44L12L26L)

000 050 100 150 200

k-values

4L

44L

12L

26L

Mandels k statistics(Compost 1 - PBD 209)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

4L

44L

12L

26L

Labo

rato

ries

NUM

-100 000 100 200

h-values

4L

44L

12L

26L

Labo

rato

ries

Mandels h statistics(Compost 1 - PBD 209)

Compost 1-PBD 209

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 209)Mandels h statistics(Sludge 1 - PBD 209)

Sample Sludge 1 Sludge 1 - PBD 209 -- Mean PARM = 0249 [mgkg]

Element PBD 209

General calcparmT1= 394542E+00T2= 107296E+00T3= 16T4= 56T5= 19723E-02

n= variabelp= 5

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 01550 0055 4 -112 148 Fail 01550 00551 4 3 -009

46L 02050 0007 2 -053 019 02050 00071 2 1 -00412L 02137 0058 4 -042 155 02137 00576 4 3 -00426L 03149 0021 2 078 057 Fail 03149 00210 2 1 00764L 03577 0007 4 129 020 Fail 03577 00074 4 3 011

Totgem 0249 0030 mgkg 1-level 172 (185) 5 02493 () 5 4Totstd= 0084 0025 5-level 157 (162)

RESULTS Mean = 024926 mgkg

Repeatability variance S2r = 000179Repeatability std Sr = 004234 --gt 1699 r = 01186Between lab variance S2L = 000743Reproducibility var S2R = 000922Reproducibility std SR = 009604 --gt 3853 R = 02689Remarks none

000 050 100 150 200

k-values

4L

46L

12L

26L

64L

Mandels k statistics(Sludge 1 - PBD 209)

-01 -01 00 01 01 02

Deviation from Mean

4L

46L

12L

26L

64L

Labo

rato

ries

Sludge 1 - PBD 209 -- Mean PARM = 0249 [mgkg]

-200 -100 000 100 200

h-values

4L

46L

12L

26L

64L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 209)

Sludge 1-PBD 209

Unit mgkg

Mandels k statistics(Soil 3 - PBD 209)Mandels h statistics(Soil 3 - PBD 209)

Sample Soil 3 Soil 3 - PBD 209 -- Mean PARM = 0258 [mgkg]

Element PBD 209

General calcparmT1= 596398E+00T2= 191917E+00T3= 22T4= 84T5= 13249E-02

n= variabelp= 6

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean26L 01162 0021 2 -108 074 Fail 01162 00207 2 1 -0144L 01303 0031 4 -097 111 Fail 01303 00312 4 3 -013

46L 01975 0036 4 -046 128 Fail 01975 00359 4 3 -00644L 02898 0035 4 024 124 Fail 02898 00346 4 3 00312L 03895 0018 4 100 065 Fail 03895 00181 4 3 01364L 04260 0022 4 127 078 Fail 04260 00219 4 3 017

Totgem 0258 0027 mgkg 1-level 187 (177) 6 02582 () 6 5Totstd= 0132 0008 5-level 166 (154)

RESULTS Mean = 025818 mgkg

Repeatability variance S2r = 000083Repeatability std Sr = 002878 --gt 1115 r = 00806Between lab variance S2L = 001640Reproducibility var S2R = 001723Reproducibility std SR = 013127 --gt 5084 R = 03676Remarks none

000 050 100 150

k-values

26L

4L

46L

44L

12L

64L

Mandels k statistics(Soil 3 - PBD 209)

-02 -01 -01 00 01 01 02 02

Deviation from Mean

26L

4L

46L

44L

12L

64L

Labo

rato

ries

Soil 3 - PBD 209 -- Mean PARM = 0258 [mgkg]

-200 -100 000 100 200

h-values

26L

4L

46L

44L

12L

64L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 209)

Soil 3-PBD 209

Unit mgkg

Mandels k statistics(Compost 1 - Sum PBD)Mandels h statistics(Compost 1 - Sum PBD)

Sample Compost 1 Compost 1 - Sum PBD -- Mean PARM = 0009 [mgkg]

Element Sum PBD

General calcparmT1= 154064E-01T2= 169065E-03T3= 18T4= 68T5= 11354E-04

n= variabelp= 5

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00031 0002 4 -067 016 00031 00016 4 3 -0014L 00055 0005 4 -056 048 00055 00047 4 3 000

46L 00085 0003 4 -042 031 00085 00030 4 3 00026L 00123 0000 2 -024 003 00123 00002 2 1 00012L 00154 0002 4 -011 021 00154 00021 4 3 00144L 00613 0023 4 200 237 Fail - - 44L - - 005

Totgem 0018 0006 mgkg 1-level 187 (177) 5 00089 (44L) 5 4Totstd= 0022 0009 5-level 166 (154) 1

RESULTS Mean = 000893 mgkg

Repeatability variance S2r = 000001Repeatability std Sr = 000296 --gt 3308 r = 00083Between lab variance S2L = 000002Reproducibility var S2R = 000003Reproducibility std SR = 000570 --gt 6374 R = 00159Remarks 1 Lab rejected (44L)

000 050 100 150 200 250

k-values

10L

4L

46L

26L

12L

44L

Mandels k statistics(Compost 1 - Sum PBD)

00 00 00 00 00 00 01 01

Deviation from Mean

10L

4L

46L

26L

12L

44L

Labo

rato

ries

Compost 1 - Sum PBD -- Mean PARM = 0009 [mgkg]

-100 000 100 200

h-values

10L

4L

46L

26L

12L

44L

Labo

rato

ries

Mandels h statistics(Compost 1 - Sum PBD)

Compost 1-Sum PBD

Unit mgkg

Mandels k statistics(Sludge 1 - Sum PBD)Mandels h statistics(Sludge 1 - Sum PBD)

Sample Sludge 1 Sludge 1 - Sum PBD -- Mean PARM = 0256 [mgkg]

Element Sum PBD

General calcparmT1= 531806E+00T2= 162188E+00T3= 22T4= 84T5= 25223E-02

n= variabelp= 6

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00423 0025 4 -156 044 Fail 00423 00252 4 3 -02146L 01808 0118 4 -049 205 - - 46L - - -0074L 01810 0056 4 -049 097 01810 00558 4 3 -007

38L 02168 0006 4 -022 010 02168 00059 4 3 -00412L 02890 0065 4 034 113 02890 00647 4 3 00364L 03958 0008 4 116 014 Fail 03958 00079 4 3 01426L 04094 0034 2 126 059 Fail 04094 00337 2 1 015

Totgem 0245 0044 mgkg 1-level 198 (179) 6 02557 (46L) 6 5Totstd= 0130 0039 5-level 171 (155) 1

RESULTS Mean = 025570 mgkg

Repeatability variance S2r = 000158Repeatability std Sr = 003970 --gt 1553 r = 01112Between lab variance S2L = 001807Reproducibility var S2R = 001964Reproducibility std SR = 014015 --gt 5481 R = 03924Remarks 1 Lab rejected (46L)

000 050 100 150 200 250

k-values

10L

46L

4L

38L

12L

64L

26L

Mandels k statistics(Sludge 1 - Sum PBD)

-03 -02 -02 -01 -01 00 01 01 02 02

Deviation from Mean

10L

46L

4L

38L

12L

64L

26L

Labo

rato

ries

Sludge 1 - Sum PBD -- Mean PARM = 0256 [mgkg]

-200 -100 000 100 200

h-values

10L

46L

4L

38L

12L

64L

26L

Labo

rato

ries

Mandels h statistics(Sludge 1 - Sum PBD)

Sludge 1-Sum PBD

Unit mgkg

Mandels k statistics(Soil 3 - Sum PBD)Mandels h statistics(Soil 3 - Sum PBD)

Sample Soil 3 Soil 3 - Sum PBD -- Mean PARM = 0227 [mgkg]

Element Sum PBD

General calcparmT1= 610980E+00T2= 200876E+00T3= 26T4= 100T5= 13106E-02

n= variabelp= 7

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00028 0001 4 -037 000 Fail 00028 00005 4 3 -02226L 01179 0021 2 -036 003 Fail 01179 00208 2 1 -0114L 01305 0031 4 -036 004 Fail 01305 00308 4 3 -010

46L 02065 0035 4 -036 005 Fail 02065 00350 4 3 -00244L 02923 0037 4 -035 005 Fail 02923 00365 4 3 00712L 04051 0015 4 -034 002 Fail 04051 00149 4 3 01864L 04314 0022 4 -033 003 Fail 04314 00223 4 3 0203L 305500 2051 2 247 283 Fail - - 3L - - 3032

Totgem 4017 0276 mgkg 1-level 206 (181) 7 02266 (3L) 7 6Totstd= 10722 0717 5-level 175 (156) 1

RESULTS Mean = 022663 mgkg

Repeatability variance S2r = 000069Repeatability std Sr = 002626 --gt 1159 r = 00735Between lab variance S2L = 002568Reproducibility var S2R = 002637Reproducibility std SR = 016238 --gt 7165 R = 04547Remarks 1 Lab rejected (3L)

000 050 100 150 200 250 300

k-values

10L

26L

4L

46L

44L

12L

64L

3L

Mandels k statistics(Soil 3 - Sum PBD)

-50 00 50 100 150 200 250 300 350

Deviation from Mean

10L

26L

4L

46L

44L

12L

64L

3L

Labo

rato

ries

Soil 3 - Sum PBD -- Mean PARM = 0227 [mgkg]

-100 000 100 200 300

h-values

10L

26L

4L

46L

44L

12L

64L

3L

Labo

rato

ries

Mandels h statistics(Soil 3 - Sum PBD)

Soil 3-Sum PBD

19

Annex 4

Raw data submitted

Sample Compost1 Sample Compost 1 Sample Compost 1Element PBD 99 Element PBD 100 Element PBD 153

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]4L 00021 10L 00008 44L 000504L 00024 10L 00008 44L 000604L 00014 10L 00007 44L 000504L 00020 10L 00011 46L 00004

10L 00029 46L 00007 46L 0001210L 00027 46L 00012 46L 0000410L 00032 46L 00009 46L 0000946L 00025 46L 00007 12L 0000446L 00052 12L 00008 12L 0000846L 00029 12L 00012 12L 0000446L 00026 12L 00008 12L 0000712L 00026 12L 00014 26L 0000512L 00043 26L 00007 26L 0000512L 00026 26L 0000612L 0004726L 0002626L 00024

Sample Compost 1 Sample Compost 1 Sample Compost 1Element PBD 154 Element PBD 183 Element PBD 196

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]4L 00010 46L 00002 46L 00011

46L 00003 46L 00024 46L 0000846L 00007 46L 00021 12L 0000246L 00003 46L 00003 12L 0000346L 00004 12L 00003 12L 0000112L 00003 12L 00011 12L 0000212L 00005 12L 0000312L 00031 12L 0000312L 00006

Sample Compost 1 Sample Compost 1 Sample Compost 1Element PBD 197 Element PBD 203 Element PBD 209

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00002 46L 00010 4L 0004146L 00023 12L 00002 4L 0008946L 00022 12L 00003 44L 0041012L 00004 12L 00002 44L 0084012L 00006 12L 00002 44L 0064012L 00003 44L 0040012L 00004 12L 00079

12L 0007312L 0006512L 0009326L 0004926L 00049

Sample Compost 1Element PBD 47

LAB PARM [mgkg]26L 0003826L 00039

Element PBD 99 Element PBD 47 Element PBD 209LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]

4L 00170 10L 00210 4L 010004L 00200 10L 00220 4L 018004L 00170 10L 00210 4L 012004L 00190 46L 00300 4L 0220010L 00280 46L 00280 46L 0210010L 00300 46L 00250 46L 0200010L 00290 46L 00260 64L 0351846L 00340 64L 00059 64L 0363846L 00330 64L 00057 64L 0364546L 00300 64L 00062 64L 0350846L 00310 64L 00060 12L 0220964L 00194 12L 00191 12L 0177164L 00154 12L 00187 12L 0292264L 00185 12L 00190 12L 0164664L 00159 12L 00186 26L 0329712L 00242 26L 00666 26L 0300012L 00223 26L 0033212L 0022112L 0022226L 0024626L 00400

Element PBD 203 Element PBD 197 Element PBD 196LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00022 46L 00027 46L 0002446L 00014 46L 00024 46L 0002264L 00036 12L 00161 64L 0005864L 00058 12L 00060 64L 0006512L 00063 12L 00061 12L 0004812L 00034 12L 00036 12L 0002512L 00038 12L 0003212L 00027 12L 00022

Element PBD 183 Element PBD 154 Element PBD 153LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00049 4L 00020 4L 0002246L 00035 4L 00022 4L 0002446L 00036 4L 00020 4L 0002246L 00034 46L 00025 4L 0002664L 00027 46L 00025 46L 0004064L 00023 46L 00025 46L 0004264L 00024 46L 00023 46L 0003564L 00020 64L 00034 46L 0003812L 00230 64L 00023 64L 0007412L 00032 64L 00017 64L 0004712L 00031 64L 00011 64L 0004612L 00030 12L 00030 64L 0003026L 00007 12L 00021 12L 0006526L 00008 12L 00021 12L 00029

12L 00021 12L 0003226L 00015 12L 0002926L 00019 26L 00039

26L 00040

Element PBD 100LAB PARM [mgkg]

4L 000384L 000414L 000374L 00038

38L 0219038L 0220038L 0208038L 0220010L 0004410L 0005010L 0004310L 0004646L 0005746L 0005946L 0005346L 0005312L 0004312L 0004512L 0004312L 0004326L 0006226L 00057

Sample Soil 3 Sample Soil 3 Sample Soil 3Element PBD 99 Element PBD 47 Element PBD 100

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]10L 00016 10L 00011 10L 0000310L 00019 10L 00010 10L 0000410L 00013 10L 00012 10L 0000410L 00019 46L 00007 10L 0000246L 00025 46L 00022 46L 0000246L 00025 46L 00005 46L 0000646L 00008 46L 00007 46L 0000246L 00011 12L 00010 46L 0000264L 00005 12L 00017 3L 29100064L 00005 12L 00010 3L 32000064L 00006 12L 00009 26L 0000564L 00007 26L 00007 26L 0000512L 00012 26L 0000712L 0001312L 0001312L 0001226L 0000526L 00006

Sample Soil 3 Sample Soil 3 Sample Soil 3Element PBD 153 Element PBD 154 Element PBD 196

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]44L 00050 4L 00010 46L 0000744L 00050 46L 00001 46L 0001146L 00002 46L 00002 46L 0000846L 00003 46L 00001 46L 0001146L 00002 46L 00002 64L 0002646L 00002 64L 00001 64L 0002664L 00001 64L 00001 64L 0002964L 00001 64L 00001 64L 0003464L 00001 64L 00002 12L 0004564L 00002 12L 00003 12L 00032

12L 00002 12L 0002212L 00002 12L 0002112L 00002

Sample Soil 3 Sample Soil 3 Sample Soil 3Element PBD 197 Element PBD 203 Element PBD 209

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00006 46L 00011 4L 0091046L 00013 46L 00017 4L 0150046L 00011 46L 00015 4L 0120046L 00013 46L 00018 4L 0160012L 00090 64L 00013 44L 0337012L 00056 64L 00014 44L 0281012L 00033 64L 00016 44L 0287012L 00032 64L 00015 44L 02540

12L 00055 46L 0230012L 00041 46L 0220012L 00027 46L 0150012L 00026 46L 01900

64L 0438164L 0401664L 0414464L 0449812L 0367112L 0397812L 0409112L 03838

Sample Soil 3 26L 0102Element PBD 183 26L 0131

LAB PARM [mgkg]46L 0000746L 0000846L 0005846L 0000764L 0000264L 0000364L 0000364L 0000312L 0001512L 0001112L 0000712L 00007

European Commission EUR 23003 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on polybrominated diphenylethers Author(s) E Sobiecka H van der Sloot D Barcelo B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 68 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07403-5 Abstract Project HORIZONTAL is interdisciplinary aiming at a harmonisation and horizontal standardisation of test procedures in particular for sludge soils and biowastes In the context of this standardization project a series of draft technical specification were designed upon an extensive desk study fine-tuned after expert consultations and finally validated in international intercomparisons exercise This report summarises the work performed within the validation study of the draft standard for the determination of polybrominated diphenylethers (PBDE) in soils sludge and treated bio-waste using gas-chromatography method with mass selective detection (GC-MS) It further explains the underlying statistical concept for the calculation of reproducibility and repeatability from intercomparisons data In addition all single values results of the statistical evaluation as well as background information on the validation materials used are described and explained

The mission of the JRC is to provide customer-driven scientific and technical support for the conception development implementation and monitoring of EU policies As a service of the European Commission the JRC functions as a reference centre of science and technology for the Union Close to the policy-making process it serves the common interest of the Member States while being independent of special interests whether private or national

LB

-NA

-23003-EN

-C

16

25 Sludge-amended-soil from Barcelona Spain

The sludge-amended soil material from Barcelona sampled upon indication from the Barcelorsquo- Group in Barcelona

Table 29 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 2 (Lleida T) 0015 0183 1138

Table 30 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 2

(Lleida T)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

159

045

nq

048

160

nq

nq

1000

1004

Table 31 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 2 (Lleida T) 059 141 327 536 405 186 184 224 lt 005 318 111

Table 32 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 2 (Lleida T) 4443 1067 1429 253 344 204 4116 780 3396 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 2 (Lleida T) 064 65 26 125 59 17 547 65

Table 33 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 2 (Lleida T) 010

17

26 Sludge amended soil from Essen Germany

The German sludge-amended soil from Essen which was provided as the three sludge materials by LUA NRW did not feature significant concentrations of the PCB congeners 28 52 101 118 153 105 138 156 180 170 but had detectable amounts of some PAHs

Table 34 ndash Analytical screening data on the German sludge-amended soil

Parameter Concentration(ngg)

Naphtalene lt10 Acenaphtylene lt10 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene lt10 Fluoranthene 28 Pyrene 20 Benz(a)anthracene 24 Chrysene 47 Benz(b)fluoranthene 76 Benz(k)fluoranthene 20 Benz(a)pyrene 35 Indeno(123-cd)pyrene 35 Dibenzo(ah)anthracene 10 Benzo(ghi)perylene 26

Table 35 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 4 (Essen) 0011 0302 055

Table 36 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 4

(Essen)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

nq

nq

nq

nq

nq

nq

128

191

203

18

Table 37 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 4 (Essen) 052 545 261 805 320 403 273 273 lt 005 295 781

Table 38 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 4 (Essen) 7947 442 085 06 086 007 2163 189 2019 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 4 (Essen) 045 19 42 87 683 60 462 61

Table 39 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 4 (Essen) 004

27 Long-term sludge exposed soil from Hohenheim-Stuttgart Germany

Similarly an additional sludge exposed soil was sampled at the University of Hohenheim Stuttgart were a test soil was long-term exposed to elevated concentrations of sewage sludge

Table 40 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 1 (Stuttgart) 0045 0263 1765

Table 41 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 1

(Stuttgart)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

230

006

004

004

nq

nd

nd

498

500

19

Table 42 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 1 (Stuttgart) 069 127 361 262 504 183 252 262 lt 005 266 142

Table 43 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 1 (Stuttgart) 7194 1006 133 186 366 088 7874 275 3571 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 1 (Stuttgart) 123 50 47 212 85 69 991 129

Table 44 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 1 (Stuttgart) 177

18

Annex 3

Statistical calculations

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 47)Mandels h statistics(Sludge 1 - PBD 47)

Sample Sludge 1 NUM

Element PBD 47

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00213 0001 3 -021 005 - - 10L - - NUM46L 00273 0002 4 016 021 - - 46L - - NUM64L 00059 0000 4 -116 002 NUM - 64L - - NUM12L 00188 0000 4 -036 002 - - 12L - - NUM26L 00499 0024 2 157 223 Fail - - 26L - - NUM

Totgem 0025 0005 mgkg 1-level 172 (185) NUM (10L46L64L12L26L) -1Totstd= 0016 0010 5-level 157 (162) 5

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 5 Labs rejected (10L46L64L12L26L)

000 050 100 150 200 250

k-values

10L

46L

64L

12L

26L

Mandels k statistics(Sludge 1 - PBD 47)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

10L

46L

64L

12L

26L

Labo

rato

ries

NUM

-200 -100 000 100 200

h-values

10L

46L

64L

12L

26L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 47)

Sludge 1-PBD 47

Unit mgkg

Mandels k statistics(Soil 3 - PBD 47)Mandels h statistics(Soil 3 - PBD 47)

Sample Soil 3 Soil 3 - PBD 47 -- Mean PARM = 0001 [mgkg]

Element PBD 47

General calcparmT1= 134814E-02T2= 142830E-05T3= 13T4= 45T5= 22767E-06

n= variabelp= 4

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean26L 00007 0000 2 -143 001 00007 00000 2 1 00046L 00010 0001 4 010 181 00010 00008 4 3 00010L 00011 0000 3 049 023 00011 00001 3 2 00012L 00012 0000 4 084 081 00012 00004 4 3 000

Totgem 0001 0000 mgkg 1-level 149 (177) 4 00010 () 4 3Totstd= 0000 0000 5-level 142 (159)

RESULTS Mean = 000100 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000050 --gt 5031 r = 00014Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000050 --gt 5031 R = 00014Remarks none

000 050 100 150 200

k-values

26L

46L

10L

12L

Mandels k statistics(Soil 3 - PBD 47)

00 00 00 00 00 00 00 00 00 00 00

Deviation from Mean

26L

46L

10L

12L

Labo

rato

ries

Soil 3 - PBD 47 -- Mean PARM = 0001 [mgkg]

-200 -100 000 100

h-values

26L

46L

10L

12L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 47)

Soil 3-PBD 47

Unit mgkg

Mandels k statistics(Compost 1 - PBD 99)Mandels h statistics(Compost 1 - PBD 99)

Sample Compost 1 Compost 1 - PBD 99 -- Mean PARM = 0003 [mgkg]

Element PBD 99

General calcparmT1= 492124E-02T2= 148747E-04T3= 17T4= 61T5= 93196E-06

n= variabelp= 5

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00020 0000 4 -137 053 00020 00004 4 3 000

26L 00025 0000 2 -058 024 00025 00002 2 1 00010L 00029 0000 3 012 032 00029 00003 3 2 00046L 00033 0001 4 069 161 00033 00013 4 3 00012L 00036 0001 4 114 140 00036 00011 4 3 000

Totgem 0003 0001 mgkg 1-level 172 (185) 5 00029 () 5 4Totstd= 0001 0001 5-level 157 (162)

RESULTS Mean = 000286 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000088 --gt 3086 r = 00025Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000101 --gt 3525 R = 00028Remarks none

000 050 100 150 200

k-values

4L

26L

10L

46L

12L

Mandels k statistics(Compost 1 - PBD 99)

00 00 00 00 00 00 00 00 00 00

Deviation from Mean

4L

26L

10L

46L

12L

Labo

rato

ries

Compost 1 - PBD 99 -- Mean PARM = 0003 [mgkg]

-200 -100 000 100 200

h-values

4L

26L

10L

46L

12L

Labo

rato

ries

Mandels h statistics(Compost 1 - PBD 99)

Compost 1-PBD 99

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 99)Mandels h statistics(Sludge 1 - PBD 99)

Sample Sludge 1 Sludge 1 - PBD 99 -- Mean PARM = 0024 [mgkg]

Element PBD 99

General calcparmT1= 448050E-01T2= 112113E-02T3= 19T4= 73T5= 32972E-05

n= variabelp= 5

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean64L 00173 0002 4 -118 041 Fail 00173 00019 4 3 -0014L 00183 0002 4 -104 032 00183 00015 4 3 -001

12L 00227 0001 4 -038 022 00227 00010 4 3 00010L 00290 0001 3 055 021 00290 00010 3 2 00146L 00320 0002 4 100 039 00320 00018 4 3 00126L 00323 0011 2 105 234 - - 26L - - 001

Totgem 0025 0003 mgkg 1-level 187 (177) 5 00239 (26L) 5 4Totstd= 0007 0004 5-level 166 (154) 1

RESULTS Mean = 002385 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000153 --gt 643 r = 00043Between lab variance S2L = 000004Reproducibility var S2R = 000004Reproducibility std SR = 000666 --gt 2791 R = 00186Remarks 1 Lab rejected (26L)

000 050 100 150 200 250

k-values

64L

4L

12L

10L

46L

26L

Mandels k statistics(Sludge 1 - PBD 99)

00 00 00 00 00 00 00 00 00 00

Deviation from Mean

64L

4L

12L

10L

46L

26L

Labo

rato

ries

Sludge 1 - PBD 99 -- Mean PARM = 0024 [mgkg]

-200 -100 000 100 200

h-values

64L

4L

12L

10L

46L

26L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 99)

Sludge 1-PBD 99

Unit mgkg

Mandels k statistics(Soil 3 - PBD 99)Mandels h statistics(Soil 3 - PBD 99)

Sample Soil 3 NUM

Element PBD 99

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00017 0000 4 091 068 - - 10L - - NUM46L 00017 0001 4 100 211 - - 46L - - NUM64L 00005 0000 4 -106 023 NUM - 64L - - NUM12L 00012 0000 4 015 014 - - 12L - - NUM26L 00006 0000 2 -101 012 - - 26L - - NUM

Totgem 0001 0000 mgkg 1-level 172 (173) NUM (10L46L64L12L26L) -1Totstd= 0001 0000 5-level 157 (153) 5

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 5 Labs rejected (10L46L64L12L26L)

000 050 100 150 200 250

k-values

10L

46L

64L

12L

26L

Mandels k statistics(Soil 3 - PBD 99)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

10L

46L

64L

12L

26L

Labo

rato

ries

NUM

-200 -100 000 100 200

h-values

10L

46L

64L

12L

26L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 99)

Soil 3-PBD 99

Unit mgkg

Mandels k statistics(Compost 1 - PBD 100)Mandels h statistics(Compost 1 - PBD 100)

Sample Compost 1 Compost 1 - PBD 100 -- Mean PARM = 0001 [mgkg]

Element PBD 100

General calcparmT1= 124272E-02T2= 113129E-05T3= 14T4= 52T5= 46584E-07

n= variabelp= 4

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean26L 00006 0000 2 -131 037 Fail 00006 00001 2 1 00010L 00009 0000 4 003 083 00009 00002 4 3 00046L 00009 0000 4 016 115 00009 00002 4 3 00012L 00011 0000 4 112 136 Fail 00011 00003 4 3 000

Totgem 0001 0000 mgkg 1-level 149 (167) 4 00009 () 4 3Totstd= 0000 0000 5-level 142 (15)

RESULTS Mean = 000085 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000022 --gt 2531 r = 00006Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000025 --gt 2882 R = 00007Remarks none

000 050 100 150

k-values

26L

10L

46L

12L

Mandels k statistics(Compost 1 - PBD 100)

00 00 00 00 00 00 00 00 00 00 00

Deviation from Mean

26L

10L

46L

12L

Labo

rato

ries

Compost 1 - PBD 100 -- Mean PARM = 0001 [mgkg]

-200 -100 000 100 200

h-values

26L

10L

46L

12L

Labo

rato

ries

Mandels h statistics(Compost 1 - PBD 100)

Compost 1-PBD 100

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 100)Mandels h statistics(Sludge 1 - PBD 100)

Sample Sludge 1 Sludge 1 - PBD 100 -- Mean PARM = 0005 [mgkg]

Element PBD 100

General calcparmT1= 852065E-02T2= 412762E-04T3= 18T4= 68T5= 78914E-07

n= variabelp= 5

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00039 0000 4 -042 007 Fail 00039 00002 4 3 000

12L 00044 0000 4 -041 005 Fail 00044 00001 4 3 00010L 00046 0000 4 -041 013 Fail 00046 00003 4 3 00046L 00056 0000 4 -040 012 Fail 00056 00003 4 3 00026L 00059 0000 2 -040 013 Fail 00059 00003 2 1 00038L 02168 0006 4 204 244 Fail - - 38L - - 021

Totgem 0040 0001 mgkg 1-level 187 (177) 5 00049 (38L) 5 4Totstd= 0087 0002 5-level 166 (154) 1

RESULTS Mean = 000486 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000025 --gt 507 r = 00007Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000084 --gt 1731 R = 00024Remarks 1 Lab rejected (38L)

000 050 100 150 200 250

k-values

4L

12L

10L

46L

26L

38L

Mandels k statistics(Sludge 1 - PBD 100)

-01 00 01 01 02 02 03

Deviation from Mean

4L

12L

10L

46L

26L

38L

Labo

rato

ries

Sludge 1 - PBD 100 -- Mean PARM = 0005 [mgkg]

-100 000 100 200 300

h-values

4L

12L

10L

46L

26L

38L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 100)

Sludge 1-PBD 100

Unit mgkg

Mandels k statistics(Soil 3 - PBD 100)Mandels h statistics(Soil 3 - PBD 100)

Sample Soil 3 NUM

Element PBD 100

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00003 0000 4 -050 000 Fail - - 10L - - NUM46L 00003 0000 4 -050 000 Fail NUM - 46L - - NUM3L 305500 2051 2 150 200 Fail - - 3L - - NUM

26L 00005 0000 2 -050 000 Fail - - 26L - - NUM

Totgem 7638 0513 mgkg 1-level 149 (177) NUM (10L46L3L26L) -1Totstd= 15275 1025 5-level 142 (159) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (10L46L3L26L)

000 050 100 150 200

k-values

10L

46L

3L

26L

Mandels k statistics(Soil 3 - PBD 100)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

10L

46L

3L

26L

Labo

rato

ries

NUM

-100 000 100 200

h-values

10L

46L

3L

26L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 100)

Soil 3-PBD 100

Unit mgkg

Mandels k statistics(Compost 1 - PBD 153)Mandels h statistics(Compost 1 - PBD 153)

Sample Compost 1 NUM

Element PBD 153

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean44L 00053 0001 3 150 157 Fail - - 44L - - NUM46L 00007 0000 4 -044 111 Fail - - 46L - - NUM12L 00005 0000 4 -051 055 Fail - - 12L - - NUM26L 00005 0000 2 -054 001 Fail NUM - 26L - - NUM

Totgem 0002 0000 mgkg 1-level 149 (177) NUM (44L46L12L26L) -1Totstd= 0002 0000 5-level 142 (159) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (44L46L12L26L)

000 050 100 150 200

k-values

44L

46L

12L

26L

Mandels k statistics(Compost 1 - PBD 153)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

44L

46L

12L

26L

Labo

rato

ries

NUM

-100 000 100 200

h-values

44L

46L

12L

26L

Labo

rato

ries

Mandels h statistics(Compost 1 - PBD 153)

Compost 1-PBD 153

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 153)Mandels h statistics(Sludge 1 - PBD 153)

Sample Sludge 1 Sludge 1 - PBD 153 -- Mean PARM = 0004 [mgkg]

Element PBD 153

General calcparmT1= 676738E-02T2= 267609E-04T3= 18T4= 68T5= 19626E-05

n= variabelp= 5

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00024 0000 4 -157 017 00024 00002 4 3 000

12L 00038 0002 4 006 154 00038 00018 4 3 00046L 00039 0000 4 011 026 00039 00003 4 3 00026L 00039 0000 2 018 004 00039 00000 2 1 00064L 00049 0002 4 122 159 00049 00018 4 3 000

Totgem 0004 0001 mgkg 1-level 172 (173) 5 00038 () 5 4Totstd= 0001 0001 5-level 157 (153)

RESULTS Mean = 000378 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000123 --gt 3252 r = 00034Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000142 --gt 3754 R = 00040Remarks none

000 050 100 150 200

k-values

4L

12L

46L

26L

64L

Mandels k statistics(Sludge 1 - PBD 153)

00 00 00 00 00 00 00

Deviation from Mean

4L

12L

46L

26L

64L

Labo

rato

ries

Sludge 1 - PBD 153 -- Mean PARM = 0004 [mgkg]

-200 -100 000 100 200

h-values

4L

12L

46L

26L

64L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 153)

Sludge 1-PBD 153

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 154)Mandels h statistics(Sludge 1 - PBD 154)

Sample Sludge 1 NA

Element PBD 154

General calcparmT1= NAT2= NAT3=T4=T5=

n= variabelp=

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00021 0000 3 -100 021 NA - 4L - - NA

46L 00025 0000 4 115 018 NA - 46L - - NA64L 00021 0001 4 -066 179 - - 64L - - NA12L 00023 0000 4 050 085 - - 12L - - NA

Totgem 0002 0000 mgkg 1-level 149 (167) NA (4L46L64L12L) -1Totstd= 0000 0000 5-level 142 (15) 4

RESULTS Mean = NA mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NAReproducibility var S2R = NAReproducibility std SR = NA --gt NA R = NARemarks 4 Labs rejected (4L46L64L12L)

000 050 100 150 200

k-values

4L

46L

64L

12L

Mandels k statistics(Sludge 1 - PBD 154)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

4L

46L

64L

12L

Labo

rato

ries

NA

-100 000 100 200

h-values

4L

46L

64L

12L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 154)

Sludge 1-PBD 154

Unit mgkg

Mandels k statistics(Soil 3 - PBD 154)Mandels h statistics(Soil 3 - PBD 154)

Sample Soil 3 NUM

Element PBD 154

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

4L 00010 - 1 150 Fail - - 4L - - NUM46L 00001 0000 4 -053 096 Fail - - 46L - - NUM64L 00001 0000 4 -056 105 Fail NUM - 64L - - NUM12L 00002 0000 4 -040 099 Fail - - 12L - - NUM

Totgem 000037 0000 mgkg 1-level 149 (164) NUM (4L46L64L12L) -1Totstd= 000042 0000 5-level 142 (153) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (4L46L64L12L)

000 050 100 150

k-values

4L

46L

64L

12L

Mandels k statistics(Soil 3 - PBD 154)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

4L

46L

64L

12L

Labo

rato

ries

NUM

-100 000 100 200

h-values

4L

46L

64L

12L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 154)

Soil 3-PBD 154

Unit mgkg

Mandels k statistics(Compost 1 - PBD 209)Mandels h statistics(Compost 1 - PBD 209)

Sample Compost 1 NUM

Element PBD 209

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00065 0003 2 -049 032 - - 4L - - NUM

44L 00573 0021 4 150 197 Fail - - 44L - - NUM12L 00078 0001 4 -045 011 - - 12L - - NUM26L 00049 0000 2 -056 000 NUM - 26L - - NUM

Totgem 0019 0006 mgkg 1-level 149 (177) NUM (4L44L12L26L) -1Totstd= 0025 0010 5-level 142 (159) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (4L44L12L26L)

000 050 100 150 200

k-values

4L

44L

12L

26L

Mandels k statistics(Compost 1 - PBD 209)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

4L

44L

12L

26L

Labo

rato

ries

NUM

-100 000 100 200

h-values

4L

44L

12L

26L

Labo

rato

ries

Mandels h statistics(Compost 1 - PBD 209)

Compost 1-PBD 209

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 209)Mandels h statistics(Sludge 1 - PBD 209)

Sample Sludge 1 Sludge 1 - PBD 209 -- Mean PARM = 0249 [mgkg]

Element PBD 209

General calcparmT1= 394542E+00T2= 107296E+00T3= 16T4= 56T5= 19723E-02

n= variabelp= 5

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 01550 0055 4 -112 148 Fail 01550 00551 4 3 -009

46L 02050 0007 2 -053 019 02050 00071 2 1 -00412L 02137 0058 4 -042 155 02137 00576 4 3 -00426L 03149 0021 2 078 057 Fail 03149 00210 2 1 00764L 03577 0007 4 129 020 Fail 03577 00074 4 3 011

Totgem 0249 0030 mgkg 1-level 172 (185) 5 02493 () 5 4Totstd= 0084 0025 5-level 157 (162)

RESULTS Mean = 024926 mgkg

Repeatability variance S2r = 000179Repeatability std Sr = 004234 --gt 1699 r = 01186Between lab variance S2L = 000743Reproducibility var S2R = 000922Reproducibility std SR = 009604 --gt 3853 R = 02689Remarks none

000 050 100 150 200

k-values

4L

46L

12L

26L

64L

Mandels k statistics(Sludge 1 - PBD 209)

-01 -01 00 01 01 02

Deviation from Mean

4L

46L

12L

26L

64L

Labo

rato

ries

Sludge 1 - PBD 209 -- Mean PARM = 0249 [mgkg]

-200 -100 000 100 200

h-values

4L

46L

12L

26L

64L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 209)

Sludge 1-PBD 209

Unit mgkg

Mandels k statistics(Soil 3 - PBD 209)Mandels h statistics(Soil 3 - PBD 209)

Sample Soil 3 Soil 3 - PBD 209 -- Mean PARM = 0258 [mgkg]

Element PBD 209

General calcparmT1= 596398E+00T2= 191917E+00T3= 22T4= 84T5= 13249E-02

n= variabelp= 6

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean26L 01162 0021 2 -108 074 Fail 01162 00207 2 1 -0144L 01303 0031 4 -097 111 Fail 01303 00312 4 3 -013

46L 01975 0036 4 -046 128 Fail 01975 00359 4 3 -00644L 02898 0035 4 024 124 Fail 02898 00346 4 3 00312L 03895 0018 4 100 065 Fail 03895 00181 4 3 01364L 04260 0022 4 127 078 Fail 04260 00219 4 3 017

Totgem 0258 0027 mgkg 1-level 187 (177) 6 02582 () 6 5Totstd= 0132 0008 5-level 166 (154)

RESULTS Mean = 025818 mgkg

Repeatability variance S2r = 000083Repeatability std Sr = 002878 --gt 1115 r = 00806Between lab variance S2L = 001640Reproducibility var S2R = 001723Reproducibility std SR = 013127 --gt 5084 R = 03676Remarks none

000 050 100 150

k-values

26L

4L

46L

44L

12L

64L

Mandels k statistics(Soil 3 - PBD 209)

-02 -01 -01 00 01 01 02 02

Deviation from Mean

26L

4L

46L

44L

12L

64L

Labo

rato

ries

Soil 3 - PBD 209 -- Mean PARM = 0258 [mgkg]

-200 -100 000 100 200

h-values

26L

4L

46L

44L

12L

64L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 209)

Soil 3-PBD 209

Unit mgkg

Mandels k statistics(Compost 1 - Sum PBD)Mandels h statistics(Compost 1 - Sum PBD)

Sample Compost 1 Compost 1 - Sum PBD -- Mean PARM = 0009 [mgkg]

Element Sum PBD

General calcparmT1= 154064E-01T2= 169065E-03T3= 18T4= 68T5= 11354E-04

n= variabelp= 5

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00031 0002 4 -067 016 00031 00016 4 3 -0014L 00055 0005 4 -056 048 00055 00047 4 3 000

46L 00085 0003 4 -042 031 00085 00030 4 3 00026L 00123 0000 2 -024 003 00123 00002 2 1 00012L 00154 0002 4 -011 021 00154 00021 4 3 00144L 00613 0023 4 200 237 Fail - - 44L - - 005

Totgem 0018 0006 mgkg 1-level 187 (177) 5 00089 (44L) 5 4Totstd= 0022 0009 5-level 166 (154) 1

RESULTS Mean = 000893 mgkg

Repeatability variance S2r = 000001Repeatability std Sr = 000296 --gt 3308 r = 00083Between lab variance S2L = 000002Reproducibility var S2R = 000003Reproducibility std SR = 000570 --gt 6374 R = 00159Remarks 1 Lab rejected (44L)

000 050 100 150 200 250

k-values

10L

4L

46L

26L

12L

44L

Mandels k statistics(Compost 1 - Sum PBD)

00 00 00 00 00 00 01 01

Deviation from Mean

10L

4L

46L

26L

12L

44L

Labo

rato

ries

Compost 1 - Sum PBD -- Mean PARM = 0009 [mgkg]

-100 000 100 200

h-values

10L

4L

46L

26L

12L

44L

Labo

rato

ries

Mandels h statistics(Compost 1 - Sum PBD)

Compost 1-Sum PBD

Unit mgkg

Mandels k statistics(Sludge 1 - Sum PBD)Mandels h statistics(Sludge 1 - Sum PBD)

Sample Sludge 1 Sludge 1 - Sum PBD -- Mean PARM = 0256 [mgkg]

Element Sum PBD

General calcparmT1= 531806E+00T2= 162188E+00T3= 22T4= 84T5= 25223E-02

n= variabelp= 6

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00423 0025 4 -156 044 Fail 00423 00252 4 3 -02146L 01808 0118 4 -049 205 - - 46L - - -0074L 01810 0056 4 -049 097 01810 00558 4 3 -007

38L 02168 0006 4 -022 010 02168 00059 4 3 -00412L 02890 0065 4 034 113 02890 00647 4 3 00364L 03958 0008 4 116 014 Fail 03958 00079 4 3 01426L 04094 0034 2 126 059 Fail 04094 00337 2 1 015

Totgem 0245 0044 mgkg 1-level 198 (179) 6 02557 (46L) 6 5Totstd= 0130 0039 5-level 171 (155) 1

RESULTS Mean = 025570 mgkg

Repeatability variance S2r = 000158Repeatability std Sr = 003970 --gt 1553 r = 01112Between lab variance S2L = 001807Reproducibility var S2R = 001964Reproducibility std SR = 014015 --gt 5481 R = 03924Remarks 1 Lab rejected (46L)

000 050 100 150 200 250

k-values

10L

46L

4L

38L

12L

64L

26L

Mandels k statistics(Sludge 1 - Sum PBD)

-03 -02 -02 -01 -01 00 01 01 02 02

Deviation from Mean

10L

46L

4L

38L

12L

64L

26L

Labo

rato

ries

Sludge 1 - Sum PBD -- Mean PARM = 0256 [mgkg]

-200 -100 000 100 200

h-values

10L

46L

4L

38L

12L

64L

26L

Labo

rato

ries

Mandels h statistics(Sludge 1 - Sum PBD)

Sludge 1-Sum PBD

Unit mgkg

Mandels k statistics(Soil 3 - Sum PBD)Mandels h statistics(Soil 3 - Sum PBD)

Sample Soil 3 Soil 3 - Sum PBD -- Mean PARM = 0227 [mgkg]

Element Sum PBD

General calcparmT1= 610980E+00T2= 200876E+00T3= 26T4= 100T5= 13106E-02

n= variabelp= 7

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00028 0001 4 -037 000 Fail 00028 00005 4 3 -02226L 01179 0021 2 -036 003 Fail 01179 00208 2 1 -0114L 01305 0031 4 -036 004 Fail 01305 00308 4 3 -010

46L 02065 0035 4 -036 005 Fail 02065 00350 4 3 -00244L 02923 0037 4 -035 005 Fail 02923 00365 4 3 00712L 04051 0015 4 -034 002 Fail 04051 00149 4 3 01864L 04314 0022 4 -033 003 Fail 04314 00223 4 3 0203L 305500 2051 2 247 283 Fail - - 3L - - 3032

Totgem 4017 0276 mgkg 1-level 206 (181) 7 02266 (3L) 7 6Totstd= 10722 0717 5-level 175 (156) 1

RESULTS Mean = 022663 mgkg

Repeatability variance S2r = 000069Repeatability std Sr = 002626 --gt 1159 r = 00735Between lab variance S2L = 002568Reproducibility var S2R = 002637Reproducibility std SR = 016238 --gt 7165 R = 04547Remarks 1 Lab rejected (3L)

000 050 100 150 200 250 300

k-values

10L

26L

4L

46L

44L

12L

64L

3L

Mandels k statistics(Soil 3 - Sum PBD)

-50 00 50 100 150 200 250 300 350

Deviation from Mean

10L

26L

4L

46L

44L

12L

64L

3L

Labo

rato

ries

Soil 3 - Sum PBD -- Mean PARM = 0227 [mgkg]

-100 000 100 200 300

h-values

10L

26L

4L

46L

44L

12L

64L

3L

Labo

rato

ries

Mandels h statistics(Soil 3 - Sum PBD)

Soil 3-Sum PBD

19

Annex 4

Raw data submitted

Sample Compost1 Sample Compost 1 Sample Compost 1Element PBD 99 Element PBD 100 Element PBD 153

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]4L 00021 10L 00008 44L 000504L 00024 10L 00008 44L 000604L 00014 10L 00007 44L 000504L 00020 10L 00011 46L 00004

10L 00029 46L 00007 46L 0001210L 00027 46L 00012 46L 0000410L 00032 46L 00009 46L 0000946L 00025 46L 00007 12L 0000446L 00052 12L 00008 12L 0000846L 00029 12L 00012 12L 0000446L 00026 12L 00008 12L 0000712L 00026 12L 00014 26L 0000512L 00043 26L 00007 26L 0000512L 00026 26L 0000612L 0004726L 0002626L 00024

Sample Compost 1 Sample Compost 1 Sample Compost 1Element PBD 154 Element PBD 183 Element PBD 196

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]4L 00010 46L 00002 46L 00011

46L 00003 46L 00024 46L 0000846L 00007 46L 00021 12L 0000246L 00003 46L 00003 12L 0000346L 00004 12L 00003 12L 0000112L 00003 12L 00011 12L 0000212L 00005 12L 0000312L 00031 12L 0000312L 00006

Sample Compost 1 Sample Compost 1 Sample Compost 1Element PBD 197 Element PBD 203 Element PBD 209

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00002 46L 00010 4L 0004146L 00023 12L 00002 4L 0008946L 00022 12L 00003 44L 0041012L 00004 12L 00002 44L 0084012L 00006 12L 00002 44L 0064012L 00003 44L 0040012L 00004 12L 00079

12L 0007312L 0006512L 0009326L 0004926L 00049

Sample Compost 1Element PBD 47

LAB PARM [mgkg]26L 0003826L 00039

Element PBD 99 Element PBD 47 Element PBD 209LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]

4L 00170 10L 00210 4L 010004L 00200 10L 00220 4L 018004L 00170 10L 00210 4L 012004L 00190 46L 00300 4L 0220010L 00280 46L 00280 46L 0210010L 00300 46L 00250 46L 0200010L 00290 46L 00260 64L 0351846L 00340 64L 00059 64L 0363846L 00330 64L 00057 64L 0364546L 00300 64L 00062 64L 0350846L 00310 64L 00060 12L 0220964L 00194 12L 00191 12L 0177164L 00154 12L 00187 12L 0292264L 00185 12L 00190 12L 0164664L 00159 12L 00186 26L 0329712L 00242 26L 00666 26L 0300012L 00223 26L 0033212L 0022112L 0022226L 0024626L 00400

Element PBD 203 Element PBD 197 Element PBD 196LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00022 46L 00027 46L 0002446L 00014 46L 00024 46L 0002264L 00036 12L 00161 64L 0005864L 00058 12L 00060 64L 0006512L 00063 12L 00061 12L 0004812L 00034 12L 00036 12L 0002512L 00038 12L 0003212L 00027 12L 00022

Element PBD 183 Element PBD 154 Element PBD 153LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00049 4L 00020 4L 0002246L 00035 4L 00022 4L 0002446L 00036 4L 00020 4L 0002246L 00034 46L 00025 4L 0002664L 00027 46L 00025 46L 0004064L 00023 46L 00025 46L 0004264L 00024 46L 00023 46L 0003564L 00020 64L 00034 46L 0003812L 00230 64L 00023 64L 0007412L 00032 64L 00017 64L 0004712L 00031 64L 00011 64L 0004612L 00030 12L 00030 64L 0003026L 00007 12L 00021 12L 0006526L 00008 12L 00021 12L 00029

12L 00021 12L 0003226L 00015 12L 0002926L 00019 26L 00039

26L 00040

Element PBD 100LAB PARM [mgkg]

4L 000384L 000414L 000374L 00038

38L 0219038L 0220038L 0208038L 0220010L 0004410L 0005010L 0004310L 0004646L 0005746L 0005946L 0005346L 0005312L 0004312L 0004512L 0004312L 0004326L 0006226L 00057

Sample Soil 3 Sample Soil 3 Sample Soil 3Element PBD 99 Element PBD 47 Element PBD 100

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]10L 00016 10L 00011 10L 0000310L 00019 10L 00010 10L 0000410L 00013 10L 00012 10L 0000410L 00019 46L 00007 10L 0000246L 00025 46L 00022 46L 0000246L 00025 46L 00005 46L 0000646L 00008 46L 00007 46L 0000246L 00011 12L 00010 46L 0000264L 00005 12L 00017 3L 29100064L 00005 12L 00010 3L 32000064L 00006 12L 00009 26L 0000564L 00007 26L 00007 26L 0000512L 00012 26L 0000712L 0001312L 0001312L 0001226L 0000526L 00006

Sample Soil 3 Sample Soil 3 Sample Soil 3Element PBD 153 Element PBD 154 Element PBD 196

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]44L 00050 4L 00010 46L 0000744L 00050 46L 00001 46L 0001146L 00002 46L 00002 46L 0000846L 00003 46L 00001 46L 0001146L 00002 46L 00002 64L 0002646L 00002 64L 00001 64L 0002664L 00001 64L 00001 64L 0002964L 00001 64L 00001 64L 0003464L 00001 64L 00002 12L 0004564L 00002 12L 00003 12L 00032

12L 00002 12L 0002212L 00002 12L 0002112L 00002

Sample Soil 3 Sample Soil 3 Sample Soil 3Element PBD 197 Element PBD 203 Element PBD 209

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00006 46L 00011 4L 0091046L 00013 46L 00017 4L 0150046L 00011 46L 00015 4L 0120046L 00013 46L 00018 4L 0160012L 00090 64L 00013 44L 0337012L 00056 64L 00014 44L 0281012L 00033 64L 00016 44L 0287012L 00032 64L 00015 44L 02540

12L 00055 46L 0230012L 00041 46L 0220012L 00027 46L 0150012L 00026 46L 01900

64L 0438164L 0401664L 0414464L 0449812L 0367112L 0397812L 0409112L 03838

Sample Soil 3 26L 0102Element PBD 183 26L 0131

LAB PARM [mgkg]46L 0000746L 0000846L 0005846L 0000764L 0000264L 0000364L 0000364L 0000312L 0001512L 0001112L 0000712L 00007

European Commission EUR 23003 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on polybrominated diphenylethers Author(s) E Sobiecka H van der Sloot D Barcelo B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 68 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07403-5 Abstract Project HORIZONTAL is interdisciplinary aiming at a harmonisation and horizontal standardisation of test procedures in particular for sludge soils and biowastes In the context of this standardization project a series of draft technical specification were designed upon an extensive desk study fine-tuned after expert consultations and finally validated in international intercomparisons exercise This report summarises the work performed within the validation study of the draft standard for the determination of polybrominated diphenylethers (PBDE) in soils sludge and treated bio-waste using gas-chromatography method with mass selective detection (GC-MS) It further explains the underlying statistical concept for the calculation of reproducibility and repeatability from intercomparisons data In addition all single values results of the statistical evaluation as well as background information on the validation materials used are described and explained

The mission of the JRC is to provide customer-driven scientific and technical support for the conception development implementation and monitoring of EU policies As a service of the European Commission the JRC functions as a reference centre of science and technology for the Union Close to the policy-making process it serves the common interest of the Member States while being independent of special interests whether private or national

LB

-NA

-23003-EN

-C

17

26 Sludge amended soil from Essen Germany

The German sludge-amended soil from Essen which was provided as the three sludge materials by LUA NRW did not feature significant concentrations of the PCB congeners 28 52 101 118 153 105 138 156 180 170 but had detectable amounts of some PAHs

Table 34 ndash Analytical screening data on the German sludge-amended soil

Parameter Concentration(ngg)

Naphtalene lt10 Acenaphtylene lt10 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene lt10 Fluoranthene 28 Pyrene 20 Benz(a)anthracene 24 Chrysene 47 Benz(b)fluoranthene 76 Benz(k)fluoranthene 20 Benz(a)pyrene 35 Indeno(123-cd)pyrene 35 Dibenzo(ah)anthracene 10 Benzo(ghi)perylene 26

Table 35 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 4 (Essen) 0011 0302 055

Table 36 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 4

(Essen)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

nq

nq

nq

nq

nq

nq

128

191

203

18

Table 37 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 4 (Essen) 052 545 261 805 320 403 273 273 lt 005 295 781

Table 38 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 4 (Essen) 7947 442 085 06 086 007 2163 189 2019 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 4 (Essen) 045 19 42 87 683 60 462 61

Table 39 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 4 (Essen) 004

27 Long-term sludge exposed soil from Hohenheim-Stuttgart Germany

Similarly an additional sludge exposed soil was sampled at the University of Hohenheim Stuttgart were a test soil was long-term exposed to elevated concentrations of sewage sludge

Table 40 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 1 (Stuttgart) 0045 0263 1765

Table 41 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 1

(Stuttgart)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

230

006

004

004

nq

nd

nd

498

500

19

Table 42 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 1 (Stuttgart) 069 127 361 262 504 183 252 262 lt 005 266 142

Table 43 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 1 (Stuttgart) 7194 1006 133 186 366 088 7874 275 3571 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 1 (Stuttgart) 123 50 47 212 85 69 991 129

Table 44 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 1 (Stuttgart) 177

18

Annex 3

Statistical calculations

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 47)Mandels h statistics(Sludge 1 - PBD 47)

Sample Sludge 1 NUM

Element PBD 47

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00213 0001 3 -021 005 - - 10L - - NUM46L 00273 0002 4 016 021 - - 46L - - NUM64L 00059 0000 4 -116 002 NUM - 64L - - NUM12L 00188 0000 4 -036 002 - - 12L - - NUM26L 00499 0024 2 157 223 Fail - - 26L - - NUM

Totgem 0025 0005 mgkg 1-level 172 (185) NUM (10L46L64L12L26L) -1Totstd= 0016 0010 5-level 157 (162) 5

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 5 Labs rejected (10L46L64L12L26L)

000 050 100 150 200 250

k-values

10L

46L

64L

12L

26L

Mandels k statistics(Sludge 1 - PBD 47)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

10L

46L

64L

12L

26L

Labo

rato

ries

NUM

-200 -100 000 100 200

h-values

10L

46L

64L

12L

26L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 47)

Sludge 1-PBD 47

Unit mgkg

Mandels k statistics(Soil 3 - PBD 47)Mandels h statistics(Soil 3 - PBD 47)

Sample Soil 3 Soil 3 - PBD 47 -- Mean PARM = 0001 [mgkg]

Element PBD 47

General calcparmT1= 134814E-02T2= 142830E-05T3= 13T4= 45T5= 22767E-06

n= variabelp= 4

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean26L 00007 0000 2 -143 001 00007 00000 2 1 00046L 00010 0001 4 010 181 00010 00008 4 3 00010L 00011 0000 3 049 023 00011 00001 3 2 00012L 00012 0000 4 084 081 00012 00004 4 3 000

Totgem 0001 0000 mgkg 1-level 149 (177) 4 00010 () 4 3Totstd= 0000 0000 5-level 142 (159)

RESULTS Mean = 000100 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000050 --gt 5031 r = 00014Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000050 --gt 5031 R = 00014Remarks none

000 050 100 150 200

k-values

26L

46L

10L

12L

Mandels k statistics(Soil 3 - PBD 47)

00 00 00 00 00 00 00 00 00 00 00

Deviation from Mean

26L

46L

10L

12L

Labo

rato

ries

Soil 3 - PBD 47 -- Mean PARM = 0001 [mgkg]

-200 -100 000 100

h-values

26L

46L

10L

12L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 47)

Soil 3-PBD 47

Unit mgkg

Mandels k statistics(Compost 1 - PBD 99)Mandels h statistics(Compost 1 - PBD 99)

Sample Compost 1 Compost 1 - PBD 99 -- Mean PARM = 0003 [mgkg]

Element PBD 99

General calcparmT1= 492124E-02T2= 148747E-04T3= 17T4= 61T5= 93196E-06

n= variabelp= 5

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00020 0000 4 -137 053 00020 00004 4 3 000

26L 00025 0000 2 -058 024 00025 00002 2 1 00010L 00029 0000 3 012 032 00029 00003 3 2 00046L 00033 0001 4 069 161 00033 00013 4 3 00012L 00036 0001 4 114 140 00036 00011 4 3 000

Totgem 0003 0001 mgkg 1-level 172 (185) 5 00029 () 5 4Totstd= 0001 0001 5-level 157 (162)

RESULTS Mean = 000286 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000088 --gt 3086 r = 00025Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000101 --gt 3525 R = 00028Remarks none

000 050 100 150 200

k-values

4L

26L

10L

46L

12L

Mandels k statistics(Compost 1 - PBD 99)

00 00 00 00 00 00 00 00 00 00

Deviation from Mean

4L

26L

10L

46L

12L

Labo

rato

ries

Compost 1 - PBD 99 -- Mean PARM = 0003 [mgkg]

-200 -100 000 100 200

h-values

4L

26L

10L

46L

12L

Labo

rato

ries

Mandels h statistics(Compost 1 - PBD 99)

Compost 1-PBD 99

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 99)Mandels h statistics(Sludge 1 - PBD 99)

Sample Sludge 1 Sludge 1 - PBD 99 -- Mean PARM = 0024 [mgkg]

Element PBD 99

General calcparmT1= 448050E-01T2= 112113E-02T3= 19T4= 73T5= 32972E-05

n= variabelp= 5

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean64L 00173 0002 4 -118 041 Fail 00173 00019 4 3 -0014L 00183 0002 4 -104 032 00183 00015 4 3 -001

12L 00227 0001 4 -038 022 00227 00010 4 3 00010L 00290 0001 3 055 021 00290 00010 3 2 00146L 00320 0002 4 100 039 00320 00018 4 3 00126L 00323 0011 2 105 234 - - 26L - - 001

Totgem 0025 0003 mgkg 1-level 187 (177) 5 00239 (26L) 5 4Totstd= 0007 0004 5-level 166 (154) 1

RESULTS Mean = 002385 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000153 --gt 643 r = 00043Between lab variance S2L = 000004Reproducibility var S2R = 000004Reproducibility std SR = 000666 --gt 2791 R = 00186Remarks 1 Lab rejected (26L)

000 050 100 150 200 250

k-values

64L

4L

12L

10L

46L

26L

Mandels k statistics(Sludge 1 - PBD 99)

00 00 00 00 00 00 00 00 00 00

Deviation from Mean

64L

4L

12L

10L

46L

26L

Labo

rato

ries

Sludge 1 - PBD 99 -- Mean PARM = 0024 [mgkg]

-200 -100 000 100 200

h-values

64L

4L

12L

10L

46L

26L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 99)

Sludge 1-PBD 99

Unit mgkg

Mandels k statistics(Soil 3 - PBD 99)Mandels h statistics(Soil 3 - PBD 99)

Sample Soil 3 NUM

Element PBD 99

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00017 0000 4 091 068 - - 10L - - NUM46L 00017 0001 4 100 211 - - 46L - - NUM64L 00005 0000 4 -106 023 NUM - 64L - - NUM12L 00012 0000 4 015 014 - - 12L - - NUM26L 00006 0000 2 -101 012 - - 26L - - NUM

Totgem 0001 0000 mgkg 1-level 172 (173) NUM (10L46L64L12L26L) -1Totstd= 0001 0000 5-level 157 (153) 5

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 5 Labs rejected (10L46L64L12L26L)

000 050 100 150 200 250

k-values

10L

46L

64L

12L

26L

Mandels k statistics(Soil 3 - PBD 99)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

10L

46L

64L

12L

26L

Labo

rato

ries

NUM

-200 -100 000 100 200

h-values

10L

46L

64L

12L

26L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 99)

Soil 3-PBD 99

Unit mgkg

Mandels k statistics(Compost 1 - PBD 100)Mandels h statistics(Compost 1 - PBD 100)

Sample Compost 1 Compost 1 - PBD 100 -- Mean PARM = 0001 [mgkg]

Element PBD 100

General calcparmT1= 124272E-02T2= 113129E-05T3= 14T4= 52T5= 46584E-07

n= variabelp= 4

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean26L 00006 0000 2 -131 037 Fail 00006 00001 2 1 00010L 00009 0000 4 003 083 00009 00002 4 3 00046L 00009 0000 4 016 115 00009 00002 4 3 00012L 00011 0000 4 112 136 Fail 00011 00003 4 3 000

Totgem 0001 0000 mgkg 1-level 149 (167) 4 00009 () 4 3Totstd= 0000 0000 5-level 142 (15)

RESULTS Mean = 000085 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000022 --gt 2531 r = 00006Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000025 --gt 2882 R = 00007Remarks none

000 050 100 150

k-values

26L

10L

46L

12L

Mandels k statistics(Compost 1 - PBD 100)

00 00 00 00 00 00 00 00 00 00 00

Deviation from Mean

26L

10L

46L

12L

Labo

rato

ries

Compost 1 - PBD 100 -- Mean PARM = 0001 [mgkg]

-200 -100 000 100 200

h-values

26L

10L

46L

12L

Labo

rato

ries

Mandels h statistics(Compost 1 - PBD 100)

Compost 1-PBD 100

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 100)Mandels h statistics(Sludge 1 - PBD 100)

Sample Sludge 1 Sludge 1 - PBD 100 -- Mean PARM = 0005 [mgkg]

Element PBD 100

General calcparmT1= 852065E-02T2= 412762E-04T3= 18T4= 68T5= 78914E-07

n= variabelp= 5

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00039 0000 4 -042 007 Fail 00039 00002 4 3 000

12L 00044 0000 4 -041 005 Fail 00044 00001 4 3 00010L 00046 0000 4 -041 013 Fail 00046 00003 4 3 00046L 00056 0000 4 -040 012 Fail 00056 00003 4 3 00026L 00059 0000 2 -040 013 Fail 00059 00003 2 1 00038L 02168 0006 4 204 244 Fail - - 38L - - 021

Totgem 0040 0001 mgkg 1-level 187 (177) 5 00049 (38L) 5 4Totstd= 0087 0002 5-level 166 (154) 1

RESULTS Mean = 000486 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000025 --gt 507 r = 00007Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000084 --gt 1731 R = 00024Remarks 1 Lab rejected (38L)

000 050 100 150 200 250

k-values

4L

12L

10L

46L

26L

38L

Mandels k statistics(Sludge 1 - PBD 100)

-01 00 01 01 02 02 03

Deviation from Mean

4L

12L

10L

46L

26L

38L

Labo

rato

ries

Sludge 1 - PBD 100 -- Mean PARM = 0005 [mgkg]

-100 000 100 200 300

h-values

4L

12L

10L

46L

26L

38L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 100)

Sludge 1-PBD 100

Unit mgkg

Mandels k statistics(Soil 3 - PBD 100)Mandels h statistics(Soil 3 - PBD 100)

Sample Soil 3 NUM

Element PBD 100

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00003 0000 4 -050 000 Fail - - 10L - - NUM46L 00003 0000 4 -050 000 Fail NUM - 46L - - NUM3L 305500 2051 2 150 200 Fail - - 3L - - NUM

26L 00005 0000 2 -050 000 Fail - - 26L - - NUM

Totgem 7638 0513 mgkg 1-level 149 (177) NUM (10L46L3L26L) -1Totstd= 15275 1025 5-level 142 (159) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (10L46L3L26L)

000 050 100 150 200

k-values

10L

46L

3L

26L

Mandels k statistics(Soil 3 - PBD 100)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

10L

46L

3L

26L

Labo

rato

ries

NUM

-100 000 100 200

h-values

10L

46L

3L

26L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 100)

Soil 3-PBD 100

Unit mgkg

Mandels k statistics(Compost 1 - PBD 153)Mandels h statistics(Compost 1 - PBD 153)

Sample Compost 1 NUM

Element PBD 153

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean44L 00053 0001 3 150 157 Fail - - 44L - - NUM46L 00007 0000 4 -044 111 Fail - - 46L - - NUM12L 00005 0000 4 -051 055 Fail - - 12L - - NUM26L 00005 0000 2 -054 001 Fail NUM - 26L - - NUM

Totgem 0002 0000 mgkg 1-level 149 (177) NUM (44L46L12L26L) -1Totstd= 0002 0000 5-level 142 (159) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (44L46L12L26L)

000 050 100 150 200

k-values

44L

46L

12L

26L

Mandels k statistics(Compost 1 - PBD 153)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

44L

46L

12L

26L

Labo

rato

ries

NUM

-100 000 100 200

h-values

44L

46L

12L

26L

Labo

rato

ries

Mandels h statistics(Compost 1 - PBD 153)

Compost 1-PBD 153

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 153)Mandels h statistics(Sludge 1 - PBD 153)

Sample Sludge 1 Sludge 1 - PBD 153 -- Mean PARM = 0004 [mgkg]

Element PBD 153

General calcparmT1= 676738E-02T2= 267609E-04T3= 18T4= 68T5= 19626E-05

n= variabelp= 5

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00024 0000 4 -157 017 00024 00002 4 3 000

12L 00038 0002 4 006 154 00038 00018 4 3 00046L 00039 0000 4 011 026 00039 00003 4 3 00026L 00039 0000 2 018 004 00039 00000 2 1 00064L 00049 0002 4 122 159 00049 00018 4 3 000

Totgem 0004 0001 mgkg 1-level 172 (173) 5 00038 () 5 4Totstd= 0001 0001 5-level 157 (153)

RESULTS Mean = 000378 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000123 --gt 3252 r = 00034Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000142 --gt 3754 R = 00040Remarks none

000 050 100 150 200

k-values

4L

12L

46L

26L

64L

Mandels k statistics(Sludge 1 - PBD 153)

00 00 00 00 00 00 00

Deviation from Mean

4L

12L

46L

26L

64L

Labo

rato

ries

Sludge 1 - PBD 153 -- Mean PARM = 0004 [mgkg]

-200 -100 000 100 200

h-values

4L

12L

46L

26L

64L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 153)

Sludge 1-PBD 153

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 154)Mandels h statistics(Sludge 1 - PBD 154)

Sample Sludge 1 NA

Element PBD 154

General calcparmT1= NAT2= NAT3=T4=T5=

n= variabelp=

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00021 0000 3 -100 021 NA - 4L - - NA

46L 00025 0000 4 115 018 NA - 46L - - NA64L 00021 0001 4 -066 179 - - 64L - - NA12L 00023 0000 4 050 085 - - 12L - - NA

Totgem 0002 0000 mgkg 1-level 149 (167) NA (4L46L64L12L) -1Totstd= 0000 0000 5-level 142 (15) 4

RESULTS Mean = NA mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NAReproducibility var S2R = NAReproducibility std SR = NA --gt NA R = NARemarks 4 Labs rejected (4L46L64L12L)

000 050 100 150 200

k-values

4L

46L

64L

12L

Mandels k statistics(Sludge 1 - PBD 154)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

4L

46L

64L

12L

Labo

rato

ries

NA

-100 000 100 200

h-values

4L

46L

64L

12L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 154)

Sludge 1-PBD 154

Unit mgkg

Mandels k statistics(Soil 3 - PBD 154)Mandels h statistics(Soil 3 - PBD 154)

Sample Soil 3 NUM

Element PBD 154

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

4L 00010 - 1 150 Fail - - 4L - - NUM46L 00001 0000 4 -053 096 Fail - - 46L - - NUM64L 00001 0000 4 -056 105 Fail NUM - 64L - - NUM12L 00002 0000 4 -040 099 Fail - - 12L - - NUM

Totgem 000037 0000 mgkg 1-level 149 (164) NUM (4L46L64L12L) -1Totstd= 000042 0000 5-level 142 (153) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (4L46L64L12L)

000 050 100 150

k-values

4L

46L

64L

12L

Mandels k statistics(Soil 3 - PBD 154)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

4L

46L

64L

12L

Labo

rato

ries

NUM

-100 000 100 200

h-values

4L

46L

64L

12L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 154)

Soil 3-PBD 154

Unit mgkg

Mandels k statistics(Compost 1 - PBD 209)Mandels h statistics(Compost 1 - PBD 209)

Sample Compost 1 NUM

Element PBD 209

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00065 0003 2 -049 032 - - 4L - - NUM

44L 00573 0021 4 150 197 Fail - - 44L - - NUM12L 00078 0001 4 -045 011 - - 12L - - NUM26L 00049 0000 2 -056 000 NUM - 26L - - NUM

Totgem 0019 0006 mgkg 1-level 149 (177) NUM (4L44L12L26L) -1Totstd= 0025 0010 5-level 142 (159) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (4L44L12L26L)

000 050 100 150 200

k-values

4L

44L

12L

26L

Mandels k statistics(Compost 1 - PBD 209)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

4L

44L

12L

26L

Labo

rato

ries

NUM

-100 000 100 200

h-values

4L

44L

12L

26L

Labo

rato

ries

Mandels h statistics(Compost 1 - PBD 209)

Compost 1-PBD 209

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 209)Mandels h statistics(Sludge 1 - PBD 209)

Sample Sludge 1 Sludge 1 - PBD 209 -- Mean PARM = 0249 [mgkg]

Element PBD 209

General calcparmT1= 394542E+00T2= 107296E+00T3= 16T4= 56T5= 19723E-02

n= variabelp= 5

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 01550 0055 4 -112 148 Fail 01550 00551 4 3 -009

46L 02050 0007 2 -053 019 02050 00071 2 1 -00412L 02137 0058 4 -042 155 02137 00576 4 3 -00426L 03149 0021 2 078 057 Fail 03149 00210 2 1 00764L 03577 0007 4 129 020 Fail 03577 00074 4 3 011

Totgem 0249 0030 mgkg 1-level 172 (185) 5 02493 () 5 4Totstd= 0084 0025 5-level 157 (162)

RESULTS Mean = 024926 mgkg

Repeatability variance S2r = 000179Repeatability std Sr = 004234 --gt 1699 r = 01186Between lab variance S2L = 000743Reproducibility var S2R = 000922Reproducibility std SR = 009604 --gt 3853 R = 02689Remarks none

000 050 100 150 200

k-values

4L

46L

12L

26L

64L

Mandels k statistics(Sludge 1 - PBD 209)

-01 -01 00 01 01 02

Deviation from Mean

4L

46L

12L

26L

64L

Labo

rato

ries

Sludge 1 - PBD 209 -- Mean PARM = 0249 [mgkg]

-200 -100 000 100 200

h-values

4L

46L

12L

26L

64L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 209)

Sludge 1-PBD 209

Unit mgkg

Mandels k statistics(Soil 3 - PBD 209)Mandels h statistics(Soil 3 - PBD 209)

Sample Soil 3 Soil 3 - PBD 209 -- Mean PARM = 0258 [mgkg]

Element PBD 209

General calcparmT1= 596398E+00T2= 191917E+00T3= 22T4= 84T5= 13249E-02

n= variabelp= 6

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean26L 01162 0021 2 -108 074 Fail 01162 00207 2 1 -0144L 01303 0031 4 -097 111 Fail 01303 00312 4 3 -013

46L 01975 0036 4 -046 128 Fail 01975 00359 4 3 -00644L 02898 0035 4 024 124 Fail 02898 00346 4 3 00312L 03895 0018 4 100 065 Fail 03895 00181 4 3 01364L 04260 0022 4 127 078 Fail 04260 00219 4 3 017

Totgem 0258 0027 mgkg 1-level 187 (177) 6 02582 () 6 5Totstd= 0132 0008 5-level 166 (154)

RESULTS Mean = 025818 mgkg

Repeatability variance S2r = 000083Repeatability std Sr = 002878 --gt 1115 r = 00806Between lab variance S2L = 001640Reproducibility var S2R = 001723Reproducibility std SR = 013127 --gt 5084 R = 03676Remarks none

000 050 100 150

k-values

26L

4L

46L

44L

12L

64L

Mandels k statistics(Soil 3 - PBD 209)

-02 -01 -01 00 01 01 02 02

Deviation from Mean

26L

4L

46L

44L

12L

64L

Labo

rato

ries

Soil 3 - PBD 209 -- Mean PARM = 0258 [mgkg]

-200 -100 000 100 200

h-values

26L

4L

46L

44L

12L

64L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 209)

Soil 3-PBD 209

Unit mgkg

Mandels k statistics(Compost 1 - Sum PBD)Mandels h statistics(Compost 1 - Sum PBD)

Sample Compost 1 Compost 1 - Sum PBD -- Mean PARM = 0009 [mgkg]

Element Sum PBD

General calcparmT1= 154064E-01T2= 169065E-03T3= 18T4= 68T5= 11354E-04

n= variabelp= 5

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00031 0002 4 -067 016 00031 00016 4 3 -0014L 00055 0005 4 -056 048 00055 00047 4 3 000

46L 00085 0003 4 -042 031 00085 00030 4 3 00026L 00123 0000 2 -024 003 00123 00002 2 1 00012L 00154 0002 4 -011 021 00154 00021 4 3 00144L 00613 0023 4 200 237 Fail - - 44L - - 005

Totgem 0018 0006 mgkg 1-level 187 (177) 5 00089 (44L) 5 4Totstd= 0022 0009 5-level 166 (154) 1

RESULTS Mean = 000893 mgkg

Repeatability variance S2r = 000001Repeatability std Sr = 000296 --gt 3308 r = 00083Between lab variance S2L = 000002Reproducibility var S2R = 000003Reproducibility std SR = 000570 --gt 6374 R = 00159Remarks 1 Lab rejected (44L)

000 050 100 150 200 250

k-values

10L

4L

46L

26L

12L

44L

Mandels k statistics(Compost 1 - Sum PBD)

00 00 00 00 00 00 01 01

Deviation from Mean

10L

4L

46L

26L

12L

44L

Labo

rato

ries

Compost 1 - Sum PBD -- Mean PARM = 0009 [mgkg]

-100 000 100 200

h-values

10L

4L

46L

26L

12L

44L

Labo

rato

ries

Mandels h statistics(Compost 1 - Sum PBD)

Compost 1-Sum PBD

Unit mgkg

Mandels k statistics(Sludge 1 - Sum PBD)Mandels h statistics(Sludge 1 - Sum PBD)

Sample Sludge 1 Sludge 1 - Sum PBD -- Mean PARM = 0256 [mgkg]

Element Sum PBD

General calcparmT1= 531806E+00T2= 162188E+00T3= 22T4= 84T5= 25223E-02

n= variabelp= 6

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00423 0025 4 -156 044 Fail 00423 00252 4 3 -02146L 01808 0118 4 -049 205 - - 46L - - -0074L 01810 0056 4 -049 097 01810 00558 4 3 -007

38L 02168 0006 4 -022 010 02168 00059 4 3 -00412L 02890 0065 4 034 113 02890 00647 4 3 00364L 03958 0008 4 116 014 Fail 03958 00079 4 3 01426L 04094 0034 2 126 059 Fail 04094 00337 2 1 015

Totgem 0245 0044 mgkg 1-level 198 (179) 6 02557 (46L) 6 5Totstd= 0130 0039 5-level 171 (155) 1

RESULTS Mean = 025570 mgkg

Repeatability variance S2r = 000158Repeatability std Sr = 003970 --gt 1553 r = 01112Between lab variance S2L = 001807Reproducibility var S2R = 001964Reproducibility std SR = 014015 --gt 5481 R = 03924Remarks 1 Lab rejected (46L)

000 050 100 150 200 250

k-values

10L

46L

4L

38L

12L

64L

26L

Mandels k statistics(Sludge 1 - Sum PBD)

-03 -02 -02 -01 -01 00 01 01 02 02

Deviation from Mean

10L

46L

4L

38L

12L

64L

26L

Labo

rato

ries

Sludge 1 - Sum PBD -- Mean PARM = 0256 [mgkg]

-200 -100 000 100 200

h-values

10L

46L

4L

38L

12L

64L

26L

Labo

rato

ries

Mandels h statistics(Sludge 1 - Sum PBD)

Sludge 1-Sum PBD

Unit mgkg

Mandels k statistics(Soil 3 - Sum PBD)Mandels h statistics(Soil 3 - Sum PBD)

Sample Soil 3 Soil 3 - Sum PBD -- Mean PARM = 0227 [mgkg]

Element Sum PBD

General calcparmT1= 610980E+00T2= 200876E+00T3= 26T4= 100T5= 13106E-02

n= variabelp= 7

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00028 0001 4 -037 000 Fail 00028 00005 4 3 -02226L 01179 0021 2 -036 003 Fail 01179 00208 2 1 -0114L 01305 0031 4 -036 004 Fail 01305 00308 4 3 -010

46L 02065 0035 4 -036 005 Fail 02065 00350 4 3 -00244L 02923 0037 4 -035 005 Fail 02923 00365 4 3 00712L 04051 0015 4 -034 002 Fail 04051 00149 4 3 01864L 04314 0022 4 -033 003 Fail 04314 00223 4 3 0203L 305500 2051 2 247 283 Fail - - 3L - - 3032

Totgem 4017 0276 mgkg 1-level 206 (181) 7 02266 (3L) 7 6Totstd= 10722 0717 5-level 175 (156) 1

RESULTS Mean = 022663 mgkg

Repeatability variance S2r = 000069Repeatability std Sr = 002626 --gt 1159 r = 00735Between lab variance S2L = 002568Reproducibility var S2R = 002637Reproducibility std SR = 016238 --gt 7165 R = 04547Remarks 1 Lab rejected (3L)

000 050 100 150 200 250 300

k-values

10L

26L

4L

46L

44L

12L

64L

3L

Mandels k statistics(Soil 3 - Sum PBD)

-50 00 50 100 150 200 250 300 350

Deviation from Mean

10L

26L

4L

46L

44L

12L

64L

3L

Labo

rato

ries

Soil 3 - Sum PBD -- Mean PARM = 0227 [mgkg]

-100 000 100 200 300

h-values

10L

26L

4L

46L

44L

12L

64L

3L

Labo

rato

ries

Mandels h statistics(Soil 3 - Sum PBD)

Soil 3-Sum PBD

19

Annex 4

Raw data submitted

Sample Compost1 Sample Compost 1 Sample Compost 1Element PBD 99 Element PBD 100 Element PBD 153

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]4L 00021 10L 00008 44L 000504L 00024 10L 00008 44L 000604L 00014 10L 00007 44L 000504L 00020 10L 00011 46L 00004

10L 00029 46L 00007 46L 0001210L 00027 46L 00012 46L 0000410L 00032 46L 00009 46L 0000946L 00025 46L 00007 12L 0000446L 00052 12L 00008 12L 0000846L 00029 12L 00012 12L 0000446L 00026 12L 00008 12L 0000712L 00026 12L 00014 26L 0000512L 00043 26L 00007 26L 0000512L 00026 26L 0000612L 0004726L 0002626L 00024

Sample Compost 1 Sample Compost 1 Sample Compost 1Element PBD 154 Element PBD 183 Element PBD 196

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]4L 00010 46L 00002 46L 00011

46L 00003 46L 00024 46L 0000846L 00007 46L 00021 12L 0000246L 00003 46L 00003 12L 0000346L 00004 12L 00003 12L 0000112L 00003 12L 00011 12L 0000212L 00005 12L 0000312L 00031 12L 0000312L 00006

Sample Compost 1 Sample Compost 1 Sample Compost 1Element PBD 197 Element PBD 203 Element PBD 209

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00002 46L 00010 4L 0004146L 00023 12L 00002 4L 0008946L 00022 12L 00003 44L 0041012L 00004 12L 00002 44L 0084012L 00006 12L 00002 44L 0064012L 00003 44L 0040012L 00004 12L 00079

12L 0007312L 0006512L 0009326L 0004926L 00049

Sample Compost 1Element PBD 47

LAB PARM [mgkg]26L 0003826L 00039

Element PBD 99 Element PBD 47 Element PBD 209LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]

4L 00170 10L 00210 4L 010004L 00200 10L 00220 4L 018004L 00170 10L 00210 4L 012004L 00190 46L 00300 4L 0220010L 00280 46L 00280 46L 0210010L 00300 46L 00250 46L 0200010L 00290 46L 00260 64L 0351846L 00340 64L 00059 64L 0363846L 00330 64L 00057 64L 0364546L 00300 64L 00062 64L 0350846L 00310 64L 00060 12L 0220964L 00194 12L 00191 12L 0177164L 00154 12L 00187 12L 0292264L 00185 12L 00190 12L 0164664L 00159 12L 00186 26L 0329712L 00242 26L 00666 26L 0300012L 00223 26L 0033212L 0022112L 0022226L 0024626L 00400

Element PBD 203 Element PBD 197 Element PBD 196LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00022 46L 00027 46L 0002446L 00014 46L 00024 46L 0002264L 00036 12L 00161 64L 0005864L 00058 12L 00060 64L 0006512L 00063 12L 00061 12L 0004812L 00034 12L 00036 12L 0002512L 00038 12L 0003212L 00027 12L 00022

Element PBD 183 Element PBD 154 Element PBD 153LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00049 4L 00020 4L 0002246L 00035 4L 00022 4L 0002446L 00036 4L 00020 4L 0002246L 00034 46L 00025 4L 0002664L 00027 46L 00025 46L 0004064L 00023 46L 00025 46L 0004264L 00024 46L 00023 46L 0003564L 00020 64L 00034 46L 0003812L 00230 64L 00023 64L 0007412L 00032 64L 00017 64L 0004712L 00031 64L 00011 64L 0004612L 00030 12L 00030 64L 0003026L 00007 12L 00021 12L 0006526L 00008 12L 00021 12L 00029

12L 00021 12L 0003226L 00015 12L 0002926L 00019 26L 00039

26L 00040

Element PBD 100LAB PARM [mgkg]

4L 000384L 000414L 000374L 00038

38L 0219038L 0220038L 0208038L 0220010L 0004410L 0005010L 0004310L 0004646L 0005746L 0005946L 0005346L 0005312L 0004312L 0004512L 0004312L 0004326L 0006226L 00057

Sample Soil 3 Sample Soil 3 Sample Soil 3Element PBD 99 Element PBD 47 Element PBD 100

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]10L 00016 10L 00011 10L 0000310L 00019 10L 00010 10L 0000410L 00013 10L 00012 10L 0000410L 00019 46L 00007 10L 0000246L 00025 46L 00022 46L 0000246L 00025 46L 00005 46L 0000646L 00008 46L 00007 46L 0000246L 00011 12L 00010 46L 0000264L 00005 12L 00017 3L 29100064L 00005 12L 00010 3L 32000064L 00006 12L 00009 26L 0000564L 00007 26L 00007 26L 0000512L 00012 26L 0000712L 0001312L 0001312L 0001226L 0000526L 00006

Sample Soil 3 Sample Soil 3 Sample Soil 3Element PBD 153 Element PBD 154 Element PBD 196

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]44L 00050 4L 00010 46L 0000744L 00050 46L 00001 46L 0001146L 00002 46L 00002 46L 0000846L 00003 46L 00001 46L 0001146L 00002 46L 00002 64L 0002646L 00002 64L 00001 64L 0002664L 00001 64L 00001 64L 0002964L 00001 64L 00001 64L 0003464L 00001 64L 00002 12L 0004564L 00002 12L 00003 12L 00032

12L 00002 12L 0002212L 00002 12L 0002112L 00002

Sample Soil 3 Sample Soil 3 Sample Soil 3Element PBD 197 Element PBD 203 Element PBD 209

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00006 46L 00011 4L 0091046L 00013 46L 00017 4L 0150046L 00011 46L 00015 4L 0120046L 00013 46L 00018 4L 0160012L 00090 64L 00013 44L 0337012L 00056 64L 00014 44L 0281012L 00033 64L 00016 44L 0287012L 00032 64L 00015 44L 02540

12L 00055 46L 0230012L 00041 46L 0220012L 00027 46L 0150012L 00026 46L 01900

64L 0438164L 0401664L 0414464L 0449812L 0367112L 0397812L 0409112L 03838

Sample Soil 3 26L 0102Element PBD 183 26L 0131

LAB PARM [mgkg]46L 0000746L 0000846L 0005846L 0000764L 0000264L 0000364L 0000364L 0000312L 0001512L 0001112L 0000712L 00007

European Commission EUR 23003 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on polybrominated diphenylethers Author(s) E Sobiecka H van der Sloot D Barcelo B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 68 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07403-5 Abstract Project HORIZONTAL is interdisciplinary aiming at a harmonisation and horizontal standardisation of test procedures in particular for sludge soils and biowastes In the context of this standardization project a series of draft technical specification were designed upon an extensive desk study fine-tuned after expert consultations and finally validated in international intercomparisons exercise This report summarises the work performed within the validation study of the draft standard for the determination of polybrominated diphenylethers (PBDE) in soils sludge and treated bio-waste using gas-chromatography method with mass selective detection (GC-MS) It further explains the underlying statistical concept for the calculation of reproducibility and repeatability from intercomparisons data In addition all single values results of the statistical evaluation as well as background information on the validation materials used are described and explained

The mission of the JRC is to provide customer-driven scientific and technical support for the conception development implementation and monitoring of EU policies As a service of the European Commission the JRC functions as a reference centre of science and technology for the Union Close to the policy-making process it serves the common interest of the Member States while being independent of special interests whether private or national

LB

-NA

-23003-EN

-C

18

Table 37 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 4 (Essen) 052 545 261 805 320 403 273 273 lt 005 295 781

Table 38 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 4 (Essen) 7947 442 085 06 086 007 2163 189 2019 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 4 (Essen) 045 19 42 87 683 60 462 61

Table 39 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 4 (Essen) 004

27 Long-term sludge exposed soil from Hohenheim-Stuttgart Germany

Similarly an additional sludge exposed soil was sampled at the University of Hohenheim Stuttgart were a test soil was long-term exposed to elevated concentrations of sewage sludge

Table 40 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 1 (Stuttgart) 0045 0263 1765

Table 41 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 1

(Stuttgart)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

230

006

004

004

nq

nd

nd

498

500

19

Table 42 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 1 (Stuttgart) 069 127 361 262 504 183 252 262 lt 005 266 142

Table 43 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 1 (Stuttgart) 7194 1006 133 186 366 088 7874 275 3571 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 1 (Stuttgart) 123 50 47 212 85 69 991 129

Table 44 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 1 (Stuttgart) 177

18

Annex 3

Statistical calculations

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 47)Mandels h statistics(Sludge 1 - PBD 47)

Sample Sludge 1 NUM

Element PBD 47

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00213 0001 3 -021 005 - - 10L - - NUM46L 00273 0002 4 016 021 - - 46L - - NUM64L 00059 0000 4 -116 002 NUM - 64L - - NUM12L 00188 0000 4 -036 002 - - 12L - - NUM26L 00499 0024 2 157 223 Fail - - 26L - - NUM

Totgem 0025 0005 mgkg 1-level 172 (185) NUM (10L46L64L12L26L) -1Totstd= 0016 0010 5-level 157 (162) 5

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 5 Labs rejected (10L46L64L12L26L)

000 050 100 150 200 250

k-values

10L

46L

64L

12L

26L

Mandels k statistics(Sludge 1 - PBD 47)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

10L

46L

64L

12L

26L

Labo

rato

ries

NUM

-200 -100 000 100 200

h-values

10L

46L

64L

12L

26L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 47)

Sludge 1-PBD 47

Unit mgkg

Mandels k statistics(Soil 3 - PBD 47)Mandels h statistics(Soil 3 - PBD 47)

Sample Soil 3 Soil 3 - PBD 47 -- Mean PARM = 0001 [mgkg]

Element PBD 47

General calcparmT1= 134814E-02T2= 142830E-05T3= 13T4= 45T5= 22767E-06

n= variabelp= 4

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean26L 00007 0000 2 -143 001 00007 00000 2 1 00046L 00010 0001 4 010 181 00010 00008 4 3 00010L 00011 0000 3 049 023 00011 00001 3 2 00012L 00012 0000 4 084 081 00012 00004 4 3 000

Totgem 0001 0000 mgkg 1-level 149 (177) 4 00010 () 4 3Totstd= 0000 0000 5-level 142 (159)

RESULTS Mean = 000100 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000050 --gt 5031 r = 00014Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000050 --gt 5031 R = 00014Remarks none

000 050 100 150 200

k-values

26L

46L

10L

12L

Mandels k statistics(Soil 3 - PBD 47)

00 00 00 00 00 00 00 00 00 00 00

Deviation from Mean

26L

46L

10L

12L

Labo

rato

ries

Soil 3 - PBD 47 -- Mean PARM = 0001 [mgkg]

-200 -100 000 100

h-values

26L

46L

10L

12L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 47)

Soil 3-PBD 47

Unit mgkg

Mandels k statistics(Compost 1 - PBD 99)Mandels h statistics(Compost 1 - PBD 99)

Sample Compost 1 Compost 1 - PBD 99 -- Mean PARM = 0003 [mgkg]

Element PBD 99

General calcparmT1= 492124E-02T2= 148747E-04T3= 17T4= 61T5= 93196E-06

n= variabelp= 5

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00020 0000 4 -137 053 00020 00004 4 3 000

26L 00025 0000 2 -058 024 00025 00002 2 1 00010L 00029 0000 3 012 032 00029 00003 3 2 00046L 00033 0001 4 069 161 00033 00013 4 3 00012L 00036 0001 4 114 140 00036 00011 4 3 000

Totgem 0003 0001 mgkg 1-level 172 (185) 5 00029 () 5 4Totstd= 0001 0001 5-level 157 (162)

RESULTS Mean = 000286 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000088 --gt 3086 r = 00025Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000101 --gt 3525 R = 00028Remarks none

000 050 100 150 200

k-values

4L

26L

10L

46L

12L

Mandels k statistics(Compost 1 - PBD 99)

00 00 00 00 00 00 00 00 00 00

Deviation from Mean

4L

26L

10L

46L

12L

Labo

rato

ries

Compost 1 - PBD 99 -- Mean PARM = 0003 [mgkg]

-200 -100 000 100 200

h-values

4L

26L

10L

46L

12L

Labo

rato

ries

Mandels h statistics(Compost 1 - PBD 99)

Compost 1-PBD 99

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 99)Mandels h statistics(Sludge 1 - PBD 99)

Sample Sludge 1 Sludge 1 - PBD 99 -- Mean PARM = 0024 [mgkg]

Element PBD 99

General calcparmT1= 448050E-01T2= 112113E-02T3= 19T4= 73T5= 32972E-05

n= variabelp= 5

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean64L 00173 0002 4 -118 041 Fail 00173 00019 4 3 -0014L 00183 0002 4 -104 032 00183 00015 4 3 -001

12L 00227 0001 4 -038 022 00227 00010 4 3 00010L 00290 0001 3 055 021 00290 00010 3 2 00146L 00320 0002 4 100 039 00320 00018 4 3 00126L 00323 0011 2 105 234 - - 26L - - 001

Totgem 0025 0003 mgkg 1-level 187 (177) 5 00239 (26L) 5 4Totstd= 0007 0004 5-level 166 (154) 1

RESULTS Mean = 002385 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000153 --gt 643 r = 00043Between lab variance S2L = 000004Reproducibility var S2R = 000004Reproducibility std SR = 000666 --gt 2791 R = 00186Remarks 1 Lab rejected (26L)

000 050 100 150 200 250

k-values

64L

4L

12L

10L

46L

26L

Mandels k statistics(Sludge 1 - PBD 99)

00 00 00 00 00 00 00 00 00 00

Deviation from Mean

64L

4L

12L

10L

46L

26L

Labo

rato

ries

Sludge 1 - PBD 99 -- Mean PARM = 0024 [mgkg]

-200 -100 000 100 200

h-values

64L

4L

12L

10L

46L

26L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 99)

Sludge 1-PBD 99

Unit mgkg

Mandels k statistics(Soil 3 - PBD 99)Mandels h statistics(Soil 3 - PBD 99)

Sample Soil 3 NUM

Element PBD 99

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00017 0000 4 091 068 - - 10L - - NUM46L 00017 0001 4 100 211 - - 46L - - NUM64L 00005 0000 4 -106 023 NUM - 64L - - NUM12L 00012 0000 4 015 014 - - 12L - - NUM26L 00006 0000 2 -101 012 - - 26L - - NUM

Totgem 0001 0000 mgkg 1-level 172 (173) NUM (10L46L64L12L26L) -1Totstd= 0001 0000 5-level 157 (153) 5

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 5 Labs rejected (10L46L64L12L26L)

000 050 100 150 200 250

k-values

10L

46L

64L

12L

26L

Mandels k statistics(Soil 3 - PBD 99)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

10L

46L

64L

12L

26L

Labo

rato

ries

NUM

-200 -100 000 100 200

h-values

10L

46L

64L

12L

26L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 99)

Soil 3-PBD 99

Unit mgkg

Mandels k statistics(Compost 1 - PBD 100)Mandels h statistics(Compost 1 - PBD 100)

Sample Compost 1 Compost 1 - PBD 100 -- Mean PARM = 0001 [mgkg]

Element PBD 100

General calcparmT1= 124272E-02T2= 113129E-05T3= 14T4= 52T5= 46584E-07

n= variabelp= 4

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean26L 00006 0000 2 -131 037 Fail 00006 00001 2 1 00010L 00009 0000 4 003 083 00009 00002 4 3 00046L 00009 0000 4 016 115 00009 00002 4 3 00012L 00011 0000 4 112 136 Fail 00011 00003 4 3 000

Totgem 0001 0000 mgkg 1-level 149 (167) 4 00009 () 4 3Totstd= 0000 0000 5-level 142 (15)

RESULTS Mean = 000085 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000022 --gt 2531 r = 00006Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000025 --gt 2882 R = 00007Remarks none

000 050 100 150

k-values

26L

10L

46L

12L

Mandels k statistics(Compost 1 - PBD 100)

00 00 00 00 00 00 00 00 00 00 00

Deviation from Mean

26L

10L

46L

12L

Labo

rato

ries

Compost 1 - PBD 100 -- Mean PARM = 0001 [mgkg]

-200 -100 000 100 200

h-values

26L

10L

46L

12L

Labo

rato

ries

Mandels h statistics(Compost 1 - PBD 100)

Compost 1-PBD 100

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 100)Mandels h statistics(Sludge 1 - PBD 100)

Sample Sludge 1 Sludge 1 - PBD 100 -- Mean PARM = 0005 [mgkg]

Element PBD 100

General calcparmT1= 852065E-02T2= 412762E-04T3= 18T4= 68T5= 78914E-07

n= variabelp= 5

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00039 0000 4 -042 007 Fail 00039 00002 4 3 000

12L 00044 0000 4 -041 005 Fail 00044 00001 4 3 00010L 00046 0000 4 -041 013 Fail 00046 00003 4 3 00046L 00056 0000 4 -040 012 Fail 00056 00003 4 3 00026L 00059 0000 2 -040 013 Fail 00059 00003 2 1 00038L 02168 0006 4 204 244 Fail - - 38L - - 021

Totgem 0040 0001 mgkg 1-level 187 (177) 5 00049 (38L) 5 4Totstd= 0087 0002 5-level 166 (154) 1

RESULTS Mean = 000486 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000025 --gt 507 r = 00007Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000084 --gt 1731 R = 00024Remarks 1 Lab rejected (38L)

000 050 100 150 200 250

k-values

4L

12L

10L

46L

26L

38L

Mandels k statistics(Sludge 1 - PBD 100)

-01 00 01 01 02 02 03

Deviation from Mean

4L

12L

10L

46L

26L

38L

Labo

rato

ries

Sludge 1 - PBD 100 -- Mean PARM = 0005 [mgkg]

-100 000 100 200 300

h-values

4L

12L

10L

46L

26L

38L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 100)

Sludge 1-PBD 100

Unit mgkg

Mandels k statistics(Soil 3 - PBD 100)Mandels h statistics(Soil 3 - PBD 100)

Sample Soil 3 NUM

Element PBD 100

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00003 0000 4 -050 000 Fail - - 10L - - NUM46L 00003 0000 4 -050 000 Fail NUM - 46L - - NUM3L 305500 2051 2 150 200 Fail - - 3L - - NUM

26L 00005 0000 2 -050 000 Fail - - 26L - - NUM

Totgem 7638 0513 mgkg 1-level 149 (177) NUM (10L46L3L26L) -1Totstd= 15275 1025 5-level 142 (159) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (10L46L3L26L)

000 050 100 150 200

k-values

10L

46L

3L

26L

Mandels k statistics(Soil 3 - PBD 100)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

10L

46L

3L

26L

Labo

rato

ries

NUM

-100 000 100 200

h-values

10L

46L

3L

26L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 100)

Soil 3-PBD 100

Unit mgkg

Mandels k statistics(Compost 1 - PBD 153)Mandels h statistics(Compost 1 - PBD 153)

Sample Compost 1 NUM

Element PBD 153

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean44L 00053 0001 3 150 157 Fail - - 44L - - NUM46L 00007 0000 4 -044 111 Fail - - 46L - - NUM12L 00005 0000 4 -051 055 Fail - - 12L - - NUM26L 00005 0000 2 -054 001 Fail NUM - 26L - - NUM

Totgem 0002 0000 mgkg 1-level 149 (177) NUM (44L46L12L26L) -1Totstd= 0002 0000 5-level 142 (159) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (44L46L12L26L)

000 050 100 150 200

k-values

44L

46L

12L

26L

Mandels k statistics(Compost 1 - PBD 153)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

44L

46L

12L

26L

Labo

rato

ries

NUM

-100 000 100 200

h-values

44L

46L

12L

26L

Labo

rato

ries

Mandels h statistics(Compost 1 - PBD 153)

Compost 1-PBD 153

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 153)Mandels h statistics(Sludge 1 - PBD 153)

Sample Sludge 1 Sludge 1 - PBD 153 -- Mean PARM = 0004 [mgkg]

Element PBD 153

General calcparmT1= 676738E-02T2= 267609E-04T3= 18T4= 68T5= 19626E-05

n= variabelp= 5

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00024 0000 4 -157 017 00024 00002 4 3 000

12L 00038 0002 4 006 154 00038 00018 4 3 00046L 00039 0000 4 011 026 00039 00003 4 3 00026L 00039 0000 2 018 004 00039 00000 2 1 00064L 00049 0002 4 122 159 00049 00018 4 3 000

Totgem 0004 0001 mgkg 1-level 172 (173) 5 00038 () 5 4Totstd= 0001 0001 5-level 157 (153)

RESULTS Mean = 000378 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000123 --gt 3252 r = 00034Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000142 --gt 3754 R = 00040Remarks none

000 050 100 150 200

k-values

4L

12L

46L

26L

64L

Mandels k statistics(Sludge 1 - PBD 153)

00 00 00 00 00 00 00

Deviation from Mean

4L

12L

46L

26L

64L

Labo

rato

ries

Sludge 1 - PBD 153 -- Mean PARM = 0004 [mgkg]

-200 -100 000 100 200

h-values

4L

12L

46L

26L

64L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 153)

Sludge 1-PBD 153

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 154)Mandels h statistics(Sludge 1 - PBD 154)

Sample Sludge 1 NA

Element PBD 154

General calcparmT1= NAT2= NAT3=T4=T5=

n= variabelp=

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00021 0000 3 -100 021 NA - 4L - - NA

46L 00025 0000 4 115 018 NA - 46L - - NA64L 00021 0001 4 -066 179 - - 64L - - NA12L 00023 0000 4 050 085 - - 12L - - NA

Totgem 0002 0000 mgkg 1-level 149 (167) NA (4L46L64L12L) -1Totstd= 0000 0000 5-level 142 (15) 4

RESULTS Mean = NA mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NAReproducibility var S2R = NAReproducibility std SR = NA --gt NA R = NARemarks 4 Labs rejected (4L46L64L12L)

000 050 100 150 200

k-values

4L

46L

64L

12L

Mandels k statistics(Sludge 1 - PBD 154)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

4L

46L

64L

12L

Labo

rato

ries

NA

-100 000 100 200

h-values

4L

46L

64L

12L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 154)

Sludge 1-PBD 154

Unit mgkg

Mandels k statistics(Soil 3 - PBD 154)Mandels h statistics(Soil 3 - PBD 154)

Sample Soil 3 NUM

Element PBD 154

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

4L 00010 - 1 150 Fail - - 4L - - NUM46L 00001 0000 4 -053 096 Fail - - 46L - - NUM64L 00001 0000 4 -056 105 Fail NUM - 64L - - NUM12L 00002 0000 4 -040 099 Fail - - 12L - - NUM

Totgem 000037 0000 mgkg 1-level 149 (164) NUM (4L46L64L12L) -1Totstd= 000042 0000 5-level 142 (153) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (4L46L64L12L)

000 050 100 150

k-values

4L

46L

64L

12L

Mandels k statistics(Soil 3 - PBD 154)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

4L

46L

64L

12L

Labo

rato

ries

NUM

-100 000 100 200

h-values

4L

46L

64L

12L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 154)

Soil 3-PBD 154

Unit mgkg

Mandels k statistics(Compost 1 - PBD 209)Mandels h statistics(Compost 1 - PBD 209)

Sample Compost 1 NUM

Element PBD 209

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00065 0003 2 -049 032 - - 4L - - NUM

44L 00573 0021 4 150 197 Fail - - 44L - - NUM12L 00078 0001 4 -045 011 - - 12L - - NUM26L 00049 0000 2 -056 000 NUM - 26L - - NUM

Totgem 0019 0006 mgkg 1-level 149 (177) NUM (4L44L12L26L) -1Totstd= 0025 0010 5-level 142 (159) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (4L44L12L26L)

000 050 100 150 200

k-values

4L

44L

12L

26L

Mandels k statistics(Compost 1 - PBD 209)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

4L

44L

12L

26L

Labo

rato

ries

NUM

-100 000 100 200

h-values

4L

44L

12L

26L

Labo

rato

ries

Mandels h statistics(Compost 1 - PBD 209)

Compost 1-PBD 209

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 209)Mandels h statistics(Sludge 1 - PBD 209)

Sample Sludge 1 Sludge 1 - PBD 209 -- Mean PARM = 0249 [mgkg]

Element PBD 209

General calcparmT1= 394542E+00T2= 107296E+00T3= 16T4= 56T5= 19723E-02

n= variabelp= 5

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 01550 0055 4 -112 148 Fail 01550 00551 4 3 -009

46L 02050 0007 2 -053 019 02050 00071 2 1 -00412L 02137 0058 4 -042 155 02137 00576 4 3 -00426L 03149 0021 2 078 057 Fail 03149 00210 2 1 00764L 03577 0007 4 129 020 Fail 03577 00074 4 3 011

Totgem 0249 0030 mgkg 1-level 172 (185) 5 02493 () 5 4Totstd= 0084 0025 5-level 157 (162)

RESULTS Mean = 024926 mgkg

Repeatability variance S2r = 000179Repeatability std Sr = 004234 --gt 1699 r = 01186Between lab variance S2L = 000743Reproducibility var S2R = 000922Reproducibility std SR = 009604 --gt 3853 R = 02689Remarks none

000 050 100 150 200

k-values

4L

46L

12L

26L

64L

Mandels k statistics(Sludge 1 - PBD 209)

-01 -01 00 01 01 02

Deviation from Mean

4L

46L

12L

26L

64L

Labo

rato

ries

Sludge 1 - PBD 209 -- Mean PARM = 0249 [mgkg]

-200 -100 000 100 200

h-values

4L

46L

12L

26L

64L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 209)

Sludge 1-PBD 209

Unit mgkg

Mandels k statistics(Soil 3 - PBD 209)Mandels h statistics(Soil 3 - PBD 209)

Sample Soil 3 Soil 3 - PBD 209 -- Mean PARM = 0258 [mgkg]

Element PBD 209

General calcparmT1= 596398E+00T2= 191917E+00T3= 22T4= 84T5= 13249E-02

n= variabelp= 6

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean26L 01162 0021 2 -108 074 Fail 01162 00207 2 1 -0144L 01303 0031 4 -097 111 Fail 01303 00312 4 3 -013

46L 01975 0036 4 -046 128 Fail 01975 00359 4 3 -00644L 02898 0035 4 024 124 Fail 02898 00346 4 3 00312L 03895 0018 4 100 065 Fail 03895 00181 4 3 01364L 04260 0022 4 127 078 Fail 04260 00219 4 3 017

Totgem 0258 0027 mgkg 1-level 187 (177) 6 02582 () 6 5Totstd= 0132 0008 5-level 166 (154)

RESULTS Mean = 025818 mgkg

Repeatability variance S2r = 000083Repeatability std Sr = 002878 --gt 1115 r = 00806Between lab variance S2L = 001640Reproducibility var S2R = 001723Reproducibility std SR = 013127 --gt 5084 R = 03676Remarks none

000 050 100 150

k-values

26L

4L

46L

44L

12L

64L

Mandels k statistics(Soil 3 - PBD 209)

-02 -01 -01 00 01 01 02 02

Deviation from Mean

26L

4L

46L

44L

12L

64L

Labo

rato

ries

Soil 3 - PBD 209 -- Mean PARM = 0258 [mgkg]

-200 -100 000 100 200

h-values

26L

4L

46L

44L

12L

64L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 209)

Soil 3-PBD 209

Unit mgkg

Mandels k statistics(Compost 1 - Sum PBD)Mandels h statistics(Compost 1 - Sum PBD)

Sample Compost 1 Compost 1 - Sum PBD -- Mean PARM = 0009 [mgkg]

Element Sum PBD

General calcparmT1= 154064E-01T2= 169065E-03T3= 18T4= 68T5= 11354E-04

n= variabelp= 5

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00031 0002 4 -067 016 00031 00016 4 3 -0014L 00055 0005 4 -056 048 00055 00047 4 3 000

46L 00085 0003 4 -042 031 00085 00030 4 3 00026L 00123 0000 2 -024 003 00123 00002 2 1 00012L 00154 0002 4 -011 021 00154 00021 4 3 00144L 00613 0023 4 200 237 Fail - - 44L - - 005

Totgem 0018 0006 mgkg 1-level 187 (177) 5 00089 (44L) 5 4Totstd= 0022 0009 5-level 166 (154) 1

RESULTS Mean = 000893 mgkg

Repeatability variance S2r = 000001Repeatability std Sr = 000296 --gt 3308 r = 00083Between lab variance S2L = 000002Reproducibility var S2R = 000003Reproducibility std SR = 000570 --gt 6374 R = 00159Remarks 1 Lab rejected (44L)

000 050 100 150 200 250

k-values

10L

4L

46L

26L

12L

44L

Mandels k statistics(Compost 1 - Sum PBD)

00 00 00 00 00 00 01 01

Deviation from Mean

10L

4L

46L

26L

12L

44L

Labo

rato

ries

Compost 1 - Sum PBD -- Mean PARM = 0009 [mgkg]

-100 000 100 200

h-values

10L

4L

46L

26L

12L

44L

Labo

rato

ries

Mandels h statistics(Compost 1 - Sum PBD)

Compost 1-Sum PBD

Unit mgkg

Mandels k statistics(Sludge 1 - Sum PBD)Mandels h statistics(Sludge 1 - Sum PBD)

Sample Sludge 1 Sludge 1 - Sum PBD -- Mean PARM = 0256 [mgkg]

Element Sum PBD

General calcparmT1= 531806E+00T2= 162188E+00T3= 22T4= 84T5= 25223E-02

n= variabelp= 6

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00423 0025 4 -156 044 Fail 00423 00252 4 3 -02146L 01808 0118 4 -049 205 - - 46L - - -0074L 01810 0056 4 -049 097 01810 00558 4 3 -007

38L 02168 0006 4 -022 010 02168 00059 4 3 -00412L 02890 0065 4 034 113 02890 00647 4 3 00364L 03958 0008 4 116 014 Fail 03958 00079 4 3 01426L 04094 0034 2 126 059 Fail 04094 00337 2 1 015

Totgem 0245 0044 mgkg 1-level 198 (179) 6 02557 (46L) 6 5Totstd= 0130 0039 5-level 171 (155) 1

RESULTS Mean = 025570 mgkg

Repeatability variance S2r = 000158Repeatability std Sr = 003970 --gt 1553 r = 01112Between lab variance S2L = 001807Reproducibility var S2R = 001964Reproducibility std SR = 014015 --gt 5481 R = 03924Remarks 1 Lab rejected (46L)

000 050 100 150 200 250

k-values

10L

46L

4L

38L

12L

64L

26L

Mandels k statistics(Sludge 1 - Sum PBD)

-03 -02 -02 -01 -01 00 01 01 02 02

Deviation from Mean

10L

46L

4L

38L

12L

64L

26L

Labo

rato

ries

Sludge 1 - Sum PBD -- Mean PARM = 0256 [mgkg]

-200 -100 000 100 200

h-values

10L

46L

4L

38L

12L

64L

26L

Labo

rato

ries

Mandels h statistics(Sludge 1 - Sum PBD)

Sludge 1-Sum PBD

Unit mgkg

Mandels k statistics(Soil 3 - Sum PBD)Mandels h statistics(Soil 3 - Sum PBD)

Sample Soil 3 Soil 3 - Sum PBD -- Mean PARM = 0227 [mgkg]

Element Sum PBD

General calcparmT1= 610980E+00T2= 200876E+00T3= 26T4= 100T5= 13106E-02

n= variabelp= 7

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00028 0001 4 -037 000 Fail 00028 00005 4 3 -02226L 01179 0021 2 -036 003 Fail 01179 00208 2 1 -0114L 01305 0031 4 -036 004 Fail 01305 00308 4 3 -010

46L 02065 0035 4 -036 005 Fail 02065 00350 4 3 -00244L 02923 0037 4 -035 005 Fail 02923 00365 4 3 00712L 04051 0015 4 -034 002 Fail 04051 00149 4 3 01864L 04314 0022 4 -033 003 Fail 04314 00223 4 3 0203L 305500 2051 2 247 283 Fail - - 3L - - 3032

Totgem 4017 0276 mgkg 1-level 206 (181) 7 02266 (3L) 7 6Totstd= 10722 0717 5-level 175 (156) 1

RESULTS Mean = 022663 mgkg

Repeatability variance S2r = 000069Repeatability std Sr = 002626 --gt 1159 r = 00735Between lab variance S2L = 002568Reproducibility var S2R = 002637Reproducibility std SR = 016238 --gt 7165 R = 04547Remarks 1 Lab rejected (3L)

000 050 100 150 200 250 300

k-values

10L

26L

4L

46L

44L

12L

64L

3L

Mandels k statistics(Soil 3 - Sum PBD)

-50 00 50 100 150 200 250 300 350

Deviation from Mean

10L

26L

4L

46L

44L

12L

64L

3L

Labo

rato

ries

Soil 3 - Sum PBD -- Mean PARM = 0227 [mgkg]

-100 000 100 200 300

h-values

10L

26L

4L

46L

44L

12L

64L

3L

Labo

rato

ries

Mandels h statistics(Soil 3 - Sum PBD)

Soil 3-Sum PBD

19

Annex 4

Raw data submitted

Sample Compost1 Sample Compost 1 Sample Compost 1Element PBD 99 Element PBD 100 Element PBD 153

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]4L 00021 10L 00008 44L 000504L 00024 10L 00008 44L 000604L 00014 10L 00007 44L 000504L 00020 10L 00011 46L 00004

10L 00029 46L 00007 46L 0001210L 00027 46L 00012 46L 0000410L 00032 46L 00009 46L 0000946L 00025 46L 00007 12L 0000446L 00052 12L 00008 12L 0000846L 00029 12L 00012 12L 0000446L 00026 12L 00008 12L 0000712L 00026 12L 00014 26L 0000512L 00043 26L 00007 26L 0000512L 00026 26L 0000612L 0004726L 0002626L 00024

Sample Compost 1 Sample Compost 1 Sample Compost 1Element PBD 154 Element PBD 183 Element PBD 196

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]4L 00010 46L 00002 46L 00011

46L 00003 46L 00024 46L 0000846L 00007 46L 00021 12L 0000246L 00003 46L 00003 12L 0000346L 00004 12L 00003 12L 0000112L 00003 12L 00011 12L 0000212L 00005 12L 0000312L 00031 12L 0000312L 00006

Sample Compost 1 Sample Compost 1 Sample Compost 1Element PBD 197 Element PBD 203 Element PBD 209

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00002 46L 00010 4L 0004146L 00023 12L 00002 4L 0008946L 00022 12L 00003 44L 0041012L 00004 12L 00002 44L 0084012L 00006 12L 00002 44L 0064012L 00003 44L 0040012L 00004 12L 00079

12L 0007312L 0006512L 0009326L 0004926L 00049

Sample Compost 1Element PBD 47

LAB PARM [mgkg]26L 0003826L 00039

Element PBD 99 Element PBD 47 Element PBD 209LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]

4L 00170 10L 00210 4L 010004L 00200 10L 00220 4L 018004L 00170 10L 00210 4L 012004L 00190 46L 00300 4L 0220010L 00280 46L 00280 46L 0210010L 00300 46L 00250 46L 0200010L 00290 46L 00260 64L 0351846L 00340 64L 00059 64L 0363846L 00330 64L 00057 64L 0364546L 00300 64L 00062 64L 0350846L 00310 64L 00060 12L 0220964L 00194 12L 00191 12L 0177164L 00154 12L 00187 12L 0292264L 00185 12L 00190 12L 0164664L 00159 12L 00186 26L 0329712L 00242 26L 00666 26L 0300012L 00223 26L 0033212L 0022112L 0022226L 0024626L 00400

Element PBD 203 Element PBD 197 Element PBD 196LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00022 46L 00027 46L 0002446L 00014 46L 00024 46L 0002264L 00036 12L 00161 64L 0005864L 00058 12L 00060 64L 0006512L 00063 12L 00061 12L 0004812L 00034 12L 00036 12L 0002512L 00038 12L 0003212L 00027 12L 00022

Element PBD 183 Element PBD 154 Element PBD 153LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00049 4L 00020 4L 0002246L 00035 4L 00022 4L 0002446L 00036 4L 00020 4L 0002246L 00034 46L 00025 4L 0002664L 00027 46L 00025 46L 0004064L 00023 46L 00025 46L 0004264L 00024 46L 00023 46L 0003564L 00020 64L 00034 46L 0003812L 00230 64L 00023 64L 0007412L 00032 64L 00017 64L 0004712L 00031 64L 00011 64L 0004612L 00030 12L 00030 64L 0003026L 00007 12L 00021 12L 0006526L 00008 12L 00021 12L 00029

12L 00021 12L 0003226L 00015 12L 0002926L 00019 26L 00039

26L 00040

Element PBD 100LAB PARM [mgkg]

4L 000384L 000414L 000374L 00038

38L 0219038L 0220038L 0208038L 0220010L 0004410L 0005010L 0004310L 0004646L 0005746L 0005946L 0005346L 0005312L 0004312L 0004512L 0004312L 0004326L 0006226L 00057

Sample Soil 3 Sample Soil 3 Sample Soil 3Element PBD 99 Element PBD 47 Element PBD 100

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]10L 00016 10L 00011 10L 0000310L 00019 10L 00010 10L 0000410L 00013 10L 00012 10L 0000410L 00019 46L 00007 10L 0000246L 00025 46L 00022 46L 0000246L 00025 46L 00005 46L 0000646L 00008 46L 00007 46L 0000246L 00011 12L 00010 46L 0000264L 00005 12L 00017 3L 29100064L 00005 12L 00010 3L 32000064L 00006 12L 00009 26L 0000564L 00007 26L 00007 26L 0000512L 00012 26L 0000712L 0001312L 0001312L 0001226L 0000526L 00006

Sample Soil 3 Sample Soil 3 Sample Soil 3Element PBD 153 Element PBD 154 Element PBD 196

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]44L 00050 4L 00010 46L 0000744L 00050 46L 00001 46L 0001146L 00002 46L 00002 46L 0000846L 00003 46L 00001 46L 0001146L 00002 46L 00002 64L 0002646L 00002 64L 00001 64L 0002664L 00001 64L 00001 64L 0002964L 00001 64L 00001 64L 0003464L 00001 64L 00002 12L 0004564L 00002 12L 00003 12L 00032

12L 00002 12L 0002212L 00002 12L 0002112L 00002

Sample Soil 3 Sample Soil 3 Sample Soil 3Element PBD 197 Element PBD 203 Element PBD 209

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00006 46L 00011 4L 0091046L 00013 46L 00017 4L 0150046L 00011 46L 00015 4L 0120046L 00013 46L 00018 4L 0160012L 00090 64L 00013 44L 0337012L 00056 64L 00014 44L 0281012L 00033 64L 00016 44L 0287012L 00032 64L 00015 44L 02540

12L 00055 46L 0230012L 00041 46L 0220012L 00027 46L 0150012L 00026 46L 01900

64L 0438164L 0401664L 0414464L 0449812L 0367112L 0397812L 0409112L 03838

Sample Soil 3 26L 0102Element PBD 183 26L 0131

LAB PARM [mgkg]46L 0000746L 0000846L 0005846L 0000764L 0000264L 0000364L 0000364L 0000312L 0001512L 0001112L 0000712L 00007

European Commission EUR 23003 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on polybrominated diphenylethers Author(s) E Sobiecka H van der Sloot D Barcelo B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 68 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07403-5 Abstract Project HORIZONTAL is interdisciplinary aiming at a harmonisation and horizontal standardisation of test procedures in particular for sludge soils and biowastes In the context of this standardization project a series of draft technical specification were designed upon an extensive desk study fine-tuned after expert consultations and finally validated in international intercomparisons exercise This report summarises the work performed within the validation study of the draft standard for the determination of polybrominated diphenylethers (PBDE) in soils sludge and treated bio-waste using gas-chromatography method with mass selective detection (GC-MS) It further explains the underlying statistical concept for the calculation of reproducibility and repeatability from intercomparisons data In addition all single values results of the statistical evaluation as well as background information on the validation materials used are described and explained

The mission of the JRC is to provide customer-driven scientific and technical support for the conception development implementation and monitoring of EU policies As a service of the European Commission the JRC functions as a reference centre of science and technology for the Union Close to the policy-making process it serves the common interest of the Member States while being independent of special interests whether private or national

LB

-NA

-23003-EN

-C

19

Table 42 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 1 (Stuttgart) 069 127 361 262 504 183 252 262 lt 005 266 142

Table 43 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 1 (Stuttgart) 7194 1006 133 186 366 088 7874 275 3571 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 1 (Stuttgart) 123 50 47 212 85 69 991 129

Table 44 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 1 (Stuttgart) 177

18

Annex 3

Statistical calculations

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 47)Mandels h statistics(Sludge 1 - PBD 47)

Sample Sludge 1 NUM

Element PBD 47

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00213 0001 3 -021 005 - - 10L - - NUM46L 00273 0002 4 016 021 - - 46L - - NUM64L 00059 0000 4 -116 002 NUM - 64L - - NUM12L 00188 0000 4 -036 002 - - 12L - - NUM26L 00499 0024 2 157 223 Fail - - 26L - - NUM

Totgem 0025 0005 mgkg 1-level 172 (185) NUM (10L46L64L12L26L) -1Totstd= 0016 0010 5-level 157 (162) 5

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 5 Labs rejected (10L46L64L12L26L)

000 050 100 150 200 250

k-values

10L

46L

64L

12L

26L

Mandels k statistics(Sludge 1 - PBD 47)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

10L

46L

64L

12L

26L

Labo

rato

ries

NUM

-200 -100 000 100 200

h-values

10L

46L

64L

12L

26L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 47)

Sludge 1-PBD 47

Unit mgkg

Mandels k statistics(Soil 3 - PBD 47)Mandels h statistics(Soil 3 - PBD 47)

Sample Soil 3 Soil 3 - PBD 47 -- Mean PARM = 0001 [mgkg]

Element PBD 47

General calcparmT1= 134814E-02T2= 142830E-05T3= 13T4= 45T5= 22767E-06

n= variabelp= 4

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean26L 00007 0000 2 -143 001 00007 00000 2 1 00046L 00010 0001 4 010 181 00010 00008 4 3 00010L 00011 0000 3 049 023 00011 00001 3 2 00012L 00012 0000 4 084 081 00012 00004 4 3 000

Totgem 0001 0000 mgkg 1-level 149 (177) 4 00010 () 4 3Totstd= 0000 0000 5-level 142 (159)

RESULTS Mean = 000100 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000050 --gt 5031 r = 00014Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000050 --gt 5031 R = 00014Remarks none

000 050 100 150 200

k-values

26L

46L

10L

12L

Mandels k statistics(Soil 3 - PBD 47)

00 00 00 00 00 00 00 00 00 00 00

Deviation from Mean

26L

46L

10L

12L

Labo

rato

ries

Soil 3 - PBD 47 -- Mean PARM = 0001 [mgkg]

-200 -100 000 100

h-values

26L

46L

10L

12L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 47)

Soil 3-PBD 47

Unit mgkg

Mandels k statistics(Compost 1 - PBD 99)Mandels h statistics(Compost 1 - PBD 99)

Sample Compost 1 Compost 1 - PBD 99 -- Mean PARM = 0003 [mgkg]

Element PBD 99

General calcparmT1= 492124E-02T2= 148747E-04T3= 17T4= 61T5= 93196E-06

n= variabelp= 5

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00020 0000 4 -137 053 00020 00004 4 3 000

26L 00025 0000 2 -058 024 00025 00002 2 1 00010L 00029 0000 3 012 032 00029 00003 3 2 00046L 00033 0001 4 069 161 00033 00013 4 3 00012L 00036 0001 4 114 140 00036 00011 4 3 000

Totgem 0003 0001 mgkg 1-level 172 (185) 5 00029 () 5 4Totstd= 0001 0001 5-level 157 (162)

RESULTS Mean = 000286 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000088 --gt 3086 r = 00025Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000101 --gt 3525 R = 00028Remarks none

000 050 100 150 200

k-values

4L

26L

10L

46L

12L

Mandels k statistics(Compost 1 - PBD 99)

00 00 00 00 00 00 00 00 00 00

Deviation from Mean

4L

26L

10L

46L

12L

Labo

rato

ries

Compost 1 - PBD 99 -- Mean PARM = 0003 [mgkg]

-200 -100 000 100 200

h-values

4L

26L

10L

46L

12L

Labo

rato

ries

Mandels h statistics(Compost 1 - PBD 99)

Compost 1-PBD 99

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 99)Mandels h statistics(Sludge 1 - PBD 99)

Sample Sludge 1 Sludge 1 - PBD 99 -- Mean PARM = 0024 [mgkg]

Element PBD 99

General calcparmT1= 448050E-01T2= 112113E-02T3= 19T4= 73T5= 32972E-05

n= variabelp= 5

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean64L 00173 0002 4 -118 041 Fail 00173 00019 4 3 -0014L 00183 0002 4 -104 032 00183 00015 4 3 -001

12L 00227 0001 4 -038 022 00227 00010 4 3 00010L 00290 0001 3 055 021 00290 00010 3 2 00146L 00320 0002 4 100 039 00320 00018 4 3 00126L 00323 0011 2 105 234 - - 26L - - 001

Totgem 0025 0003 mgkg 1-level 187 (177) 5 00239 (26L) 5 4Totstd= 0007 0004 5-level 166 (154) 1

RESULTS Mean = 002385 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000153 --gt 643 r = 00043Between lab variance S2L = 000004Reproducibility var S2R = 000004Reproducibility std SR = 000666 --gt 2791 R = 00186Remarks 1 Lab rejected (26L)

000 050 100 150 200 250

k-values

64L

4L

12L

10L

46L

26L

Mandels k statistics(Sludge 1 - PBD 99)

00 00 00 00 00 00 00 00 00 00

Deviation from Mean

64L

4L

12L

10L

46L

26L

Labo

rato

ries

Sludge 1 - PBD 99 -- Mean PARM = 0024 [mgkg]

-200 -100 000 100 200

h-values

64L

4L

12L

10L

46L

26L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 99)

Sludge 1-PBD 99

Unit mgkg

Mandels k statistics(Soil 3 - PBD 99)Mandels h statistics(Soil 3 - PBD 99)

Sample Soil 3 NUM

Element PBD 99

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00017 0000 4 091 068 - - 10L - - NUM46L 00017 0001 4 100 211 - - 46L - - NUM64L 00005 0000 4 -106 023 NUM - 64L - - NUM12L 00012 0000 4 015 014 - - 12L - - NUM26L 00006 0000 2 -101 012 - - 26L - - NUM

Totgem 0001 0000 mgkg 1-level 172 (173) NUM (10L46L64L12L26L) -1Totstd= 0001 0000 5-level 157 (153) 5

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 5 Labs rejected (10L46L64L12L26L)

000 050 100 150 200 250

k-values

10L

46L

64L

12L

26L

Mandels k statistics(Soil 3 - PBD 99)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

10L

46L

64L

12L

26L

Labo

rato

ries

NUM

-200 -100 000 100 200

h-values

10L

46L

64L

12L

26L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 99)

Soil 3-PBD 99

Unit mgkg

Mandels k statistics(Compost 1 - PBD 100)Mandels h statistics(Compost 1 - PBD 100)

Sample Compost 1 Compost 1 - PBD 100 -- Mean PARM = 0001 [mgkg]

Element PBD 100

General calcparmT1= 124272E-02T2= 113129E-05T3= 14T4= 52T5= 46584E-07

n= variabelp= 4

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean26L 00006 0000 2 -131 037 Fail 00006 00001 2 1 00010L 00009 0000 4 003 083 00009 00002 4 3 00046L 00009 0000 4 016 115 00009 00002 4 3 00012L 00011 0000 4 112 136 Fail 00011 00003 4 3 000

Totgem 0001 0000 mgkg 1-level 149 (167) 4 00009 () 4 3Totstd= 0000 0000 5-level 142 (15)

RESULTS Mean = 000085 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000022 --gt 2531 r = 00006Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000025 --gt 2882 R = 00007Remarks none

000 050 100 150

k-values

26L

10L

46L

12L

Mandels k statistics(Compost 1 - PBD 100)

00 00 00 00 00 00 00 00 00 00 00

Deviation from Mean

26L

10L

46L

12L

Labo

rato

ries

Compost 1 - PBD 100 -- Mean PARM = 0001 [mgkg]

-200 -100 000 100 200

h-values

26L

10L

46L

12L

Labo

rato

ries

Mandels h statistics(Compost 1 - PBD 100)

Compost 1-PBD 100

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 100)Mandels h statistics(Sludge 1 - PBD 100)

Sample Sludge 1 Sludge 1 - PBD 100 -- Mean PARM = 0005 [mgkg]

Element PBD 100

General calcparmT1= 852065E-02T2= 412762E-04T3= 18T4= 68T5= 78914E-07

n= variabelp= 5

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00039 0000 4 -042 007 Fail 00039 00002 4 3 000

12L 00044 0000 4 -041 005 Fail 00044 00001 4 3 00010L 00046 0000 4 -041 013 Fail 00046 00003 4 3 00046L 00056 0000 4 -040 012 Fail 00056 00003 4 3 00026L 00059 0000 2 -040 013 Fail 00059 00003 2 1 00038L 02168 0006 4 204 244 Fail - - 38L - - 021

Totgem 0040 0001 mgkg 1-level 187 (177) 5 00049 (38L) 5 4Totstd= 0087 0002 5-level 166 (154) 1

RESULTS Mean = 000486 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000025 --gt 507 r = 00007Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000084 --gt 1731 R = 00024Remarks 1 Lab rejected (38L)

000 050 100 150 200 250

k-values

4L

12L

10L

46L

26L

38L

Mandels k statistics(Sludge 1 - PBD 100)

-01 00 01 01 02 02 03

Deviation from Mean

4L

12L

10L

46L

26L

38L

Labo

rato

ries

Sludge 1 - PBD 100 -- Mean PARM = 0005 [mgkg]

-100 000 100 200 300

h-values

4L

12L

10L

46L

26L

38L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 100)

Sludge 1-PBD 100

Unit mgkg

Mandels k statistics(Soil 3 - PBD 100)Mandels h statistics(Soil 3 - PBD 100)

Sample Soil 3 NUM

Element PBD 100

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00003 0000 4 -050 000 Fail - - 10L - - NUM46L 00003 0000 4 -050 000 Fail NUM - 46L - - NUM3L 305500 2051 2 150 200 Fail - - 3L - - NUM

26L 00005 0000 2 -050 000 Fail - - 26L - - NUM

Totgem 7638 0513 mgkg 1-level 149 (177) NUM (10L46L3L26L) -1Totstd= 15275 1025 5-level 142 (159) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (10L46L3L26L)

000 050 100 150 200

k-values

10L

46L

3L

26L

Mandels k statistics(Soil 3 - PBD 100)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

10L

46L

3L

26L

Labo

rato

ries

NUM

-100 000 100 200

h-values

10L

46L

3L

26L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 100)

Soil 3-PBD 100

Unit mgkg

Mandels k statistics(Compost 1 - PBD 153)Mandels h statistics(Compost 1 - PBD 153)

Sample Compost 1 NUM

Element PBD 153

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean44L 00053 0001 3 150 157 Fail - - 44L - - NUM46L 00007 0000 4 -044 111 Fail - - 46L - - NUM12L 00005 0000 4 -051 055 Fail - - 12L - - NUM26L 00005 0000 2 -054 001 Fail NUM - 26L - - NUM

Totgem 0002 0000 mgkg 1-level 149 (177) NUM (44L46L12L26L) -1Totstd= 0002 0000 5-level 142 (159) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (44L46L12L26L)

000 050 100 150 200

k-values

44L

46L

12L

26L

Mandels k statistics(Compost 1 - PBD 153)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

44L

46L

12L

26L

Labo

rato

ries

NUM

-100 000 100 200

h-values

44L

46L

12L

26L

Labo

rato

ries

Mandels h statistics(Compost 1 - PBD 153)

Compost 1-PBD 153

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 153)Mandels h statistics(Sludge 1 - PBD 153)

Sample Sludge 1 Sludge 1 - PBD 153 -- Mean PARM = 0004 [mgkg]

Element PBD 153

General calcparmT1= 676738E-02T2= 267609E-04T3= 18T4= 68T5= 19626E-05

n= variabelp= 5

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00024 0000 4 -157 017 00024 00002 4 3 000

12L 00038 0002 4 006 154 00038 00018 4 3 00046L 00039 0000 4 011 026 00039 00003 4 3 00026L 00039 0000 2 018 004 00039 00000 2 1 00064L 00049 0002 4 122 159 00049 00018 4 3 000

Totgem 0004 0001 mgkg 1-level 172 (173) 5 00038 () 5 4Totstd= 0001 0001 5-level 157 (153)

RESULTS Mean = 000378 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000123 --gt 3252 r = 00034Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000142 --gt 3754 R = 00040Remarks none

000 050 100 150 200

k-values

4L

12L

46L

26L

64L

Mandels k statistics(Sludge 1 - PBD 153)

00 00 00 00 00 00 00

Deviation from Mean

4L

12L

46L

26L

64L

Labo

rato

ries

Sludge 1 - PBD 153 -- Mean PARM = 0004 [mgkg]

-200 -100 000 100 200

h-values

4L

12L

46L

26L

64L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 153)

Sludge 1-PBD 153

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 154)Mandels h statistics(Sludge 1 - PBD 154)

Sample Sludge 1 NA

Element PBD 154

General calcparmT1= NAT2= NAT3=T4=T5=

n= variabelp=

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00021 0000 3 -100 021 NA - 4L - - NA

46L 00025 0000 4 115 018 NA - 46L - - NA64L 00021 0001 4 -066 179 - - 64L - - NA12L 00023 0000 4 050 085 - - 12L - - NA

Totgem 0002 0000 mgkg 1-level 149 (167) NA (4L46L64L12L) -1Totstd= 0000 0000 5-level 142 (15) 4

RESULTS Mean = NA mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NAReproducibility var S2R = NAReproducibility std SR = NA --gt NA R = NARemarks 4 Labs rejected (4L46L64L12L)

000 050 100 150 200

k-values

4L

46L

64L

12L

Mandels k statistics(Sludge 1 - PBD 154)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

4L

46L

64L

12L

Labo

rato

ries

NA

-100 000 100 200

h-values

4L

46L

64L

12L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 154)

Sludge 1-PBD 154

Unit mgkg

Mandels k statistics(Soil 3 - PBD 154)Mandels h statistics(Soil 3 - PBD 154)

Sample Soil 3 NUM

Element PBD 154

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

4L 00010 - 1 150 Fail - - 4L - - NUM46L 00001 0000 4 -053 096 Fail - - 46L - - NUM64L 00001 0000 4 -056 105 Fail NUM - 64L - - NUM12L 00002 0000 4 -040 099 Fail - - 12L - - NUM

Totgem 000037 0000 mgkg 1-level 149 (164) NUM (4L46L64L12L) -1Totstd= 000042 0000 5-level 142 (153) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (4L46L64L12L)

000 050 100 150

k-values

4L

46L

64L

12L

Mandels k statistics(Soil 3 - PBD 154)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

4L

46L

64L

12L

Labo

rato

ries

NUM

-100 000 100 200

h-values

4L

46L

64L

12L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 154)

Soil 3-PBD 154

Unit mgkg

Mandels k statistics(Compost 1 - PBD 209)Mandels h statistics(Compost 1 - PBD 209)

Sample Compost 1 NUM

Element PBD 209

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00065 0003 2 -049 032 - - 4L - - NUM

44L 00573 0021 4 150 197 Fail - - 44L - - NUM12L 00078 0001 4 -045 011 - - 12L - - NUM26L 00049 0000 2 -056 000 NUM - 26L - - NUM

Totgem 0019 0006 mgkg 1-level 149 (177) NUM (4L44L12L26L) -1Totstd= 0025 0010 5-level 142 (159) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (4L44L12L26L)

000 050 100 150 200

k-values

4L

44L

12L

26L

Mandels k statistics(Compost 1 - PBD 209)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

4L

44L

12L

26L

Labo

rato

ries

NUM

-100 000 100 200

h-values

4L

44L

12L

26L

Labo

rato

ries

Mandels h statistics(Compost 1 - PBD 209)

Compost 1-PBD 209

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 209)Mandels h statistics(Sludge 1 - PBD 209)

Sample Sludge 1 Sludge 1 - PBD 209 -- Mean PARM = 0249 [mgkg]

Element PBD 209

General calcparmT1= 394542E+00T2= 107296E+00T3= 16T4= 56T5= 19723E-02

n= variabelp= 5

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 01550 0055 4 -112 148 Fail 01550 00551 4 3 -009

46L 02050 0007 2 -053 019 02050 00071 2 1 -00412L 02137 0058 4 -042 155 02137 00576 4 3 -00426L 03149 0021 2 078 057 Fail 03149 00210 2 1 00764L 03577 0007 4 129 020 Fail 03577 00074 4 3 011

Totgem 0249 0030 mgkg 1-level 172 (185) 5 02493 () 5 4Totstd= 0084 0025 5-level 157 (162)

RESULTS Mean = 024926 mgkg

Repeatability variance S2r = 000179Repeatability std Sr = 004234 --gt 1699 r = 01186Between lab variance S2L = 000743Reproducibility var S2R = 000922Reproducibility std SR = 009604 --gt 3853 R = 02689Remarks none

000 050 100 150 200

k-values

4L

46L

12L

26L

64L

Mandels k statistics(Sludge 1 - PBD 209)

-01 -01 00 01 01 02

Deviation from Mean

4L

46L

12L

26L

64L

Labo

rato

ries

Sludge 1 - PBD 209 -- Mean PARM = 0249 [mgkg]

-200 -100 000 100 200

h-values

4L

46L

12L

26L

64L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 209)

Sludge 1-PBD 209

Unit mgkg

Mandels k statistics(Soil 3 - PBD 209)Mandels h statistics(Soil 3 - PBD 209)

Sample Soil 3 Soil 3 - PBD 209 -- Mean PARM = 0258 [mgkg]

Element PBD 209

General calcparmT1= 596398E+00T2= 191917E+00T3= 22T4= 84T5= 13249E-02

n= variabelp= 6

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean26L 01162 0021 2 -108 074 Fail 01162 00207 2 1 -0144L 01303 0031 4 -097 111 Fail 01303 00312 4 3 -013

46L 01975 0036 4 -046 128 Fail 01975 00359 4 3 -00644L 02898 0035 4 024 124 Fail 02898 00346 4 3 00312L 03895 0018 4 100 065 Fail 03895 00181 4 3 01364L 04260 0022 4 127 078 Fail 04260 00219 4 3 017

Totgem 0258 0027 mgkg 1-level 187 (177) 6 02582 () 6 5Totstd= 0132 0008 5-level 166 (154)

RESULTS Mean = 025818 mgkg

Repeatability variance S2r = 000083Repeatability std Sr = 002878 --gt 1115 r = 00806Between lab variance S2L = 001640Reproducibility var S2R = 001723Reproducibility std SR = 013127 --gt 5084 R = 03676Remarks none

000 050 100 150

k-values

26L

4L

46L

44L

12L

64L

Mandels k statistics(Soil 3 - PBD 209)

-02 -01 -01 00 01 01 02 02

Deviation from Mean

26L

4L

46L

44L

12L

64L

Labo

rato

ries

Soil 3 - PBD 209 -- Mean PARM = 0258 [mgkg]

-200 -100 000 100 200

h-values

26L

4L

46L

44L

12L

64L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 209)

Soil 3-PBD 209

Unit mgkg

Mandels k statistics(Compost 1 - Sum PBD)Mandels h statistics(Compost 1 - Sum PBD)

Sample Compost 1 Compost 1 - Sum PBD -- Mean PARM = 0009 [mgkg]

Element Sum PBD

General calcparmT1= 154064E-01T2= 169065E-03T3= 18T4= 68T5= 11354E-04

n= variabelp= 5

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00031 0002 4 -067 016 00031 00016 4 3 -0014L 00055 0005 4 -056 048 00055 00047 4 3 000

46L 00085 0003 4 -042 031 00085 00030 4 3 00026L 00123 0000 2 -024 003 00123 00002 2 1 00012L 00154 0002 4 -011 021 00154 00021 4 3 00144L 00613 0023 4 200 237 Fail - - 44L - - 005

Totgem 0018 0006 mgkg 1-level 187 (177) 5 00089 (44L) 5 4Totstd= 0022 0009 5-level 166 (154) 1

RESULTS Mean = 000893 mgkg

Repeatability variance S2r = 000001Repeatability std Sr = 000296 --gt 3308 r = 00083Between lab variance S2L = 000002Reproducibility var S2R = 000003Reproducibility std SR = 000570 --gt 6374 R = 00159Remarks 1 Lab rejected (44L)

000 050 100 150 200 250

k-values

10L

4L

46L

26L

12L

44L

Mandels k statistics(Compost 1 - Sum PBD)

00 00 00 00 00 00 01 01

Deviation from Mean

10L

4L

46L

26L

12L

44L

Labo

rato

ries

Compost 1 - Sum PBD -- Mean PARM = 0009 [mgkg]

-100 000 100 200

h-values

10L

4L

46L

26L

12L

44L

Labo

rato

ries

Mandels h statistics(Compost 1 - Sum PBD)

Compost 1-Sum PBD

Unit mgkg

Mandels k statistics(Sludge 1 - Sum PBD)Mandels h statistics(Sludge 1 - Sum PBD)

Sample Sludge 1 Sludge 1 - Sum PBD -- Mean PARM = 0256 [mgkg]

Element Sum PBD

General calcparmT1= 531806E+00T2= 162188E+00T3= 22T4= 84T5= 25223E-02

n= variabelp= 6

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00423 0025 4 -156 044 Fail 00423 00252 4 3 -02146L 01808 0118 4 -049 205 - - 46L - - -0074L 01810 0056 4 -049 097 01810 00558 4 3 -007

38L 02168 0006 4 -022 010 02168 00059 4 3 -00412L 02890 0065 4 034 113 02890 00647 4 3 00364L 03958 0008 4 116 014 Fail 03958 00079 4 3 01426L 04094 0034 2 126 059 Fail 04094 00337 2 1 015

Totgem 0245 0044 mgkg 1-level 198 (179) 6 02557 (46L) 6 5Totstd= 0130 0039 5-level 171 (155) 1

RESULTS Mean = 025570 mgkg

Repeatability variance S2r = 000158Repeatability std Sr = 003970 --gt 1553 r = 01112Between lab variance S2L = 001807Reproducibility var S2R = 001964Reproducibility std SR = 014015 --gt 5481 R = 03924Remarks 1 Lab rejected (46L)

000 050 100 150 200 250

k-values

10L

46L

4L

38L

12L

64L

26L

Mandels k statistics(Sludge 1 - Sum PBD)

-03 -02 -02 -01 -01 00 01 01 02 02

Deviation from Mean

10L

46L

4L

38L

12L

64L

26L

Labo

rato

ries

Sludge 1 - Sum PBD -- Mean PARM = 0256 [mgkg]

-200 -100 000 100 200

h-values

10L

46L

4L

38L

12L

64L

26L

Labo

rato

ries

Mandels h statistics(Sludge 1 - Sum PBD)

Sludge 1-Sum PBD

Unit mgkg

Mandels k statistics(Soil 3 - Sum PBD)Mandels h statistics(Soil 3 - Sum PBD)

Sample Soil 3 Soil 3 - Sum PBD -- Mean PARM = 0227 [mgkg]

Element Sum PBD

General calcparmT1= 610980E+00T2= 200876E+00T3= 26T4= 100T5= 13106E-02

n= variabelp= 7

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00028 0001 4 -037 000 Fail 00028 00005 4 3 -02226L 01179 0021 2 -036 003 Fail 01179 00208 2 1 -0114L 01305 0031 4 -036 004 Fail 01305 00308 4 3 -010

46L 02065 0035 4 -036 005 Fail 02065 00350 4 3 -00244L 02923 0037 4 -035 005 Fail 02923 00365 4 3 00712L 04051 0015 4 -034 002 Fail 04051 00149 4 3 01864L 04314 0022 4 -033 003 Fail 04314 00223 4 3 0203L 305500 2051 2 247 283 Fail - - 3L - - 3032

Totgem 4017 0276 mgkg 1-level 206 (181) 7 02266 (3L) 7 6Totstd= 10722 0717 5-level 175 (156) 1

RESULTS Mean = 022663 mgkg

Repeatability variance S2r = 000069Repeatability std Sr = 002626 --gt 1159 r = 00735Between lab variance S2L = 002568Reproducibility var S2R = 002637Reproducibility std SR = 016238 --gt 7165 R = 04547Remarks 1 Lab rejected (3L)

000 050 100 150 200 250 300

k-values

10L

26L

4L

46L

44L

12L

64L

3L

Mandels k statistics(Soil 3 - Sum PBD)

-50 00 50 100 150 200 250 300 350

Deviation from Mean

10L

26L

4L

46L

44L

12L

64L

3L

Labo

rato

ries

Soil 3 - Sum PBD -- Mean PARM = 0227 [mgkg]

-100 000 100 200 300

h-values

10L

26L

4L

46L

44L

12L

64L

3L

Labo

rato

ries

Mandels h statistics(Soil 3 - Sum PBD)

Soil 3-Sum PBD

19

Annex 4

Raw data submitted

Sample Compost1 Sample Compost 1 Sample Compost 1Element PBD 99 Element PBD 100 Element PBD 153

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]4L 00021 10L 00008 44L 000504L 00024 10L 00008 44L 000604L 00014 10L 00007 44L 000504L 00020 10L 00011 46L 00004

10L 00029 46L 00007 46L 0001210L 00027 46L 00012 46L 0000410L 00032 46L 00009 46L 0000946L 00025 46L 00007 12L 0000446L 00052 12L 00008 12L 0000846L 00029 12L 00012 12L 0000446L 00026 12L 00008 12L 0000712L 00026 12L 00014 26L 0000512L 00043 26L 00007 26L 0000512L 00026 26L 0000612L 0004726L 0002626L 00024

Sample Compost 1 Sample Compost 1 Sample Compost 1Element PBD 154 Element PBD 183 Element PBD 196

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]4L 00010 46L 00002 46L 00011

46L 00003 46L 00024 46L 0000846L 00007 46L 00021 12L 0000246L 00003 46L 00003 12L 0000346L 00004 12L 00003 12L 0000112L 00003 12L 00011 12L 0000212L 00005 12L 0000312L 00031 12L 0000312L 00006

Sample Compost 1 Sample Compost 1 Sample Compost 1Element PBD 197 Element PBD 203 Element PBD 209

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00002 46L 00010 4L 0004146L 00023 12L 00002 4L 0008946L 00022 12L 00003 44L 0041012L 00004 12L 00002 44L 0084012L 00006 12L 00002 44L 0064012L 00003 44L 0040012L 00004 12L 00079

12L 0007312L 0006512L 0009326L 0004926L 00049

Sample Compost 1Element PBD 47

LAB PARM [mgkg]26L 0003826L 00039

Element PBD 99 Element PBD 47 Element PBD 209LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]

4L 00170 10L 00210 4L 010004L 00200 10L 00220 4L 018004L 00170 10L 00210 4L 012004L 00190 46L 00300 4L 0220010L 00280 46L 00280 46L 0210010L 00300 46L 00250 46L 0200010L 00290 46L 00260 64L 0351846L 00340 64L 00059 64L 0363846L 00330 64L 00057 64L 0364546L 00300 64L 00062 64L 0350846L 00310 64L 00060 12L 0220964L 00194 12L 00191 12L 0177164L 00154 12L 00187 12L 0292264L 00185 12L 00190 12L 0164664L 00159 12L 00186 26L 0329712L 00242 26L 00666 26L 0300012L 00223 26L 0033212L 0022112L 0022226L 0024626L 00400

Element PBD 203 Element PBD 197 Element PBD 196LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00022 46L 00027 46L 0002446L 00014 46L 00024 46L 0002264L 00036 12L 00161 64L 0005864L 00058 12L 00060 64L 0006512L 00063 12L 00061 12L 0004812L 00034 12L 00036 12L 0002512L 00038 12L 0003212L 00027 12L 00022

Element PBD 183 Element PBD 154 Element PBD 153LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00049 4L 00020 4L 0002246L 00035 4L 00022 4L 0002446L 00036 4L 00020 4L 0002246L 00034 46L 00025 4L 0002664L 00027 46L 00025 46L 0004064L 00023 46L 00025 46L 0004264L 00024 46L 00023 46L 0003564L 00020 64L 00034 46L 0003812L 00230 64L 00023 64L 0007412L 00032 64L 00017 64L 0004712L 00031 64L 00011 64L 0004612L 00030 12L 00030 64L 0003026L 00007 12L 00021 12L 0006526L 00008 12L 00021 12L 00029

12L 00021 12L 0003226L 00015 12L 0002926L 00019 26L 00039

26L 00040

Element PBD 100LAB PARM [mgkg]

4L 000384L 000414L 000374L 00038

38L 0219038L 0220038L 0208038L 0220010L 0004410L 0005010L 0004310L 0004646L 0005746L 0005946L 0005346L 0005312L 0004312L 0004512L 0004312L 0004326L 0006226L 00057

Sample Soil 3 Sample Soil 3 Sample Soil 3Element PBD 99 Element PBD 47 Element PBD 100

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]10L 00016 10L 00011 10L 0000310L 00019 10L 00010 10L 0000410L 00013 10L 00012 10L 0000410L 00019 46L 00007 10L 0000246L 00025 46L 00022 46L 0000246L 00025 46L 00005 46L 0000646L 00008 46L 00007 46L 0000246L 00011 12L 00010 46L 0000264L 00005 12L 00017 3L 29100064L 00005 12L 00010 3L 32000064L 00006 12L 00009 26L 0000564L 00007 26L 00007 26L 0000512L 00012 26L 0000712L 0001312L 0001312L 0001226L 0000526L 00006

Sample Soil 3 Sample Soil 3 Sample Soil 3Element PBD 153 Element PBD 154 Element PBD 196

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]44L 00050 4L 00010 46L 0000744L 00050 46L 00001 46L 0001146L 00002 46L 00002 46L 0000846L 00003 46L 00001 46L 0001146L 00002 46L 00002 64L 0002646L 00002 64L 00001 64L 0002664L 00001 64L 00001 64L 0002964L 00001 64L 00001 64L 0003464L 00001 64L 00002 12L 0004564L 00002 12L 00003 12L 00032

12L 00002 12L 0002212L 00002 12L 0002112L 00002

Sample Soil 3 Sample Soil 3 Sample Soil 3Element PBD 197 Element PBD 203 Element PBD 209

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00006 46L 00011 4L 0091046L 00013 46L 00017 4L 0150046L 00011 46L 00015 4L 0120046L 00013 46L 00018 4L 0160012L 00090 64L 00013 44L 0337012L 00056 64L 00014 44L 0281012L 00033 64L 00016 44L 0287012L 00032 64L 00015 44L 02540

12L 00055 46L 0230012L 00041 46L 0220012L 00027 46L 0150012L 00026 46L 01900

64L 0438164L 0401664L 0414464L 0449812L 0367112L 0397812L 0409112L 03838

Sample Soil 3 26L 0102Element PBD 183 26L 0131

LAB PARM [mgkg]46L 0000746L 0000846L 0005846L 0000764L 0000264L 0000364L 0000364L 0000312L 0001512L 0001112L 0000712L 00007

European Commission EUR 23003 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on polybrominated diphenylethers Author(s) E Sobiecka H van der Sloot D Barcelo B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 68 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07403-5 Abstract Project HORIZONTAL is interdisciplinary aiming at a harmonisation and horizontal standardisation of test procedures in particular for sludge soils and biowastes In the context of this standardization project a series of draft technical specification were designed upon an extensive desk study fine-tuned after expert consultations and finally validated in international intercomparisons exercise This report summarises the work performed within the validation study of the draft standard for the determination of polybrominated diphenylethers (PBDE) in soils sludge and treated bio-waste using gas-chromatography method with mass selective detection (GC-MS) It further explains the underlying statistical concept for the calculation of reproducibility and repeatability from intercomparisons data In addition all single values results of the statistical evaluation as well as background information on the validation materials used are described and explained

The mission of the JRC is to provide customer-driven scientific and technical support for the conception development implementation and monitoring of EU policies As a service of the European Commission the JRC functions as a reference centre of science and technology for the Union Close to the policy-making process it serves the common interest of the Member States while being independent of special interests whether private or national

LB

-NA

-23003-EN

-C

18

Annex 3

Statistical calculations

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 47)Mandels h statistics(Sludge 1 - PBD 47)

Sample Sludge 1 NUM

Element PBD 47

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00213 0001 3 -021 005 - - 10L - - NUM46L 00273 0002 4 016 021 - - 46L - - NUM64L 00059 0000 4 -116 002 NUM - 64L - - NUM12L 00188 0000 4 -036 002 - - 12L - - NUM26L 00499 0024 2 157 223 Fail - - 26L - - NUM

Totgem 0025 0005 mgkg 1-level 172 (185) NUM (10L46L64L12L26L) -1Totstd= 0016 0010 5-level 157 (162) 5

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 5 Labs rejected (10L46L64L12L26L)

000 050 100 150 200 250

k-values

10L

46L

64L

12L

26L

Mandels k statistics(Sludge 1 - PBD 47)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

10L

46L

64L

12L

26L

Labo

rato

ries

NUM

-200 -100 000 100 200

h-values

10L

46L

64L

12L

26L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 47)

Sludge 1-PBD 47

Unit mgkg

Mandels k statistics(Soil 3 - PBD 47)Mandels h statistics(Soil 3 - PBD 47)

Sample Soil 3 Soil 3 - PBD 47 -- Mean PARM = 0001 [mgkg]

Element PBD 47

General calcparmT1= 134814E-02T2= 142830E-05T3= 13T4= 45T5= 22767E-06

n= variabelp= 4

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean26L 00007 0000 2 -143 001 00007 00000 2 1 00046L 00010 0001 4 010 181 00010 00008 4 3 00010L 00011 0000 3 049 023 00011 00001 3 2 00012L 00012 0000 4 084 081 00012 00004 4 3 000

Totgem 0001 0000 mgkg 1-level 149 (177) 4 00010 () 4 3Totstd= 0000 0000 5-level 142 (159)

RESULTS Mean = 000100 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000050 --gt 5031 r = 00014Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000050 --gt 5031 R = 00014Remarks none

000 050 100 150 200

k-values

26L

46L

10L

12L

Mandels k statistics(Soil 3 - PBD 47)

00 00 00 00 00 00 00 00 00 00 00

Deviation from Mean

26L

46L

10L

12L

Labo

rato

ries

Soil 3 - PBD 47 -- Mean PARM = 0001 [mgkg]

-200 -100 000 100

h-values

26L

46L

10L

12L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 47)

Soil 3-PBD 47

Unit mgkg

Mandels k statistics(Compost 1 - PBD 99)Mandels h statistics(Compost 1 - PBD 99)

Sample Compost 1 Compost 1 - PBD 99 -- Mean PARM = 0003 [mgkg]

Element PBD 99

General calcparmT1= 492124E-02T2= 148747E-04T3= 17T4= 61T5= 93196E-06

n= variabelp= 5

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00020 0000 4 -137 053 00020 00004 4 3 000

26L 00025 0000 2 -058 024 00025 00002 2 1 00010L 00029 0000 3 012 032 00029 00003 3 2 00046L 00033 0001 4 069 161 00033 00013 4 3 00012L 00036 0001 4 114 140 00036 00011 4 3 000

Totgem 0003 0001 mgkg 1-level 172 (185) 5 00029 () 5 4Totstd= 0001 0001 5-level 157 (162)

RESULTS Mean = 000286 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000088 --gt 3086 r = 00025Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000101 --gt 3525 R = 00028Remarks none

000 050 100 150 200

k-values

4L

26L

10L

46L

12L

Mandels k statistics(Compost 1 - PBD 99)

00 00 00 00 00 00 00 00 00 00

Deviation from Mean

4L

26L

10L

46L

12L

Labo

rato

ries

Compost 1 - PBD 99 -- Mean PARM = 0003 [mgkg]

-200 -100 000 100 200

h-values

4L

26L

10L

46L

12L

Labo

rato

ries

Mandels h statistics(Compost 1 - PBD 99)

Compost 1-PBD 99

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 99)Mandels h statistics(Sludge 1 - PBD 99)

Sample Sludge 1 Sludge 1 - PBD 99 -- Mean PARM = 0024 [mgkg]

Element PBD 99

General calcparmT1= 448050E-01T2= 112113E-02T3= 19T4= 73T5= 32972E-05

n= variabelp= 5

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean64L 00173 0002 4 -118 041 Fail 00173 00019 4 3 -0014L 00183 0002 4 -104 032 00183 00015 4 3 -001

12L 00227 0001 4 -038 022 00227 00010 4 3 00010L 00290 0001 3 055 021 00290 00010 3 2 00146L 00320 0002 4 100 039 00320 00018 4 3 00126L 00323 0011 2 105 234 - - 26L - - 001

Totgem 0025 0003 mgkg 1-level 187 (177) 5 00239 (26L) 5 4Totstd= 0007 0004 5-level 166 (154) 1

RESULTS Mean = 002385 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000153 --gt 643 r = 00043Between lab variance S2L = 000004Reproducibility var S2R = 000004Reproducibility std SR = 000666 --gt 2791 R = 00186Remarks 1 Lab rejected (26L)

000 050 100 150 200 250

k-values

64L

4L

12L

10L

46L

26L

Mandels k statistics(Sludge 1 - PBD 99)

00 00 00 00 00 00 00 00 00 00

Deviation from Mean

64L

4L

12L

10L

46L

26L

Labo

rato

ries

Sludge 1 - PBD 99 -- Mean PARM = 0024 [mgkg]

-200 -100 000 100 200

h-values

64L

4L

12L

10L

46L

26L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 99)

Sludge 1-PBD 99

Unit mgkg

Mandels k statistics(Soil 3 - PBD 99)Mandels h statistics(Soil 3 - PBD 99)

Sample Soil 3 NUM

Element PBD 99

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00017 0000 4 091 068 - - 10L - - NUM46L 00017 0001 4 100 211 - - 46L - - NUM64L 00005 0000 4 -106 023 NUM - 64L - - NUM12L 00012 0000 4 015 014 - - 12L - - NUM26L 00006 0000 2 -101 012 - - 26L - - NUM

Totgem 0001 0000 mgkg 1-level 172 (173) NUM (10L46L64L12L26L) -1Totstd= 0001 0000 5-level 157 (153) 5

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 5 Labs rejected (10L46L64L12L26L)

000 050 100 150 200 250

k-values

10L

46L

64L

12L

26L

Mandels k statistics(Soil 3 - PBD 99)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

10L

46L

64L

12L

26L

Labo

rato

ries

NUM

-200 -100 000 100 200

h-values

10L

46L

64L

12L

26L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 99)

Soil 3-PBD 99

Unit mgkg

Mandels k statistics(Compost 1 - PBD 100)Mandels h statistics(Compost 1 - PBD 100)

Sample Compost 1 Compost 1 - PBD 100 -- Mean PARM = 0001 [mgkg]

Element PBD 100

General calcparmT1= 124272E-02T2= 113129E-05T3= 14T4= 52T5= 46584E-07

n= variabelp= 4

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean26L 00006 0000 2 -131 037 Fail 00006 00001 2 1 00010L 00009 0000 4 003 083 00009 00002 4 3 00046L 00009 0000 4 016 115 00009 00002 4 3 00012L 00011 0000 4 112 136 Fail 00011 00003 4 3 000

Totgem 0001 0000 mgkg 1-level 149 (167) 4 00009 () 4 3Totstd= 0000 0000 5-level 142 (15)

RESULTS Mean = 000085 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000022 --gt 2531 r = 00006Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000025 --gt 2882 R = 00007Remarks none

000 050 100 150

k-values

26L

10L

46L

12L

Mandels k statistics(Compost 1 - PBD 100)

00 00 00 00 00 00 00 00 00 00 00

Deviation from Mean

26L

10L

46L

12L

Labo

rato

ries

Compost 1 - PBD 100 -- Mean PARM = 0001 [mgkg]

-200 -100 000 100 200

h-values

26L

10L

46L

12L

Labo

rato

ries

Mandels h statistics(Compost 1 - PBD 100)

Compost 1-PBD 100

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 100)Mandels h statistics(Sludge 1 - PBD 100)

Sample Sludge 1 Sludge 1 - PBD 100 -- Mean PARM = 0005 [mgkg]

Element PBD 100

General calcparmT1= 852065E-02T2= 412762E-04T3= 18T4= 68T5= 78914E-07

n= variabelp= 5

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00039 0000 4 -042 007 Fail 00039 00002 4 3 000

12L 00044 0000 4 -041 005 Fail 00044 00001 4 3 00010L 00046 0000 4 -041 013 Fail 00046 00003 4 3 00046L 00056 0000 4 -040 012 Fail 00056 00003 4 3 00026L 00059 0000 2 -040 013 Fail 00059 00003 2 1 00038L 02168 0006 4 204 244 Fail - - 38L - - 021

Totgem 0040 0001 mgkg 1-level 187 (177) 5 00049 (38L) 5 4Totstd= 0087 0002 5-level 166 (154) 1

RESULTS Mean = 000486 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000025 --gt 507 r = 00007Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000084 --gt 1731 R = 00024Remarks 1 Lab rejected (38L)

000 050 100 150 200 250

k-values

4L

12L

10L

46L

26L

38L

Mandels k statistics(Sludge 1 - PBD 100)

-01 00 01 01 02 02 03

Deviation from Mean

4L

12L

10L

46L

26L

38L

Labo

rato

ries

Sludge 1 - PBD 100 -- Mean PARM = 0005 [mgkg]

-100 000 100 200 300

h-values

4L

12L

10L

46L

26L

38L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 100)

Sludge 1-PBD 100

Unit mgkg

Mandels k statistics(Soil 3 - PBD 100)Mandels h statistics(Soil 3 - PBD 100)

Sample Soil 3 NUM

Element PBD 100

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00003 0000 4 -050 000 Fail - - 10L - - NUM46L 00003 0000 4 -050 000 Fail NUM - 46L - - NUM3L 305500 2051 2 150 200 Fail - - 3L - - NUM

26L 00005 0000 2 -050 000 Fail - - 26L - - NUM

Totgem 7638 0513 mgkg 1-level 149 (177) NUM (10L46L3L26L) -1Totstd= 15275 1025 5-level 142 (159) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (10L46L3L26L)

000 050 100 150 200

k-values

10L

46L

3L

26L

Mandels k statistics(Soil 3 - PBD 100)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

10L

46L

3L

26L

Labo

rato

ries

NUM

-100 000 100 200

h-values

10L

46L

3L

26L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 100)

Soil 3-PBD 100

Unit mgkg

Mandels k statistics(Compost 1 - PBD 153)Mandels h statistics(Compost 1 - PBD 153)

Sample Compost 1 NUM

Element PBD 153

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean44L 00053 0001 3 150 157 Fail - - 44L - - NUM46L 00007 0000 4 -044 111 Fail - - 46L - - NUM12L 00005 0000 4 -051 055 Fail - - 12L - - NUM26L 00005 0000 2 -054 001 Fail NUM - 26L - - NUM

Totgem 0002 0000 mgkg 1-level 149 (177) NUM (44L46L12L26L) -1Totstd= 0002 0000 5-level 142 (159) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (44L46L12L26L)

000 050 100 150 200

k-values

44L

46L

12L

26L

Mandels k statistics(Compost 1 - PBD 153)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

44L

46L

12L

26L

Labo

rato

ries

NUM

-100 000 100 200

h-values

44L

46L

12L

26L

Labo

rato

ries

Mandels h statistics(Compost 1 - PBD 153)

Compost 1-PBD 153

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 153)Mandels h statistics(Sludge 1 - PBD 153)

Sample Sludge 1 Sludge 1 - PBD 153 -- Mean PARM = 0004 [mgkg]

Element PBD 153

General calcparmT1= 676738E-02T2= 267609E-04T3= 18T4= 68T5= 19626E-05

n= variabelp= 5

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00024 0000 4 -157 017 00024 00002 4 3 000

12L 00038 0002 4 006 154 00038 00018 4 3 00046L 00039 0000 4 011 026 00039 00003 4 3 00026L 00039 0000 2 018 004 00039 00000 2 1 00064L 00049 0002 4 122 159 00049 00018 4 3 000

Totgem 0004 0001 mgkg 1-level 172 (173) 5 00038 () 5 4Totstd= 0001 0001 5-level 157 (153)

RESULTS Mean = 000378 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000123 --gt 3252 r = 00034Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000142 --gt 3754 R = 00040Remarks none

000 050 100 150 200

k-values

4L

12L

46L

26L

64L

Mandels k statistics(Sludge 1 - PBD 153)

00 00 00 00 00 00 00

Deviation from Mean

4L

12L

46L

26L

64L

Labo

rato

ries

Sludge 1 - PBD 153 -- Mean PARM = 0004 [mgkg]

-200 -100 000 100 200

h-values

4L

12L

46L

26L

64L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 153)

Sludge 1-PBD 153

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 154)Mandels h statistics(Sludge 1 - PBD 154)

Sample Sludge 1 NA

Element PBD 154

General calcparmT1= NAT2= NAT3=T4=T5=

n= variabelp=

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00021 0000 3 -100 021 NA - 4L - - NA

46L 00025 0000 4 115 018 NA - 46L - - NA64L 00021 0001 4 -066 179 - - 64L - - NA12L 00023 0000 4 050 085 - - 12L - - NA

Totgem 0002 0000 mgkg 1-level 149 (167) NA (4L46L64L12L) -1Totstd= 0000 0000 5-level 142 (15) 4

RESULTS Mean = NA mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NAReproducibility var S2R = NAReproducibility std SR = NA --gt NA R = NARemarks 4 Labs rejected (4L46L64L12L)

000 050 100 150 200

k-values

4L

46L

64L

12L

Mandels k statistics(Sludge 1 - PBD 154)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

4L

46L

64L

12L

Labo

rato

ries

NA

-100 000 100 200

h-values

4L

46L

64L

12L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 154)

Sludge 1-PBD 154

Unit mgkg

Mandels k statistics(Soil 3 - PBD 154)Mandels h statistics(Soil 3 - PBD 154)

Sample Soil 3 NUM

Element PBD 154

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

4L 00010 - 1 150 Fail - - 4L - - NUM46L 00001 0000 4 -053 096 Fail - - 46L - - NUM64L 00001 0000 4 -056 105 Fail NUM - 64L - - NUM12L 00002 0000 4 -040 099 Fail - - 12L - - NUM

Totgem 000037 0000 mgkg 1-level 149 (164) NUM (4L46L64L12L) -1Totstd= 000042 0000 5-level 142 (153) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (4L46L64L12L)

000 050 100 150

k-values

4L

46L

64L

12L

Mandels k statistics(Soil 3 - PBD 154)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

4L

46L

64L

12L

Labo

rato

ries

NUM

-100 000 100 200

h-values

4L

46L

64L

12L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 154)

Soil 3-PBD 154

Unit mgkg

Mandels k statistics(Compost 1 - PBD 209)Mandels h statistics(Compost 1 - PBD 209)

Sample Compost 1 NUM

Element PBD 209

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00065 0003 2 -049 032 - - 4L - - NUM

44L 00573 0021 4 150 197 Fail - - 44L - - NUM12L 00078 0001 4 -045 011 - - 12L - - NUM26L 00049 0000 2 -056 000 NUM - 26L - - NUM

Totgem 0019 0006 mgkg 1-level 149 (177) NUM (4L44L12L26L) -1Totstd= 0025 0010 5-level 142 (159) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (4L44L12L26L)

000 050 100 150 200

k-values

4L

44L

12L

26L

Mandels k statistics(Compost 1 - PBD 209)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

4L

44L

12L

26L

Labo

rato

ries

NUM

-100 000 100 200

h-values

4L

44L

12L

26L

Labo

rato

ries

Mandels h statistics(Compost 1 - PBD 209)

Compost 1-PBD 209

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 209)Mandels h statistics(Sludge 1 - PBD 209)

Sample Sludge 1 Sludge 1 - PBD 209 -- Mean PARM = 0249 [mgkg]

Element PBD 209

General calcparmT1= 394542E+00T2= 107296E+00T3= 16T4= 56T5= 19723E-02

n= variabelp= 5

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 01550 0055 4 -112 148 Fail 01550 00551 4 3 -009

46L 02050 0007 2 -053 019 02050 00071 2 1 -00412L 02137 0058 4 -042 155 02137 00576 4 3 -00426L 03149 0021 2 078 057 Fail 03149 00210 2 1 00764L 03577 0007 4 129 020 Fail 03577 00074 4 3 011

Totgem 0249 0030 mgkg 1-level 172 (185) 5 02493 () 5 4Totstd= 0084 0025 5-level 157 (162)

RESULTS Mean = 024926 mgkg

Repeatability variance S2r = 000179Repeatability std Sr = 004234 --gt 1699 r = 01186Between lab variance S2L = 000743Reproducibility var S2R = 000922Reproducibility std SR = 009604 --gt 3853 R = 02689Remarks none

000 050 100 150 200

k-values

4L

46L

12L

26L

64L

Mandels k statistics(Sludge 1 - PBD 209)

-01 -01 00 01 01 02

Deviation from Mean

4L

46L

12L

26L

64L

Labo

rato

ries

Sludge 1 - PBD 209 -- Mean PARM = 0249 [mgkg]

-200 -100 000 100 200

h-values

4L

46L

12L

26L

64L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 209)

Sludge 1-PBD 209

Unit mgkg

Mandels k statistics(Soil 3 - PBD 209)Mandels h statistics(Soil 3 - PBD 209)

Sample Soil 3 Soil 3 - PBD 209 -- Mean PARM = 0258 [mgkg]

Element PBD 209

General calcparmT1= 596398E+00T2= 191917E+00T3= 22T4= 84T5= 13249E-02

n= variabelp= 6

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean26L 01162 0021 2 -108 074 Fail 01162 00207 2 1 -0144L 01303 0031 4 -097 111 Fail 01303 00312 4 3 -013

46L 01975 0036 4 -046 128 Fail 01975 00359 4 3 -00644L 02898 0035 4 024 124 Fail 02898 00346 4 3 00312L 03895 0018 4 100 065 Fail 03895 00181 4 3 01364L 04260 0022 4 127 078 Fail 04260 00219 4 3 017

Totgem 0258 0027 mgkg 1-level 187 (177) 6 02582 () 6 5Totstd= 0132 0008 5-level 166 (154)

RESULTS Mean = 025818 mgkg

Repeatability variance S2r = 000083Repeatability std Sr = 002878 --gt 1115 r = 00806Between lab variance S2L = 001640Reproducibility var S2R = 001723Reproducibility std SR = 013127 --gt 5084 R = 03676Remarks none

000 050 100 150

k-values

26L

4L

46L

44L

12L

64L

Mandels k statistics(Soil 3 - PBD 209)

-02 -01 -01 00 01 01 02 02

Deviation from Mean

26L

4L

46L

44L

12L

64L

Labo

rato

ries

Soil 3 - PBD 209 -- Mean PARM = 0258 [mgkg]

-200 -100 000 100 200

h-values

26L

4L

46L

44L

12L

64L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 209)

Soil 3-PBD 209

Unit mgkg

Mandels k statistics(Compost 1 - Sum PBD)Mandels h statistics(Compost 1 - Sum PBD)

Sample Compost 1 Compost 1 - Sum PBD -- Mean PARM = 0009 [mgkg]

Element Sum PBD

General calcparmT1= 154064E-01T2= 169065E-03T3= 18T4= 68T5= 11354E-04

n= variabelp= 5

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00031 0002 4 -067 016 00031 00016 4 3 -0014L 00055 0005 4 -056 048 00055 00047 4 3 000

46L 00085 0003 4 -042 031 00085 00030 4 3 00026L 00123 0000 2 -024 003 00123 00002 2 1 00012L 00154 0002 4 -011 021 00154 00021 4 3 00144L 00613 0023 4 200 237 Fail - - 44L - - 005

Totgem 0018 0006 mgkg 1-level 187 (177) 5 00089 (44L) 5 4Totstd= 0022 0009 5-level 166 (154) 1

RESULTS Mean = 000893 mgkg

Repeatability variance S2r = 000001Repeatability std Sr = 000296 --gt 3308 r = 00083Between lab variance S2L = 000002Reproducibility var S2R = 000003Reproducibility std SR = 000570 --gt 6374 R = 00159Remarks 1 Lab rejected (44L)

000 050 100 150 200 250

k-values

10L

4L

46L

26L

12L

44L

Mandels k statistics(Compost 1 - Sum PBD)

00 00 00 00 00 00 01 01

Deviation from Mean

10L

4L

46L

26L

12L

44L

Labo

rato

ries

Compost 1 - Sum PBD -- Mean PARM = 0009 [mgkg]

-100 000 100 200

h-values

10L

4L

46L

26L

12L

44L

Labo

rato

ries

Mandels h statistics(Compost 1 - Sum PBD)

Compost 1-Sum PBD

Unit mgkg

Mandels k statistics(Sludge 1 - Sum PBD)Mandels h statistics(Sludge 1 - Sum PBD)

Sample Sludge 1 Sludge 1 - Sum PBD -- Mean PARM = 0256 [mgkg]

Element Sum PBD

General calcparmT1= 531806E+00T2= 162188E+00T3= 22T4= 84T5= 25223E-02

n= variabelp= 6

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00423 0025 4 -156 044 Fail 00423 00252 4 3 -02146L 01808 0118 4 -049 205 - - 46L - - -0074L 01810 0056 4 -049 097 01810 00558 4 3 -007

38L 02168 0006 4 -022 010 02168 00059 4 3 -00412L 02890 0065 4 034 113 02890 00647 4 3 00364L 03958 0008 4 116 014 Fail 03958 00079 4 3 01426L 04094 0034 2 126 059 Fail 04094 00337 2 1 015

Totgem 0245 0044 mgkg 1-level 198 (179) 6 02557 (46L) 6 5Totstd= 0130 0039 5-level 171 (155) 1

RESULTS Mean = 025570 mgkg

Repeatability variance S2r = 000158Repeatability std Sr = 003970 --gt 1553 r = 01112Between lab variance S2L = 001807Reproducibility var S2R = 001964Reproducibility std SR = 014015 --gt 5481 R = 03924Remarks 1 Lab rejected (46L)

000 050 100 150 200 250

k-values

10L

46L

4L

38L

12L

64L

26L

Mandels k statistics(Sludge 1 - Sum PBD)

-03 -02 -02 -01 -01 00 01 01 02 02

Deviation from Mean

10L

46L

4L

38L

12L

64L

26L

Labo

rato

ries

Sludge 1 - Sum PBD -- Mean PARM = 0256 [mgkg]

-200 -100 000 100 200

h-values

10L

46L

4L

38L

12L

64L

26L

Labo

rato

ries

Mandels h statistics(Sludge 1 - Sum PBD)

Sludge 1-Sum PBD

Unit mgkg

Mandels k statistics(Soil 3 - Sum PBD)Mandels h statistics(Soil 3 - Sum PBD)

Sample Soil 3 Soil 3 - Sum PBD -- Mean PARM = 0227 [mgkg]

Element Sum PBD

General calcparmT1= 610980E+00T2= 200876E+00T3= 26T4= 100T5= 13106E-02

n= variabelp= 7

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00028 0001 4 -037 000 Fail 00028 00005 4 3 -02226L 01179 0021 2 -036 003 Fail 01179 00208 2 1 -0114L 01305 0031 4 -036 004 Fail 01305 00308 4 3 -010

46L 02065 0035 4 -036 005 Fail 02065 00350 4 3 -00244L 02923 0037 4 -035 005 Fail 02923 00365 4 3 00712L 04051 0015 4 -034 002 Fail 04051 00149 4 3 01864L 04314 0022 4 -033 003 Fail 04314 00223 4 3 0203L 305500 2051 2 247 283 Fail - - 3L - - 3032

Totgem 4017 0276 mgkg 1-level 206 (181) 7 02266 (3L) 7 6Totstd= 10722 0717 5-level 175 (156) 1

RESULTS Mean = 022663 mgkg

Repeatability variance S2r = 000069Repeatability std Sr = 002626 --gt 1159 r = 00735Between lab variance S2L = 002568Reproducibility var S2R = 002637Reproducibility std SR = 016238 --gt 7165 R = 04547Remarks 1 Lab rejected (3L)

000 050 100 150 200 250 300

k-values

10L

26L

4L

46L

44L

12L

64L

3L

Mandels k statistics(Soil 3 - Sum PBD)

-50 00 50 100 150 200 250 300 350

Deviation from Mean

10L

26L

4L

46L

44L

12L

64L

3L

Labo

rato

ries

Soil 3 - Sum PBD -- Mean PARM = 0227 [mgkg]

-100 000 100 200 300

h-values

10L

26L

4L

46L

44L

12L

64L

3L

Labo

rato

ries

Mandels h statistics(Soil 3 - Sum PBD)

Soil 3-Sum PBD

19

Annex 4

Raw data submitted

Sample Compost1 Sample Compost 1 Sample Compost 1Element PBD 99 Element PBD 100 Element PBD 153

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]4L 00021 10L 00008 44L 000504L 00024 10L 00008 44L 000604L 00014 10L 00007 44L 000504L 00020 10L 00011 46L 00004

10L 00029 46L 00007 46L 0001210L 00027 46L 00012 46L 0000410L 00032 46L 00009 46L 0000946L 00025 46L 00007 12L 0000446L 00052 12L 00008 12L 0000846L 00029 12L 00012 12L 0000446L 00026 12L 00008 12L 0000712L 00026 12L 00014 26L 0000512L 00043 26L 00007 26L 0000512L 00026 26L 0000612L 0004726L 0002626L 00024

Sample Compost 1 Sample Compost 1 Sample Compost 1Element PBD 154 Element PBD 183 Element PBD 196

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]4L 00010 46L 00002 46L 00011

46L 00003 46L 00024 46L 0000846L 00007 46L 00021 12L 0000246L 00003 46L 00003 12L 0000346L 00004 12L 00003 12L 0000112L 00003 12L 00011 12L 0000212L 00005 12L 0000312L 00031 12L 0000312L 00006

Sample Compost 1 Sample Compost 1 Sample Compost 1Element PBD 197 Element PBD 203 Element PBD 209

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00002 46L 00010 4L 0004146L 00023 12L 00002 4L 0008946L 00022 12L 00003 44L 0041012L 00004 12L 00002 44L 0084012L 00006 12L 00002 44L 0064012L 00003 44L 0040012L 00004 12L 00079

12L 0007312L 0006512L 0009326L 0004926L 00049

Sample Compost 1Element PBD 47

LAB PARM [mgkg]26L 0003826L 00039

Element PBD 99 Element PBD 47 Element PBD 209LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]

4L 00170 10L 00210 4L 010004L 00200 10L 00220 4L 018004L 00170 10L 00210 4L 012004L 00190 46L 00300 4L 0220010L 00280 46L 00280 46L 0210010L 00300 46L 00250 46L 0200010L 00290 46L 00260 64L 0351846L 00340 64L 00059 64L 0363846L 00330 64L 00057 64L 0364546L 00300 64L 00062 64L 0350846L 00310 64L 00060 12L 0220964L 00194 12L 00191 12L 0177164L 00154 12L 00187 12L 0292264L 00185 12L 00190 12L 0164664L 00159 12L 00186 26L 0329712L 00242 26L 00666 26L 0300012L 00223 26L 0033212L 0022112L 0022226L 0024626L 00400

Element PBD 203 Element PBD 197 Element PBD 196LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00022 46L 00027 46L 0002446L 00014 46L 00024 46L 0002264L 00036 12L 00161 64L 0005864L 00058 12L 00060 64L 0006512L 00063 12L 00061 12L 0004812L 00034 12L 00036 12L 0002512L 00038 12L 0003212L 00027 12L 00022

Element PBD 183 Element PBD 154 Element PBD 153LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00049 4L 00020 4L 0002246L 00035 4L 00022 4L 0002446L 00036 4L 00020 4L 0002246L 00034 46L 00025 4L 0002664L 00027 46L 00025 46L 0004064L 00023 46L 00025 46L 0004264L 00024 46L 00023 46L 0003564L 00020 64L 00034 46L 0003812L 00230 64L 00023 64L 0007412L 00032 64L 00017 64L 0004712L 00031 64L 00011 64L 0004612L 00030 12L 00030 64L 0003026L 00007 12L 00021 12L 0006526L 00008 12L 00021 12L 00029

12L 00021 12L 0003226L 00015 12L 0002926L 00019 26L 00039

26L 00040

Element PBD 100LAB PARM [mgkg]

4L 000384L 000414L 000374L 00038

38L 0219038L 0220038L 0208038L 0220010L 0004410L 0005010L 0004310L 0004646L 0005746L 0005946L 0005346L 0005312L 0004312L 0004512L 0004312L 0004326L 0006226L 00057

Sample Soil 3 Sample Soil 3 Sample Soil 3Element PBD 99 Element PBD 47 Element PBD 100

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]10L 00016 10L 00011 10L 0000310L 00019 10L 00010 10L 0000410L 00013 10L 00012 10L 0000410L 00019 46L 00007 10L 0000246L 00025 46L 00022 46L 0000246L 00025 46L 00005 46L 0000646L 00008 46L 00007 46L 0000246L 00011 12L 00010 46L 0000264L 00005 12L 00017 3L 29100064L 00005 12L 00010 3L 32000064L 00006 12L 00009 26L 0000564L 00007 26L 00007 26L 0000512L 00012 26L 0000712L 0001312L 0001312L 0001226L 0000526L 00006

Sample Soil 3 Sample Soil 3 Sample Soil 3Element PBD 153 Element PBD 154 Element PBD 196

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]44L 00050 4L 00010 46L 0000744L 00050 46L 00001 46L 0001146L 00002 46L 00002 46L 0000846L 00003 46L 00001 46L 0001146L 00002 46L 00002 64L 0002646L 00002 64L 00001 64L 0002664L 00001 64L 00001 64L 0002964L 00001 64L 00001 64L 0003464L 00001 64L 00002 12L 0004564L 00002 12L 00003 12L 00032

12L 00002 12L 0002212L 00002 12L 0002112L 00002

Sample Soil 3 Sample Soil 3 Sample Soil 3Element PBD 197 Element PBD 203 Element PBD 209

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00006 46L 00011 4L 0091046L 00013 46L 00017 4L 0150046L 00011 46L 00015 4L 0120046L 00013 46L 00018 4L 0160012L 00090 64L 00013 44L 0337012L 00056 64L 00014 44L 0281012L 00033 64L 00016 44L 0287012L 00032 64L 00015 44L 02540

12L 00055 46L 0230012L 00041 46L 0220012L 00027 46L 0150012L 00026 46L 01900

64L 0438164L 0401664L 0414464L 0449812L 0367112L 0397812L 0409112L 03838

Sample Soil 3 26L 0102Element PBD 183 26L 0131

LAB PARM [mgkg]46L 0000746L 0000846L 0005846L 0000764L 0000264L 0000364L 0000364L 0000312L 0001512L 0001112L 0000712L 00007

European Commission EUR 23003 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on polybrominated diphenylethers Author(s) E Sobiecka H van der Sloot D Barcelo B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 68 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07403-5 Abstract Project HORIZONTAL is interdisciplinary aiming at a harmonisation and horizontal standardisation of test procedures in particular for sludge soils and biowastes In the context of this standardization project a series of draft technical specification were designed upon an extensive desk study fine-tuned after expert consultations and finally validated in international intercomparisons exercise This report summarises the work performed within the validation study of the draft standard for the determination of polybrominated diphenylethers (PBDE) in soils sludge and treated bio-waste using gas-chromatography method with mass selective detection (GC-MS) It further explains the underlying statistical concept for the calculation of reproducibility and repeatability from intercomparisons data In addition all single values results of the statistical evaluation as well as background information on the validation materials used are described and explained

The mission of the JRC is to provide customer-driven scientific and technical support for the conception development implementation and monitoring of EU policies As a service of the European Commission the JRC functions as a reference centre of science and technology for the Union Close to the policy-making process it serves the common interest of the Member States while being independent of special interests whether private or national

LB

-NA

-23003-EN

-C

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 47)Mandels h statistics(Sludge 1 - PBD 47)

Sample Sludge 1 NUM

Element PBD 47

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00213 0001 3 -021 005 - - 10L - - NUM46L 00273 0002 4 016 021 - - 46L - - NUM64L 00059 0000 4 -116 002 NUM - 64L - - NUM12L 00188 0000 4 -036 002 - - 12L - - NUM26L 00499 0024 2 157 223 Fail - - 26L - - NUM

Totgem 0025 0005 mgkg 1-level 172 (185) NUM (10L46L64L12L26L) -1Totstd= 0016 0010 5-level 157 (162) 5

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 5 Labs rejected (10L46L64L12L26L)

000 050 100 150 200 250

k-values

10L

46L

64L

12L

26L

Mandels k statistics(Sludge 1 - PBD 47)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

10L

46L

64L

12L

26L

Labo

rato

ries

NUM

-200 -100 000 100 200

h-values

10L

46L

64L

12L

26L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 47)

Sludge 1-PBD 47

Unit mgkg

Mandels k statistics(Soil 3 - PBD 47)Mandels h statistics(Soil 3 - PBD 47)

Sample Soil 3 Soil 3 - PBD 47 -- Mean PARM = 0001 [mgkg]

Element PBD 47

General calcparmT1= 134814E-02T2= 142830E-05T3= 13T4= 45T5= 22767E-06

n= variabelp= 4

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean26L 00007 0000 2 -143 001 00007 00000 2 1 00046L 00010 0001 4 010 181 00010 00008 4 3 00010L 00011 0000 3 049 023 00011 00001 3 2 00012L 00012 0000 4 084 081 00012 00004 4 3 000

Totgem 0001 0000 mgkg 1-level 149 (177) 4 00010 () 4 3Totstd= 0000 0000 5-level 142 (159)

RESULTS Mean = 000100 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000050 --gt 5031 r = 00014Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000050 --gt 5031 R = 00014Remarks none

000 050 100 150 200

k-values

26L

46L

10L

12L

Mandels k statistics(Soil 3 - PBD 47)

00 00 00 00 00 00 00 00 00 00 00

Deviation from Mean

26L

46L

10L

12L

Labo

rato

ries

Soil 3 - PBD 47 -- Mean PARM = 0001 [mgkg]

-200 -100 000 100

h-values

26L

46L

10L

12L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 47)

Soil 3-PBD 47

Unit mgkg

Mandels k statistics(Compost 1 - PBD 99)Mandels h statistics(Compost 1 - PBD 99)

Sample Compost 1 Compost 1 - PBD 99 -- Mean PARM = 0003 [mgkg]

Element PBD 99

General calcparmT1= 492124E-02T2= 148747E-04T3= 17T4= 61T5= 93196E-06

n= variabelp= 5

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00020 0000 4 -137 053 00020 00004 4 3 000

26L 00025 0000 2 -058 024 00025 00002 2 1 00010L 00029 0000 3 012 032 00029 00003 3 2 00046L 00033 0001 4 069 161 00033 00013 4 3 00012L 00036 0001 4 114 140 00036 00011 4 3 000

Totgem 0003 0001 mgkg 1-level 172 (185) 5 00029 () 5 4Totstd= 0001 0001 5-level 157 (162)

RESULTS Mean = 000286 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000088 --gt 3086 r = 00025Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000101 --gt 3525 R = 00028Remarks none

000 050 100 150 200

k-values

4L

26L

10L

46L

12L

Mandels k statistics(Compost 1 - PBD 99)

00 00 00 00 00 00 00 00 00 00

Deviation from Mean

4L

26L

10L

46L

12L

Labo

rato

ries

Compost 1 - PBD 99 -- Mean PARM = 0003 [mgkg]

-200 -100 000 100 200

h-values

4L

26L

10L

46L

12L

Labo

rato

ries

Mandels h statistics(Compost 1 - PBD 99)

Compost 1-PBD 99

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 99)Mandels h statistics(Sludge 1 - PBD 99)

Sample Sludge 1 Sludge 1 - PBD 99 -- Mean PARM = 0024 [mgkg]

Element PBD 99

General calcparmT1= 448050E-01T2= 112113E-02T3= 19T4= 73T5= 32972E-05

n= variabelp= 5

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean64L 00173 0002 4 -118 041 Fail 00173 00019 4 3 -0014L 00183 0002 4 -104 032 00183 00015 4 3 -001

12L 00227 0001 4 -038 022 00227 00010 4 3 00010L 00290 0001 3 055 021 00290 00010 3 2 00146L 00320 0002 4 100 039 00320 00018 4 3 00126L 00323 0011 2 105 234 - - 26L - - 001

Totgem 0025 0003 mgkg 1-level 187 (177) 5 00239 (26L) 5 4Totstd= 0007 0004 5-level 166 (154) 1

RESULTS Mean = 002385 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000153 --gt 643 r = 00043Between lab variance S2L = 000004Reproducibility var S2R = 000004Reproducibility std SR = 000666 --gt 2791 R = 00186Remarks 1 Lab rejected (26L)

000 050 100 150 200 250

k-values

64L

4L

12L

10L

46L

26L

Mandels k statistics(Sludge 1 - PBD 99)

00 00 00 00 00 00 00 00 00 00

Deviation from Mean

64L

4L

12L

10L

46L

26L

Labo

rato

ries

Sludge 1 - PBD 99 -- Mean PARM = 0024 [mgkg]

-200 -100 000 100 200

h-values

64L

4L

12L

10L

46L

26L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 99)

Sludge 1-PBD 99

Unit mgkg

Mandels k statistics(Soil 3 - PBD 99)Mandels h statistics(Soil 3 - PBD 99)

Sample Soil 3 NUM

Element PBD 99

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00017 0000 4 091 068 - - 10L - - NUM46L 00017 0001 4 100 211 - - 46L - - NUM64L 00005 0000 4 -106 023 NUM - 64L - - NUM12L 00012 0000 4 015 014 - - 12L - - NUM26L 00006 0000 2 -101 012 - - 26L - - NUM

Totgem 0001 0000 mgkg 1-level 172 (173) NUM (10L46L64L12L26L) -1Totstd= 0001 0000 5-level 157 (153) 5

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 5 Labs rejected (10L46L64L12L26L)

000 050 100 150 200 250

k-values

10L

46L

64L

12L

26L

Mandels k statistics(Soil 3 - PBD 99)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

10L

46L

64L

12L

26L

Labo

rato

ries

NUM

-200 -100 000 100 200

h-values

10L

46L

64L

12L

26L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 99)

Soil 3-PBD 99

Unit mgkg

Mandels k statistics(Compost 1 - PBD 100)Mandels h statistics(Compost 1 - PBD 100)

Sample Compost 1 Compost 1 - PBD 100 -- Mean PARM = 0001 [mgkg]

Element PBD 100

General calcparmT1= 124272E-02T2= 113129E-05T3= 14T4= 52T5= 46584E-07

n= variabelp= 4

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean26L 00006 0000 2 -131 037 Fail 00006 00001 2 1 00010L 00009 0000 4 003 083 00009 00002 4 3 00046L 00009 0000 4 016 115 00009 00002 4 3 00012L 00011 0000 4 112 136 Fail 00011 00003 4 3 000

Totgem 0001 0000 mgkg 1-level 149 (167) 4 00009 () 4 3Totstd= 0000 0000 5-level 142 (15)

RESULTS Mean = 000085 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000022 --gt 2531 r = 00006Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000025 --gt 2882 R = 00007Remarks none

000 050 100 150

k-values

26L

10L

46L

12L

Mandels k statistics(Compost 1 - PBD 100)

00 00 00 00 00 00 00 00 00 00 00

Deviation from Mean

26L

10L

46L

12L

Labo

rato

ries

Compost 1 - PBD 100 -- Mean PARM = 0001 [mgkg]

-200 -100 000 100 200

h-values

26L

10L

46L

12L

Labo

rato

ries

Mandels h statistics(Compost 1 - PBD 100)

Compost 1-PBD 100

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 100)Mandels h statistics(Sludge 1 - PBD 100)

Sample Sludge 1 Sludge 1 - PBD 100 -- Mean PARM = 0005 [mgkg]

Element PBD 100

General calcparmT1= 852065E-02T2= 412762E-04T3= 18T4= 68T5= 78914E-07

n= variabelp= 5

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00039 0000 4 -042 007 Fail 00039 00002 4 3 000

12L 00044 0000 4 -041 005 Fail 00044 00001 4 3 00010L 00046 0000 4 -041 013 Fail 00046 00003 4 3 00046L 00056 0000 4 -040 012 Fail 00056 00003 4 3 00026L 00059 0000 2 -040 013 Fail 00059 00003 2 1 00038L 02168 0006 4 204 244 Fail - - 38L - - 021

Totgem 0040 0001 mgkg 1-level 187 (177) 5 00049 (38L) 5 4Totstd= 0087 0002 5-level 166 (154) 1

RESULTS Mean = 000486 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000025 --gt 507 r = 00007Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000084 --gt 1731 R = 00024Remarks 1 Lab rejected (38L)

000 050 100 150 200 250

k-values

4L

12L

10L

46L

26L

38L

Mandels k statistics(Sludge 1 - PBD 100)

-01 00 01 01 02 02 03

Deviation from Mean

4L

12L

10L

46L

26L

38L

Labo

rato

ries

Sludge 1 - PBD 100 -- Mean PARM = 0005 [mgkg]

-100 000 100 200 300

h-values

4L

12L

10L

46L

26L

38L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 100)

Sludge 1-PBD 100

Unit mgkg

Mandels k statistics(Soil 3 - PBD 100)Mandels h statistics(Soil 3 - PBD 100)

Sample Soil 3 NUM

Element PBD 100

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00003 0000 4 -050 000 Fail - - 10L - - NUM46L 00003 0000 4 -050 000 Fail NUM - 46L - - NUM3L 305500 2051 2 150 200 Fail - - 3L - - NUM

26L 00005 0000 2 -050 000 Fail - - 26L - - NUM

Totgem 7638 0513 mgkg 1-level 149 (177) NUM (10L46L3L26L) -1Totstd= 15275 1025 5-level 142 (159) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (10L46L3L26L)

000 050 100 150 200

k-values

10L

46L

3L

26L

Mandels k statistics(Soil 3 - PBD 100)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

10L

46L

3L

26L

Labo

rato

ries

NUM

-100 000 100 200

h-values

10L

46L

3L

26L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 100)

Soil 3-PBD 100

Unit mgkg

Mandels k statistics(Compost 1 - PBD 153)Mandels h statistics(Compost 1 - PBD 153)

Sample Compost 1 NUM

Element PBD 153

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean44L 00053 0001 3 150 157 Fail - - 44L - - NUM46L 00007 0000 4 -044 111 Fail - - 46L - - NUM12L 00005 0000 4 -051 055 Fail - - 12L - - NUM26L 00005 0000 2 -054 001 Fail NUM - 26L - - NUM

Totgem 0002 0000 mgkg 1-level 149 (177) NUM (44L46L12L26L) -1Totstd= 0002 0000 5-level 142 (159) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (44L46L12L26L)

000 050 100 150 200

k-values

44L

46L

12L

26L

Mandels k statistics(Compost 1 - PBD 153)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

44L

46L

12L

26L

Labo

rato

ries

NUM

-100 000 100 200

h-values

44L

46L

12L

26L

Labo

rato

ries

Mandels h statistics(Compost 1 - PBD 153)

Compost 1-PBD 153

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 153)Mandels h statistics(Sludge 1 - PBD 153)

Sample Sludge 1 Sludge 1 - PBD 153 -- Mean PARM = 0004 [mgkg]

Element PBD 153

General calcparmT1= 676738E-02T2= 267609E-04T3= 18T4= 68T5= 19626E-05

n= variabelp= 5

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00024 0000 4 -157 017 00024 00002 4 3 000

12L 00038 0002 4 006 154 00038 00018 4 3 00046L 00039 0000 4 011 026 00039 00003 4 3 00026L 00039 0000 2 018 004 00039 00000 2 1 00064L 00049 0002 4 122 159 00049 00018 4 3 000

Totgem 0004 0001 mgkg 1-level 172 (173) 5 00038 () 5 4Totstd= 0001 0001 5-level 157 (153)

RESULTS Mean = 000378 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000123 --gt 3252 r = 00034Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000142 --gt 3754 R = 00040Remarks none

000 050 100 150 200

k-values

4L

12L

46L

26L

64L

Mandels k statistics(Sludge 1 - PBD 153)

00 00 00 00 00 00 00

Deviation from Mean

4L

12L

46L

26L

64L

Labo

rato

ries

Sludge 1 - PBD 153 -- Mean PARM = 0004 [mgkg]

-200 -100 000 100 200

h-values

4L

12L

46L

26L

64L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 153)

Sludge 1-PBD 153

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 154)Mandels h statistics(Sludge 1 - PBD 154)

Sample Sludge 1 NA

Element PBD 154

General calcparmT1= NAT2= NAT3=T4=T5=

n= variabelp=

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00021 0000 3 -100 021 NA - 4L - - NA

46L 00025 0000 4 115 018 NA - 46L - - NA64L 00021 0001 4 -066 179 - - 64L - - NA12L 00023 0000 4 050 085 - - 12L - - NA

Totgem 0002 0000 mgkg 1-level 149 (167) NA (4L46L64L12L) -1Totstd= 0000 0000 5-level 142 (15) 4

RESULTS Mean = NA mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NAReproducibility var S2R = NAReproducibility std SR = NA --gt NA R = NARemarks 4 Labs rejected (4L46L64L12L)

000 050 100 150 200

k-values

4L

46L

64L

12L

Mandels k statistics(Sludge 1 - PBD 154)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

4L

46L

64L

12L

Labo

rato

ries

NA

-100 000 100 200

h-values

4L

46L

64L

12L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 154)

Sludge 1-PBD 154

Unit mgkg

Mandels k statistics(Soil 3 - PBD 154)Mandels h statistics(Soil 3 - PBD 154)

Sample Soil 3 NUM

Element PBD 154

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

4L 00010 - 1 150 Fail - - 4L - - NUM46L 00001 0000 4 -053 096 Fail - - 46L - - NUM64L 00001 0000 4 -056 105 Fail NUM - 64L - - NUM12L 00002 0000 4 -040 099 Fail - - 12L - - NUM

Totgem 000037 0000 mgkg 1-level 149 (164) NUM (4L46L64L12L) -1Totstd= 000042 0000 5-level 142 (153) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (4L46L64L12L)

000 050 100 150

k-values

4L

46L

64L

12L

Mandels k statistics(Soil 3 - PBD 154)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

4L

46L

64L

12L

Labo

rato

ries

NUM

-100 000 100 200

h-values

4L

46L

64L

12L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 154)

Soil 3-PBD 154

Unit mgkg

Mandels k statistics(Compost 1 - PBD 209)Mandels h statistics(Compost 1 - PBD 209)

Sample Compost 1 NUM

Element PBD 209

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00065 0003 2 -049 032 - - 4L - - NUM

44L 00573 0021 4 150 197 Fail - - 44L - - NUM12L 00078 0001 4 -045 011 - - 12L - - NUM26L 00049 0000 2 -056 000 NUM - 26L - - NUM

Totgem 0019 0006 mgkg 1-level 149 (177) NUM (4L44L12L26L) -1Totstd= 0025 0010 5-level 142 (159) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (4L44L12L26L)

000 050 100 150 200

k-values

4L

44L

12L

26L

Mandels k statistics(Compost 1 - PBD 209)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

4L

44L

12L

26L

Labo

rato

ries

NUM

-100 000 100 200

h-values

4L

44L

12L

26L

Labo

rato

ries

Mandels h statistics(Compost 1 - PBD 209)

Compost 1-PBD 209

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 209)Mandels h statistics(Sludge 1 - PBD 209)

Sample Sludge 1 Sludge 1 - PBD 209 -- Mean PARM = 0249 [mgkg]

Element PBD 209

General calcparmT1= 394542E+00T2= 107296E+00T3= 16T4= 56T5= 19723E-02

n= variabelp= 5

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 01550 0055 4 -112 148 Fail 01550 00551 4 3 -009

46L 02050 0007 2 -053 019 02050 00071 2 1 -00412L 02137 0058 4 -042 155 02137 00576 4 3 -00426L 03149 0021 2 078 057 Fail 03149 00210 2 1 00764L 03577 0007 4 129 020 Fail 03577 00074 4 3 011

Totgem 0249 0030 mgkg 1-level 172 (185) 5 02493 () 5 4Totstd= 0084 0025 5-level 157 (162)

RESULTS Mean = 024926 mgkg

Repeatability variance S2r = 000179Repeatability std Sr = 004234 --gt 1699 r = 01186Between lab variance S2L = 000743Reproducibility var S2R = 000922Reproducibility std SR = 009604 --gt 3853 R = 02689Remarks none

000 050 100 150 200

k-values

4L

46L

12L

26L

64L

Mandels k statistics(Sludge 1 - PBD 209)

-01 -01 00 01 01 02

Deviation from Mean

4L

46L

12L

26L

64L

Labo

rato

ries

Sludge 1 - PBD 209 -- Mean PARM = 0249 [mgkg]

-200 -100 000 100 200

h-values

4L

46L

12L

26L

64L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 209)

Sludge 1-PBD 209

Unit mgkg

Mandels k statistics(Soil 3 - PBD 209)Mandels h statistics(Soil 3 - PBD 209)

Sample Soil 3 Soil 3 - PBD 209 -- Mean PARM = 0258 [mgkg]

Element PBD 209

General calcparmT1= 596398E+00T2= 191917E+00T3= 22T4= 84T5= 13249E-02

n= variabelp= 6

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean26L 01162 0021 2 -108 074 Fail 01162 00207 2 1 -0144L 01303 0031 4 -097 111 Fail 01303 00312 4 3 -013

46L 01975 0036 4 -046 128 Fail 01975 00359 4 3 -00644L 02898 0035 4 024 124 Fail 02898 00346 4 3 00312L 03895 0018 4 100 065 Fail 03895 00181 4 3 01364L 04260 0022 4 127 078 Fail 04260 00219 4 3 017

Totgem 0258 0027 mgkg 1-level 187 (177) 6 02582 () 6 5Totstd= 0132 0008 5-level 166 (154)

RESULTS Mean = 025818 mgkg

Repeatability variance S2r = 000083Repeatability std Sr = 002878 --gt 1115 r = 00806Between lab variance S2L = 001640Reproducibility var S2R = 001723Reproducibility std SR = 013127 --gt 5084 R = 03676Remarks none

000 050 100 150

k-values

26L

4L

46L

44L

12L

64L

Mandels k statistics(Soil 3 - PBD 209)

-02 -01 -01 00 01 01 02 02

Deviation from Mean

26L

4L

46L

44L

12L

64L

Labo

rato

ries

Soil 3 - PBD 209 -- Mean PARM = 0258 [mgkg]

-200 -100 000 100 200

h-values

26L

4L

46L

44L

12L

64L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 209)

Soil 3-PBD 209

Unit mgkg

Mandels k statistics(Compost 1 - Sum PBD)Mandels h statistics(Compost 1 - Sum PBD)

Sample Compost 1 Compost 1 - Sum PBD -- Mean PARM = 0009 [mgkg]

Element Sum PBD

General calcparmT1= 154064E-01T2= 169065E-03T3= 18T4= 68T5= 11354E-04

n= variabelp= 5

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00031 0002 4 -067 016 00031 00016 4 3 -0014L 00055 0005 4 -056 048 00055 00047 4 3 000

46L 00085 0003 4 -042 031 00085 00030 4 3 00026L 00123 0000 2 -024 003 00123 00002 2 1 00012L 00154 0002 4 -011 021 00154 00021 4 3 00144L 00613 0023 4 200 237 Fail - - 44L - - 005

Totgem 0018 0006 mgkg 1-level 187 (177) 5 00089 (44L) 5 4Totstd= 0022 0009 5-level 166 (154) 1

RESULTS Mean = 000893 mgkg

Repeatability variance S2r = 000001Repeatability std Sr = 000296 --gt 3308 r = 00083Between lab variance S2L = 000002Reproducibility var S2R = 000003Reproducibility std SR = 000570 --gt 6374 R = 00159Remarks 1 Lab rejected (44L)

000 050 100 150 200 250

k-values

10L

4L

46L

26L

12L

44L

Mandels k statistics(Compost 1 - Sum PBD)

00 00 00 00 00 00 01 01

Deviation from Mean

10L

4L

46L

26L

12L

44L

Labo

rato

ries

Compost 1 - Sum PBD -- Mean PARM = 0009 [mgkg]

-100 000 100 200

h-values

10L

4L

46L

26L

12L

44L

Labo

rato

ries

Mandels h statistics(Compost 1 - Sum PBD)

Compost 1-Sum PBD

Unit mgkg

Mandels k statistics(Sludge 1 - Sum PBD)Mandels h statistics(Sludge 1 - Sum PBD)

Sample Sludge 1 Sludge 1 - Sum PBD -- Mean PARM = 0256 [mgkg]

Element Sum PBD

General calcparmT1= 531806E+00T2= 162188E+00T3= 22T4= 84T5= 25223E-02

n= variabelp= 6

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00423 0025 4 -156 044 Fail 00423 00252 4 3 -02146L 01808 0118 4 -049 205 - - 46L - - -0074L 01810 0056 4 -049 097 01810 00558 4 3 -007

38L 02168 0006 4 -022 010 02168 00059 4 3 -00412L 02890 0065 4 034 113 02890 00647 4 3 00364L 03958 0008 4 116 014 Fail 03958 00079 4 3 01426L 04094 0034 2 126 059 Fail 04094 00337 2 1 015

Totgem 0245 0044 mgkg 1-level 198 (179) 6 02557 (46L) 6 5Totstd= 0130 0039 5-level 171 (155) 1

RESULTS Mean = 025570 mgkg

Repeatability variance S2r = 000158Repeatability std Sr = 003970 --gt 1553 r = 01112Between lab variance S2L = 001807Reproducibility var S2R = 001964Reproducibility std SR = 014015 --gt 5481 R = 03924Remarks 1 Lab rejected (46L)

000 050 100 150 200 250

k-values

10L

46L

4L

38L

12L

64L

26L

Mandels k statistics(Sludge 1 - Sum PBD)

-03 -02 -02 -01 -01 00 01 01 02 02

Deviation from Mean

10L

46L

4L

38L

12L

64L

26L

Labo

rato

ries

Sludge 1 - Sum PBD -- Mean PARM = 0256 [mgkg]

-200 -100 000 100 200

h-values

10L

46L

4L

38L

12L

64L

26L

Labo

rato

ries

Mandels h statistics(Sludge 1 - Sum PBD)

Sludge 1-Sum PBD

Unit mgkg

Mandels k statistics(Soil 3 - Sum PBD)Mandels h statistics(Soil 3 - Sum PBD)

Sample Soil 3 Soil 3 - Sum PBD -- Mean PARM = 0227 [mgkg]

Element Sum PBD

General calcparmT1= 610980E+00T2= 200876E+00T3= 26T4= 100T5= 13106E-02

n= variabelp= 7

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00028 0001 4 -037 000 Fail 00028 00005 4 3 -02226L 01179 0021 2 -036 003 Fail 01179 00208 2 1 -0114L 01305 0031 4 -036 004 Fail 01305 00308 4 3 -010

46L 02065 0035 4 -036 005 Fail 02065 00350 4 3 -00244L 02923 0037 4 -035 005 Fail 02923 00365 4 3 00712L 04051 0015 4 -034 002 Fail 04051 00149 4 3 01864L 04314 0022 4 -033 003 Fail 04314 00223 4 3 0203L 305500 2051 2 247 283 Fail - - 3L - - 3032

Totgem 4017 0276 mgkg 1-level 206 (181) 7 02266 (3L) 7 6Totstd= 10722 0717 5-level 175 (156) 1

RESULTS Mean = 022663 mgkg

Repeatability variance S2r = 000069Repeatability std Sr = 002626 --gt 1159 r = 00735Between lab variance S2L = 002568Reproducibility var S2R = 002637Reproducibility std SR = 016238 --gt 7165 R = 04547Remarks 1 Lab rejected (3L)

000 050 100 150 200 250 300

k-values

10L

26L

4L

46L

44L

12L

64L

3L

Mandels k statistics(Soil 3 - Sum PBD)

-50 00 50 100 150 200 250 300 350

Deviation from Mean

10L

26L

4L

46L

44L

12L

64L

3L

Labo

rato

ries

Soil 3 - Sum PBD -- Mean PARM = 0227 [mgkg]

-100 000 100 200 300

h-values

10L

26L

4L

46L

44L

12L

64L

3L

Labo

rato

ries

Mandels h statistics(Soil 3 - Sum PBD)

Soil 3-Sum PBD

19

Annex 4

Raw data submitted

Sample Compost1 Sample Compost 1 Sample Compost 1Element PBD 99 Element PBD 100 Element PBD 153

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]4L 00021 10L 00008 44L 000504L 00024 10L 00008 44L 000604L 00014 10L 00007 44L 000504L 00020 10L 00011 46L 00004

10L 00029 46L 00007 46L 0001210L 00027 46L 00012 46L 0000410L 00032 46L 00009 46L 0000946L 00025 46L 00007 12L 0000446L 00052 12L 00008 12L 0000846L 00029 12L 00012 12L 0000446L 00026 12L 00008 12L 0000712L 00026 12L 00014 26L 0000512L 00043 26L 00007 26L 0000512L 00026 26L 0000612L 0004726L 0002626L 00024

Sample Compost 1 Sample Compost 1 Sample Compost 1Element PBD 154 Element PBD 183 Element PBD 196

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]4L 00010 46L 00002 46L 00011

46L 00003 46L 00024 46L 0000846L 00007 46L 00021 12L 0000246L 00003 46L 00003 12L 0000346L 00004 12L 00003 12L 0000112L 00003 12L 00011 12L 0000212L 00005 12L 0000312L 00031 12L 0000312L 00006

Sample Compost 1 Sample Compost 1 Sample Compost 1Element PBD 197 Element PBD 203 Element PBD 209

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00002 46L 00010 4L 0004146L 00023 12L 00002 4L 0008946L 00022 12L 00003 44L 0041012L 00004 12L 00002 44L 0084012L 00006 12L 00002 44L 0064012L 00003 44L 0040012L 00004 12L 00079

12L 0007312L 0006512L 0009326L 0004926L 00049

Sample Compost 1Element PBD 47

LAB PARM [mgkg]26L 0003826L 00039

Element PBD 99 Element PBD 47 Element PBD 209LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]

4L 00170 10L 00210 4L 010004L 00200 10L 00220 4L 018004L 00170 10L 00210 4L 012004L 00190 46L 00300 4L 0220010L 00280 46L 00280 46L 0210010L 00300 46L 00250 46L 0200010L 00290 46L 00260 64L 0351846L 00340 64L 00059 64L 0363846L 00330 64L 00057 64L 0364546L 00300 64L 00062 64L 0350846L 00310 64L 00060 12L 0220964L 00194 12L 00191 12L 0177164L 00154 12L 00187 12L 0292264L 00185 12L 00190 12L 0164664L 00159 12L 00186 26L 0329712L 00242 26L 00666 26L 0300012L 00223 26L 0033212L 0022112L 0022226L 0024626L 00400

Element PBD 203 Element PBD 197 Element PBD 196LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00022 46L 00027 46L 0002446L 00014 46L 00024 46L 0002264L 00036 12L 00161 64L 0005864L 00058 12L 00060 64L 0006512L 00063 12L 00061 12L 0004812L 00034 12L 00036 12L 0002512L 00038 12L 0003212L 00027 12L 00022

Element PBD 183 Element PBD 154 Element PBD 153LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00049 4L 00020 4L 0002246L 00035 4L 00022 4L 0002446L 00036 4L 00020 4L 0002246L 00034 46L 00025 4L 0002664L 00027 46L 00025 46L 0004064L 00023 46L 00025 46L 0004264L 00024 46L 00023 46L 0003564L 00020 64L 00034 46L 0003812L 00230 64L 00023 64L 0007412L 00032 64L 00017 64L 0004712L 00031 64L 00011 64L 0004612L 00030 12L 00030 64L 0003026L 00007 12L 00021 12L 0006526L 00008 12L 00021 12L 00029

12L 00021 12L 0003226L 00015 12L 0002926L 00019 26L 00039

26L 00040

Element PBD 100LAB PARM [mgkg]

4L 000384L 000414L 000374L 00038

38L 0219038L 0220038L 0208038L 0220010L 0004410L 0005010L 0004310L 0004646L 0005746L 0005946L 0005346L 0005312L 0004312L 0004512L 0004312L 0004326L 0006226L 00057

Sample Soil 3 Sample Soil 3 Sample Soil 3Element PBD 99 Element PBD 47 Element PBD 100

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]10L 00016 10L 00011 10L 0000310L 00019 10L 00010 10L 0000410L 00013 10L 00012 10L 0000410L 00019 46L 00007 10L 0000246L 00025 46L 00022 46L 0000246L 00025 46L 00005 46L 0000646L 00008 46L 00007 46L 0000246L 00011 12L 00010 46L 0000264L 00005 12L 00017 3L 29100064L 00005 12L 00010 3L 32000064L 00006 12L 00009 26L 0000564L 00007 26L 00007 26L 0000512L 00012 26L 0000712L 0001312L 0001312L 0001226L 0000526L 00006

Sample Soil 3 Sample Soil 3 Sample Soil 3Element PBD 153 Element PBD 154 Element PBD 196

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]44L 00050 4L 00010 46L 0000744L 00050 46L 00001 46L 0001146L 00002 46L 00002 46L 0000846L 00003 46L 00001 46L 0001146L 00002 46L 00002 64L 0002646L 00002 64L 00001 64L 0002664L 00001 64L 00001 64L 0002964L 00001 64L 00001 64L 0003464L 00001 64L 00002 12L 0004564L 00002 12L 00003 12L 00032

12L 00002 12L 0002212L 00002 12L 0002112L 00002

Sample Soil 3 Sample Soil 3 Sample Soil 3Element PBD 197 Element PBD 203 Element PBD 209

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00006 46L 00011 4L 0091046L 00013 46L 00017 4L 0150046L 00011 46L 00015 4L 0120046L 00013 46L 00018 4L 0160012L 00090 64L 00013 44L 0337012L 00056 64L 00014 44L 0281012L 00033 64L 00016 44L 0287012L 00032 64L 00015 44L 02540

12L 00055 46L 0230012L 00041 46L 0220012L 00027 46L 0150012L 00026 46L 01900

64L 0438164L 0401664L 0414464L 0449812L 0367112L 0397812L 0409112L 03838

Sample Soil 3 26L 0102Element PBD 183 26L 0131

LAB PARM [mgkg]46L 0000746L 0000846L 0005846L 0000764L 0000264L 0000364L 0000364L 0000312L 0001512L 0001112L 0000712L 00007

European Commission EUR 23003 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on polybrominated diphenylethers Author(s) E Sobiecka H van der Sloot D Barcelo B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 68 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07403-5 Abstract Project HORIZONTAL is interdisciplinary aiming at a harmonisation and horizontal standardisation of test procedures in particular for sludge soils and biowastes In the context of this standardization project a series of draft technical specification were designed upon an extensive desk study fine-tuned after expert consultations and finally validated in international intercomparisons exercise This report summarises the work performed within the validation study of the draft standard for the determination of polybrominated diphenylethers (PBDE) in soils sludge and treated bio-waste using gas-chromatography method with mass selective detection (GC-MS) It further explains the underlying statistical concept for the calculation of reproducibility and repeatability from intercomparisons data In addition all single values results of the statistical evaluation as well as background information on the validation materials used are described and explained

The mission of the JRC is to provide customer-driven scientific and technical support for the conception development implementation and monitoring of EU policies As a service of the European Commission the JRC functions as a reference centre of science and technology for the Union Close to the policy-making process it serves the common interest of the Member States while being independent of special interests whether private or national

LB

-NA

-23003-EN

-C

Unit mgkg

Mandels k statistics(Soil 3 - PBD 47)Mandels h statistics(Soil 3 - PBD 47)

Sample Soil 3 Soil 3 - PBD 47 -- Mean PARM = 0001 [mgkg]

Element PBD 47

General calcparmT1= 134814E-02T2= 142830E-05T3= 13T4= 45T5= 22767E-06

n= variabelp= 4

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean26L 00007 0000 2 -143 001 00007 00000 2 1 00046L 00010 0001 4 010 181 00010 00008 4 3 00010L 00011 0000 3 049 023 00011 00001 3 2 00012L 00012 0000 4 084 081 00012 00004 4 3 000

Totgem 0001 0000 mgkg 1-level 149 (177) 4 00010 () 4 3Totstd= 0000 0000 5-level 142 (159)

RESULTS Mean = 000100 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000050 --gt 5031 r = 00014Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000050 --gt 5031 R = 00014Remarks none

000 050 100 150 200

k-values

26L

46L

10L

12L

Mandels k statistics(Soil 3 - PBD 47)

00 00 00 00 00 00 00 00 00 00 00

Deviation from Mean

26L

46L

10L

12L

Labo

rato

ries

Soil 3 - PBD 47 -- Mean PARM = 0001 [mgkg]

-200 -100 000 100

h-values

26L

46L

10L

12L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 47)

Soil 3-PBD 47

Unit mgkg

Mandels k statistics(Compost 1 - PBD 99)Mandels h statistics(Compost 1 - PBD 99)

Sample Compost 1 Compost 1 - PBD 99 -- Mean PARM = 0003 [mgkg]

Element PBD 99

General calcparmT1= 492124E-02T2= 148747E-04T3= 17T4= 61T5= 93196E-06

n= variabelp= 5

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00020 0000 4 -137 053 00020 00004 4 3 000

26L 00025 0000 2 -058 024 00025 00002 2 1 00010L 00029 0000 3 012 032 00029 00003 3 2 00046L 00033 0001 4 069 161 00033 00013 4 3 00012L 00036 0001 4 114 140 00036 00011 4 3 000

Totgem 0003 0001 mgkg 1-level 172 (185) 5 00029 () 5 4Totstd= 0001 0001 5-level 157 (162)

RESULTS Mean = 000286 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000088 --gt 3086 r = 00025Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000101 --gt 3525 R = 00028Remarks none

000 050 100 150 200

k-values

4L

26L

10L

46L

12L

Mandels k statistics(Compost 1 - PBD 99)

00 00 00 00 00 00 00 00 00 00

Deviation from Mean

4L

26L

10L

46L

12L

Labo

rato

ries

Compost 1 - PBD 99 -- Mean PARM = 0003 [mgkg]

-200 -100 000 100 200

h-values

4L

26L

10L

46L

12L

Labo

rato

ries

Mandels h statistics(Compost 1 - PBD 99)

Compost 1-PBD 99

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 99)Mandels h statistics(Sludge 1 - PBD 99)

Sample Sludge 1 Sludge 1 - PBD 99 -- Mean PARM = 0024 [mgkg]

Element PBD 99

General calcparmT1= 448050E-01T2= 112113E-02T3= 19T4= 73T5= 32972E-05

n= variabelp= 5

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean64L 00173 0002 4 -118 041 Fail 00173 00019 4 3 -0014L 00183 0002 4 -104 032 00183 00015 4 3 -001

12L 00227 0001 4 -038 022 00227 00010 4 3 00010L 00290 0001 3 055 021 00290 00010 3 2 00146L 00320 0002 4 100 039 00320 00018 4 3 00126L 00323 0011 2 105 234 - - 26L - - 001

Totgem 0025 0003 mgkg 1-level 187 (177) 5 00239 (26L) 5 4Totstd= 0007 0004 5-level 166 (154) 1

RESULTS Mean = 002385 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000153 --gt 643 r = 00043Between lab variance S2L = 000004Reproducibility var S2R = 000004Reproducibility std SR = 000666 --gt 2791 R = 00186Remarks 1 Lab rejected (26L)

000 050 100 150 200 250

k-values

64L

4L

12L

10L

46L

26L

Mandels k statistics(Sludge 1 - PBD 99)

00 00 00 00 00 00 00 00 00 00

Deviation from Mean

64L

4L

12L

10L

46L

26L

Labo

rato

ries

Sludge 1 - PBD 99 -- Mean PARM = 0024 [mgkg]

-200 -100 000 100 200

h-values

64L

4L

12L

10L

46L

26L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 99)

Sludge 1-PBD 99

Unit mgkg

Mandels k statistics(Soil 3 - PBD 99)Mandels h statistics(Soil 3 - PBD 99)

Sample Soil 3 NUM

Element PBD 99

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00017 0000 4 091 068 - - 10L - - NUM46L 00017 0001 4 100 211 - - 46L - - NUM64L 00005 0000 4 -106 023 NUM - 64L - - NUM12L 00012 0000 4 015 014 - - 12L - - NUM26L 00006 0000 2 -101 012 - - 26L - - NUM

Totgem 0001 0000 mgkg 1-level 172 (173) NUM (10L46L64L12L26L) -1Totstd= 0001 0000 5-level 157 (153) 5

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 5 Labs rejected (10L46L64L12L26L)

000 050 100 150 200 250

k-values

10L

46L

64L

12L

26L

Mandels k statistics(Soil 3 - PBD 99)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

10L

46L

64L

12L

26L

Labo

rato

ries

NUM

-200 -100 000 100 200

h-values

10L

46L

64L

12L

26L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 99)

Soil 3-PBD 99

Unit mgkg

Mandels k statistics(Compost 1 - PBD 100)Mandels h statistics(Compost 1 - PBD 100)

Sample Compost 1 Compost 1 - PBD 100 -- Mean PARM = 0001 [mgkg]

Element PBD 100

General calcparmT1= 124272E-02T2= 113129E-05T3= 14T4= 52T5= 46584E-07

n= variabelp= 4

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean26L 00006 0000 2 -131 037 Fail 00006 00001 2 1 00010L 00009 0000 4 003 083 00009 00002 4 3 00046L 00009 0000 4 016 115 00009 00002 4 3 00012L 00011 0000 4 112 136 Fail 00011 00003 4 3 000

Totgem 0001 0000 mgkg 1-level 149 (167) 4 00009 () 4 3Totstd= 0000 0000 5-level 142 (15)

RESULTS Mean = 000085 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000022 --gt 2531 r = 00006Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000025 --gt 2882 R = 00007Remarks none

000 050 100 150

k-values

26L

10L

46L

12L

Mandels k statistics(Compost 1 - PBD 100)

00 00 00 00 00 00 00 00 00 00 00

Deviation from Mean

26L

10L

46L

12L

Labo

rato

ries

Compost 1 - PBD 100 -- Mean PARM = 0001 [mgkg]

-200 -100 000 100 200

h-values

26L

10L

46L

12L

Labo

rato

ries

Mandels h statistics(Compost 1 - PBD 100)

Compost 1-PBD 100

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 100)Mandels h statistics(Sludge 1 - PBD 100)

Sample Sludge 1 Sludge 1 - PBD 100 -- Mean PARM = 0005 [mgkg]

Element PBD 100

General calcparmT1= 852065E-02T2= 412762E-04T3= 18T4= 68T5= 78914E-07

n= variabelp= 5

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00039 0000 4 -042 007 Fail 00039 00002 4 3 000

12L 00044 0000 4 -041 005 Fail 00044 00001 4 3 00010L 00046 0000 4 -041 013 Fail 00046 00003 4 3 00046L 00056 0000 4 -040 012 Fail 00056 00003 4 3 00026L 00059 0000 2 -040 013 Fail 00059 00003 2 1 00038L 02168 0006 4 204 244 Fail - - 38L - - 021

Totgem 0040 0001 mgkg 1-level 187 (177) 5 00049 (38L) 5 4Totstd= 0087 0002 5-level 166 (154) 1

RESULTS Mean = 000486 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000025 --gt 507 r = 00007Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000084 --gt 1731 R = 00024Remarks 1 Lab rejected (38L)

000 050 100 150 200 250

k-values

4L

12L

10L

46L

26L

38L

Mandels k statistics(Sludge 1 - PBD 100)

-01 00 01 01 02 02 03

Deviation from Mean

4L

12L

10L

46L

26L

38L

Labo

rato

ries

Sludge 1 - PBD 100 -- Mean PARM = 0005 [mgkg]

-100 000 100 200 300

h-values

4L

12L

10L

46L

26L

38L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 100)

Sludge 1-PBD 100

Unit mgkg

Mandels k statistics(Soil 3 - PBD 100)Mandels h statistics(Soil 3 - PBD 100)

Sample Soil 3 NUM

Element PBD 100

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00003 0000 4 -050 000 Fail - - 10L - - NUM46L 00003 0000 4 -050 000 Fail NUM - 46L - - NUM3L 305500 2051 2 150 200 Fail - - 3L - - NUM

26L 00005 0000 2 -050 000 Fail - - 26L - - NUM

Totgem 7638 0513 mgkg 1-level 149 (177) NUM (10L46L3L26L) -1Totstd= 15275 1025 5-level 142 (159) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (10L46L3L26L)

000 050 100 150 200

k-values

10L

46L

3L

26L

Mandels k statistics(Soil 3 - PBD 100)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

10L

46L

3L

26L

Labo

rato

ries

NUM

-100 000 100 200

h-values

10L

46L

3L

26L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 100)

Soil 3-PBD 100

Unit mgkg

Mandels k statistics(Compost 1 - PBD 153)Mandels h statistics(Compost 1 - PBD 153)

Sample Compost 1 NUM

Element PBD 153

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean44L 00053 0001 3 150 157 Fail - - 44L - - NUM46L 00007 0000 4 -044 111 Fail - - 46L - - NUM12L 00005 0000 4 -051 055 Fail - - 12L - - NUM26L 00005 0000 2 -054 001 Fail NUM - 26L - - NUM

Totgem 0002 0000 mgkg 1-level 149 (177) NUM (44L46L12L26L) -1Totstd= 0002 0000 5-level 142 (159) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (44L46L12L26L)

000 050 100 150 200

k-values

44L

46L

12L

26L

Mandels k statistics(Compost 1 - PBD 153)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

44L

46L

12L

26L

Labo

rato

ries

NUM

-100 000 100 200

h-values

44L

46L

12L

26L

Labo

rato

ries

Mandels h statistics(Compost 1 - PBD 153)

Compost 1-PBD 153

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 153)Mandels h statistics(Sludge 1 - PBD 153)

Sample Sludge 1 Sludge 1 - PBD 153 -- Mean PARM = 0004 [mgkg]

Element PBD 153

General calcparmT1= 676738E-02T2= 267609E-04T3= 18T4= 68T5= 19626E-05

n= variabelp= 5

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00024 0000 4 -157 017 00024 00002 4 3 000

12L 00038 0002 4 006 154 00038 00018 4 3 00046L 00039 0000 4 011 026 00039 00003 4 3 00026L 00039 0000 2 018 004 00039 00000 2 1 00064L 00049 0002 4 122 159 00049 00018 4 3 000

Totgem 0004 0001 mgkg 1-level 172 (173) 5 00038 () 5 4Totstd= 0001 0001 5-level 157 (153)

RESULTS Mean = 000378 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000123 --gt 3252 r = 00034Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000142 --gt 3754 R = 00040Remarks none

000 050 100 150 200

k-values

4L

12L

46L

26L

64L

Mandels k statistics(Sludge 1 - PBD 153)

00 00 00 00 00 00 00

Deviation from Mean

4L

12L

46L

26L

64L

Labo

rato

ries

Sludge 1 - PBD 153 -- Mean PARM = 0004 [mgkg]

-200 -100 000 100 200

h-values

4L

12L

46L

26L

64L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 153)

Sludge 1-PBD 153

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 154)Mandels h statistics(Sludge 1 - PBD 154)

Sample Sludge 1 NA

Element PBD 154

General calcparmT1= NAT2= NAT3=T4=T5=

n= variabelp=

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00021 0000 3 -100 021 NA - 4L - - NA

46L 00025 0000 4 115 018 NA - 46L - - NA64L 00021 0001 4 -066 179 - - 64L - - NA12L 00023 0000 4 050 085 - - 12L - - NA

Totgem 0002 0000 mgkg 1-level 149 (167) NA (4L46L64L12L) -1Totstd= 0000 0000 5-level 142 (15) 4

RESULTS Mean = NA mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NAReproducibility var S2R = NAReproducibility std SR = NA --gt NA R = NARemarks 4 Labs rejected (4L46L64L12L)

000 050 100 150 200

k-values

4L

46L

64L

12L

Mandels k statistics(Sludge 1 - PBD 154)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

4L

46L

64L

12L

Labo

rato

ries

NA

-100 000 100 200

h-values

4L

46L

64L

12L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 154)

Sludge 1-PBD 154

Unit mgkg

Mandels k statistics(Soil 3 - PBD 154)Mandels h statistics(Soil 3 - PBD 154)

Sample Soil 3 NUM

Element PBD 154

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

4L 00010 - 1 150 Fail - - 4L - - NUM46L 00001 0000 4 -053 096 Fail - - 46L - - NUM64L 00001 0000 4 -056 105 Fail NUM - 64L - - NUM12L 00002 0000 4 -040 099 Fail - - 12L - - NUM

Totgem 000037 0000 mgkg 1-level 149 (164) NUM (4L46L64L12L) -1Totstd= 000042 0000 5-level 142 (153) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (4L46L64L12L)

000 050 100 150

k-values

4L

46L

64L

12L

Mandels k statistics(Soil 3 - PBD 154)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

4L

46L

64L

12L

Labo

rato

ries

NUM

-100 000 100 200

h-values

4L

46L

64L

12L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 154)

Soil 3-PBD 154

Unit mgkg

Mandels k statistics(Compost 1 - PBD 209)Mandels h statistics(Compost 1 - PBD 209)

Sample Compost 1 NUM

Element PBD 209

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00065 0003 2 -049 032 - - 4L - - NUM

44L 00573 0021 4 150 197 Fail - - 44L - - NUM12L 00078 0001 4 -045 011 - - 12L - - NUM26L 00049 0000 2 -056 000 NUM - 26L - - NUM

Totgem 0019 0006 mgkg 1-level 149 (177) NUM (4L44L12L26L) -1Totstd= 0025 0010 5-level 142 (159) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (4L44L12L26L)

000 050 100 150 200

k-values

4L

44L

12L

26L

Mandels k statistics(Compost 1 - PBD 209)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

4L

44L

12L

26L

Labo

rato

ries

NUM

-100 000 100 200

h-values

4L

44L

12L

26L

Labo

rato

ries

Mandels h statistics(Compost 1 - PBD 209)

Compost 1-PBD 209

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 209)Mandels h statistics(Sludge 1 - PBD 209)

Sample Sludge 1 Sludge 1 - PBD 209 -- Mean PARM = 0249 [mgkg]

Element PBD 209

General calcparmT1= 394542E+00T2= 107296E+00T3= 16T4= 56T5= 19723E-02

n= variabelp= 5

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 01550 0055 4 -112 148 Fail 01550 00551 4 3 -009

46L 02050 0007 2 -053 019 02050 00071 2 1 -00412L 02137 0058 4 -042 155 02137 00576 4 3 -00426L 03149 0021 2 078 057 Fail 03149 00210 2 1 00764L 03577 0007 4 129 020 Fail 03577 00074 4 3 011

Totgem 0249 0030 mgkg 1-level 172 (185) 5 02493 () 5 4Totstd= 0084 0025 5-level 157 (162)

RESULTS Mean = 024926 mgkg

Repeatability variance S2r = 000179Repeatability std Sr = 004234 --gt 1699 r = 01186Between lab variance S2L = 000743Reproducibility var S2R = 000922Reproducibility std SR = 009604 --gt 3853 R = 02689Remarks none

000 050 100 150 200

k-values

4L

46L

12L

26L

64L

Mandels k statistics(Sludge 1 - PBD 209)

-01 -01 00 01 01 02

Deviation from Mean

4L

46L

12L

26L

64L

Labo

rato

ries

Sludge 1 - PBD 209 -- Mean PARM = 0249 [mgkg]

-200 -100 000 100 200

h-values

4L

46L

12L

26L

64L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 209)

Sludge 1-PBD 209

Unit mgkg

Mandels k statistics(Soil 3 - PBD 209)Mandels h statistics(Soil 3 - PBD 209)

Sample Soil 3 Soil 3 - PBD 209 -- Mean PARM = 0258 [mgkg]

Element PBD 209

General calcparmT1= 596398E+00T2= 191917E+00T3= 22T4= 84T5= 13249E-02

n= variabelp= 6

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean26L 01162 0021 2 -108 074 Fail 01162 00207 2 1 -0144L 01303 0031 4 -097 111 Fail 01303 00312 4 3 -013

46L 01975 0036 4 -046 128 Fail 01975 00359 4 3 -00644L 02898 0035 4 024 124 Fail 02898 00346 4 3 00312L 03895 0018 4 100 065 Fail 03895 00181 4 3 01364L 04260 0022 4 127 078 Fail 04260 00219 4 3 017

Totgem 0258 0027 mgkg 1-level 187 (177) 6 02582 () 6 5Totstd= 0132 0008 5-level 166 (154)

RESULTS Mean = 025818 mgkg

Repeatability variance S2r = 000083Repeatability std Sr = 002878 --gt 1115 r = 00806Between lab variance S2L = 001640Reproducibility var S2R = 001723Reproducibility std SR = 013127 --gt 5084 R = 03676Remarks none

000 050 100 150

k-values

26L

4L

46L

44L

12L

64L

Mandels k statistics(Soil 3 - PBD 209)

-02 -01 -01 00 01 01 02 02

Deviation from Mean

26L

4L

46L

44L

12L

64L

Labo

rato

ries

Soil 3 - PBD 209 -- Mean PARM = 0258 [mgkg]

-200 -100 000 100 200

h-values

26L

4L

46L

44L

12L

64L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 209)

Soil 3-PBD 209

Unit mgkg

Mandels k statistics(Compost 1 - Sum PBD)Mandels h statistics(Compost 1 - Sum PBD)

Sample Compost 1 Compost 1 - Sum PBD -- Mean PARM = 0009 [mgkg]

Element Sum PBD

General calcparmT1= 154064E-01T2= 169065E-03T3= 18T4= 68T5= 11354E-04

n= variabelp= 5

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00031 0002 4 -067 016 00031 00016 4 3 -0014L 00055 0005 4 -056 048 00055 00047 4 3 000

46L 00085 0003 4 -042 031 00085 00030 4 3 00026L 00123 0000 2 -024 003 00123 00002 2 1 00012L 00154 0002 4 -011 021 00154 00021 4 3 00144L 00613 0023 4 200 237 Fail - - 44L - - 005

Totgem 0018 0006 mgkg 1-level 187 (177) 5 00089 (44L) 5 4Totstd= 0022 0009 5-level 166 (154) 1

RESULTS Mean = 000893 mgkg

Repeatability variance S2r = 000001Repeatability std Sr = 000296 --gt 3308 r = 00083Between lab variance S2L = 000002Reproducibility var S2R = 000003Reproducibility std SR = 000570 --gt 6374 R = 00159Remarks 1 Lab rejected (44L)

000 050 100 150 200 250

k-values

10L

4L

46L

26L

12L

44L

Mandels k statistics(Compost 1 - Sum PBD)

00 00 00 00 00 00 01 01

Deviation from Mean

10L

4L

46L

26L

12L

44L

Labo

rato

ries

Compost 1 - Sum PBD -- Mean PARM = 0009 [mgkg]

-100 000 100 200

h-values

10L

4L

46L

26L

12L

44L

Labo

rato

ries

Mandels h statistics(Compost 1 - Sum PBD)

Compost 1-Sum PBD

Unit mgkg

Mandels k statistics(Sludge 1 - Sum PBD)Mandels h statistics(Sludge 1 - Sum PBD)

Sample Sludge 1 Sludge 1 - Sum PBD -- Mean PARM = 0256 [mgkg]

Element Sum PBD

General calcparmT1= 531806E+00T2= 162188E+00T3= 22T4= 84T5= 25223E-02

n= variabelp= 6

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00423 0025 4 -156 044 Fail 00423 00252 4 3 -02146L 01808 0118 4 -049 205 - - 46L - - -0074L 01810 0056 4 -049 097 01810 00558 4 3 -007

38L 02168 0006 4 -022 010 02168 00059 4 3 -00412L 02890 0065 4 034 113 02890 00647 4 3 00364L 03958 0008 4 116 014 Fail 03958 00079 4 3 01426L 04094 0034 2 126 059 Fail 04094 00337 2 1 015

Totgem 0245 0044 mgkg 1-level 198 (179) 6 02557 (46L) 6 5Totstd= 0130 0039 5-level 171 (155) 1

RESULTS Mean = 025570 mgkg

Repeatability variance S2r = 000158Repeatability std Sr = 003970 --gt 1553 r = 01112Between lab variance S2L = 001807Reproducibility var S2R = 001964Reproducibility std SR = 014015 --gt 5481 R = 03924Remarks 1 Lab rejected (46L)

000 050 100 150 200 250

k-values

10L

46L

4L

38L

12L

64L

26L

Mandels k statistics(Sludge 1 - Sum PBD)

-03 -02 -02 -01 -01 00 01 01 02 02

Deviation from Mean

10L

46L

4L

38L

12L

64L

26L

Labo

rato

ries

Sludge 1 - Sum PBD -- Mean PARM = 0256 [mgkg]

-200 -100 000 100 200

h-values

10L

46L

4L

38L

12L

64L

26L

Labo

rato

ries

Mandels h statistics(Sludge 1 - Sum PBD)

Sludge 1-Sum PBD

Unit mgkg

Mandels k statistics(Soil 3 - Sum PBD)Mandels h statistics(Soil 3 - Sum PBD)

Sample Soil 3 Soil 3 - Sum PBD -- Mean PARM = 0227 [mgkg]

Element Sum PBD

General calcparmT1= 610980E+00T2= 200876E+00T3= 26T4= 100T5= 13106E-02

n= variabelp= 7

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00028 0001 4 -037 000 Fail 00028 00005 4 3 -02226L 01179 0021 2 -036 003 Fail 01179 00208 2 1 -0114L 01305 0031 4 -036 004 Fail 01305 00308 4 3 -010

46L 02065 0035 4 -036 005 Fail 02065 00350 4 3 -00244L 02923 0037 4 -035 005 Fail 02923 00365 4 3 00712L 04051 0015 4 -034 002 Fail 04051 00149 4 3 01864L 04314 0022 4 -033 003 Fail 04314 00223 4 3 0203L 305500 2051 2 247 283 Fail - - 3L - - 3032

Totgem 4017 0276 mgkg 1-level 206 (181) 7 02266 (3L) 7 6Totstd= 10722 0717 5-level 175 (156) 1

RESULTS Mean = 022663 mgkg

Repeatability variance S2r = 000069Repeatability std Sr = 002626 --gt 1159 r = 00735Between lab variance S2L = 002568Reproducibility var S2R = 002637Reproducibility std SR = 016238 --gt 7165 R = 04547Remarks 1 Lab rejected (3L)

000 050 100 150 200 250 300

k-values

10L

26L

4L

46L

44L

12L

64L

3L

Mandels k statistics(Soil 3 - Sum PBD)

-50 00 50 100 150 200 250 300 350

Deviation from Mean

10L

26L

4L

46L

44L

12L

64L

3L

Labo

rato

ries

Soil 3 - Sum PBD -- Mean PARM = 0227 [mgkg]

-100 000 100 200 300

h-values

10L

26L

4L

46L

44L

12L

64L

3L

Labo

rato

ries

Mandels h statistics(Soil 3 - Sum PBD)

Soil 3-Sum PBD

19

Annex 4

Raw data submitted

Sample Compost1 Sample Compost 1 Sample Compost 1Element PBD 99 Element PBD 100 Element PBD 153

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]4L 00021 10L 00008 44L 000504L 00024 10L 00008 44L 000604L 00014 10L 00007 44L 000504L 00020 10L 00011 46L 00004

10L 00029 46L 00007 46L 0001210L 00027 46L 00012 46L 0000410L 00032 46L 00009 46L 0000946L 00025 46L 00007 12L 0000446L 00052 12L 00008 12L 0000846L 00029 12L 00012 12L 0000446L 00026 12L 00008 12L 0000712L 00026 12L 00014 26L 0000512L 00043 26L 00007 26L 0000512L 00026 26L 0000612L 0004726L 0002626L 00024

Sample Compost 1 Sample Compost 1 Sample Compost 1Element PBD 154 Element PBD 183 Element PBD 196

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]4L 00010 46L 00002 46L 00011

46L 00003 46L 00024 46L 0000846L 00007 46L 00021 12L 0000246L 00003 46L 00003 12L 0000346L 00004 12L 00003 12L 0000112L 00003 12L 00011 12L 0000212L 00005 12L 0000312L 00031 12L 0000312L 00006

Sample Compost 1 Sample Compost 1 Sample Compost 1Element PBD 197 Element PBD 203 Element PBD 209

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00002 46L 00010 4L 0004146L 00023 12L 00002 4L 0008946L 00022 12L 00003 44L 0041012L 00004 12L 00002 44L 0084012L 00006 12L 00002 44L 0064012L 00003 44L 0040012L 00004 12L 00079

12L 0007312L 0006512L 0009326L 0004926L 00049

Sample Compost 1Element PBD 47

LAB PARM [mgkg]26L 0003826L 00039

Element PBD 99 Element PBD 47 Element PBD 209LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]

4L 00170 10L 00210 4L 010004L 00200 10L 00220 4L 018004L 00170 10L 00210 4L 012004L 00190 46L 00300 4L 0220010L 00280 46L 00280 46L 0210010L 00300 46L 00250 46L 0200010L 00290 46L 00260 64L 0351846L 00340 64L 00059 64L 0363846L 00330 64L 00057 64L 0364546L 00300 64L 00062 64L 0350846L 00310 64L 00060 12L 0220964L 00194 12L 00191 12L 0177164L 00154 12L 00187 12L 0292264L 00185 12L 00190 12L 0164664L 00159 12L 00186 26L 0329712L 00242 26L 00666 26L 0300012L 00223 26L 0033212L 0022112L 0022226L 0024626L 00400

Element PBD 203 Element PBD 197 Element PBD 196LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00022 46L 00027 46L 0002446L 00014 46L 00024 46L 0002264L 00036 12L 00161 64L 0005864L 00058 12L 00060 64L 0006512L 00063 12L 00061 12L 0004812L 00034 12L 00036 12L 0002512L 00038 12L 0003212L 00027 12L 00022

Element PBD 183 Element PBD 154 Element PBD 153LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00049 4L 00020 4L 0002246L 00035 4L 00022 4L 0002446L 00036 4L 00020 4L 0002246L 00034 46L 00025 4L 0002664L 00027 46L 00025 46L 0004064L 00023 46L 00025 46L 0004264L 00024 46L 00023 46L 0003564L 00020 64L 00034 46L 0003812L 00230 64L 00023 64L 0007412L 00032 64L 00017 64L 0004712L 00031 64L 00011 64L 0004612L 00030 12L 00030 64L 0003026L 00007 12L 00021 12L 0006526L 00008 12L 00021 12L 00029

12L 00021 12L 0003226L 00015 12L 0002926L 00019 26L 00039

26L 00040

Element PBD 100LAB PARM [mgkg]

4L 000384L 000414L 000374L 00038

38L 0219038L 0220038L 0208038L 0220010L 0004410L 0005010L 0004310L 0004646L 0005746L 0005946L 0005346L 0005312L 0004312L 0004512L 0004312L 0004326L 0006226L 00057

Sample Soil 3 Sample Soil 3 Sample Soil 3Element PBD 99 Element PBD 47 Element PBD 100

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]10L 00016 10L 00011 10L 0000310L 00019 10L 00010 10L 0000410L 00013 10L 00012 10L 0000410L 00019 46L 00007 10L 0000246L 00025 46L 00022 46L 0000246L 00025 46L 00005 46L 0000646L 00008 46L 00007 46L 0000246L 00011 12L 00010 46L 0000264L 00005 12L 00017 3L 29100064L 00005 12L 00010 3L 32000064L 00006 12L 00009 26L 0000564L 00007 26L 00007 26L 0000512L 00012 26L 0000712L 0001312L 0001312L 0001226L 0000526L 00006

Sample Soil 3 Sample Soil 3 Sample Soil 3Element PBD 153 Element PBD 154 Element PBD 196

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]44L 00050 4L 00010 46L 0000744L 00050 46L 00001 46L 0001146L 00002 46L 00002 46L 0000846L 00003 46L 00001 46L 0001146L 00002 46L 00002 64L 0002646L 00002 64L 00001 64L 0002664L 00001 64L 00001 64L 0002964L 00001 64L 00001 64L 0003464L 00001 64L 00002 12L 0004564L 00002 12L 00003 12L 00032

12L 00002 12L 0002212L 00002 12L 0002112L 00002

Sample Soil 3 Sample Soil 3 Sample Soil 3Element PBD 197 Element PBD 203 Element PBD 209

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00006 46L 00011 4L 0091046L 00013 46L 00017 4L 0150046L 00011 46L 00015 4L 0120046L 00013 46L 00018 4L 0160012L 00090 64L 00013 44L 0337012L 00056 64L 00014 44L 0281012L 00033 64L 00016 44L 0287012L 00032 64L 00015 44L 02540

12L 00055 46L 0230012L 00041 46L 0220012L 00027 46L 0150012L 00026 46L 01900

64L 0438164L 0401664L 0414464L 0449812L 0367112L 0397812L 0409112L 03838

Sample Soil 3 26L 0102Element PBD 183 26L 0131

LAB PARM [mgkg]46L 0000746L 0000846L 0005846L 0000764L 0000264L 0000364L 0000364L 0000312L 0001512L 0001112L 0000712L 00007

European Commission EUR 23003 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on polybrominated diphenylethers Author(s) E Sobiecka H van der Sloot D Barcelo B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 68 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07403-5 Abstract Project HORIZONTAL is interdisciplinary aiming at a harmonisation and horizontal standardisation of test procedures in particular for sludge soils and biowastes In the context of this standardization project a series of draft technical specification were designed upon an extensive desk study fine-tuned after expert consultations and finally validated in international intercomparisons exercise This report summarises the work performed within the validation study of the draft standard for the determination of polybrominated diphenylethers (PBDE) in soils sludge and treated bio-waste using gas-chromatography method with mass selective detection (GC-MS) It further explains the underlying statistical concept for the calculation of reproducibility and repeatability from intercomparisons data In addition all single values results of the statistical evaluation as well as background information on the validation materials used are described and explained

The mission of the JRC is to provide customer-driven scientific and technical support for the conception development implementation and monitoring of EU policies As a service of the European Commission the JRC functions as a reference centre of science and technology for the Union Close to the policy-making process it serves the common interest of the Member States while being independent of special interests whether private or national

LB

-NA

-23003-EN

-C

Unit mgkg

Mandels k statistics(Compost 1 - PBD 99)Mandels h statistics(Compost 1 - PBD 99)

Sample Compost 1 Compost 1 - PBD 99 -- Mean PARM = 0003 [mgkg]

Element PBD 99

General calcparmT1= 492124E-02T2= 148747E-04T3= 17T4= 61T5= 93196E-06

n= variabelp= 5

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00020 0000 4 -137 053 00020 00004 4 3 000

26L 00025 0000 2 -058 024 00025 00002 2 1 00010L 00029 0000 3 012 032 00029 00003 3 2 00046L 00033 0001 4 069 161 00033 00013 4 3 00012L 00036 0001 4 114 140 00036 00011 4 3 000

Totgem 0003 0001 mgkg 1-level 172 (185) 5 00029 () 5 4Totstd= 0001 0001 5-level 157 (162)

RESULTS Mean = 000286 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000088 --gt 3086 r = 00025Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000101 --gt 3525 R = 00028Remarks none

000 050 100 150 200

k-values

4L

26L

10L

46L

12L

Mandels k statistics(Compost 1 - PBD 99)

00 00 00 00 00 00 00 00 00 00

Deviation from Mean

4L

26L

10L

46L

12L

Labo

rato

ries

Compost 1 - PBD 99 -- Mean PARM = 0003 [mgkg]

-200 -100 000 100 200

h-values

4L

26L

10L

46L

12L

Labo

rato

ries

Mandels h statistics(Compost 1 - PBD 99)

Compost 1-PBD 99

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 99)Mandels h statistics(Sludge 1 - PBD 99)

Sample Sludge 1 Sludge 1 - PBD 99 -- Mean PARM = 0024 [mgkg]

Element PBD 99

General calcparmT1= 448050E-01T2= 112113E-02T3= 19T4= 73T5= 32972E-05

n= variabelp= 5

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean64L 00173 0002 4 -118 041 Fail 00173 00019 4 3 -0014L 00183 0002 4 -104 032 00183 00015 4 3 -001

12L 00227 0001 4 -038 022 00227 00010 4 3 00010L 00290 0001 3 055 021 00290 00010 3 2 00146L 00320 0002 4 100 039 00320 00018 4 3 00126L 00323 0011 2 105 234 - - 26L - - 001

Totgem 0025 0003 mgkg 1-level 187 (177) 5 00239 (26L) 5 4Totstd= 0007 0004 5-level 166 (154) 1

RESULTS Mean = 002385 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000153 --gt 643 r = 00043Between lab variance S2L = 000004Reproducibility var S2R = 000004Reproducibility std SR = 000666 --gt 2791 R = 00186Remarks 1 Lab rejected (26L)

000 050 100 150 200 250

k-values

64L

4L

12L

10L

46L

26L

Mandels k statistics(Sludge 1 - PBD 99)

00 00 00 00 00 00 00 00 00 00

Deviation from Mean

64L

4L

12L

10L

46L

26L

Labo

rato

ries

Sludge 1 - PBD 99 -- Mean PARM = 0024 [mgkg]

-200 -100 000 100 200

h-values

64L

4L

12L

10L

46L

26L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 99)

Sludge 1-PBD 99

Unit mgkg

Mandels k statistics(Soil 3 - PBD 99)Mandels h statistics(Soil 3 - PBD 99)

Sample Soil 3 NUM

Element PBD 99

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00017 0000 4 091 068 - - 10L - - NUM46L 00017 0001 4 100 211 - - 46L - - NUM64L 00005 0000 4 -106 023 NUM - 64L - - NUM12L 00012 0000 4 015 014 - - 12L - - NUM26L 00006 0000 2 -101 012 - - 26L - - NUM

Totgem 0001 0000 mgkg 1-level 172 (173) NUM (10L46L64L12L26L) -1Totstd= 0001 0000 5-level 157 (153) 5

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 5 Labs rejected (10L46L64L12L26L)

000 050 100 150 200 250

k-values

10L

46L

64L

12L

26L

Mandels k statistics(Soil 3 - PBD 99)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

10L

46L

64L

12L

26L

Labo

rato

ries

NUM

-200 -100 000 100 200

h-values

10L

46L

64L

12L

26L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 99)

Soil 3-PBD 99

Unit mgkg

Mandels k statistics(Compost 1 - PBD 100)Mandels h statistics(Compost 1 - PBD 100)

Sample Compost 1 Compost 1 - PBD 100 -- Mean PARM = 0001 [mgkg]

Element PBD 100

General calcparmT1= 124272E-02T2= 113129E-05T3= 14T4= 52T5= 46584E-07

n= variabelp= 4

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean26L 00006 0000 2 -131 037 Fail 00006 00001 2 1 00010L 00009 0000 4 003 083 00009 00002 4 3 00046L 00009 0000 4 016 115 00009 00002 4 3 00012L 00011 0000 4 112 136 Fail 00011 00003 4 3 000

Totgem 0001 0000 mgkg 1-level 149 (167) 4 00009 () 4 3Totstd= 0000 0000 5-level 142 (15)

RESULTS Mean = 000085 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000022 --gt 2531 r = 00006Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000025 --gt 2882 R = 00007Remarks none

000 050 100 150

k-values

26L

10L

46L

12L

Mandels k statistics(Compost 1 - PBD 100)

00 00 00 00 00 00 00 00 00 00 00

Deviation from Mean

26L

10L

46L

12L

Labo

rato

ries

Compost 1 - PBD 100 -- Mean PARM = 0001 [mgkg]

-200 -100 000 100 200

h-values

26L

10L

46L

12L

Labo

rato

ries

Mandels h statistics(Compost 1 - PBD 100)

Compost 1-PBD 100

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 100)Mandels h statistics(Sludge 1 - PBD 100)

Sample Sludge 1 Sludge 1 - PBD 100 -- Mean PARM = 0005 [mgkg]

Element PBD 100

General calcparmT1= 852065E-02T2= 412762E-04T3= 18T4= 68T5= 78914E-07

n= variabelp= 5

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00039 0000 4 -042 007 Fail 00039 00002 4 3 000

12L 00044 0000 4 -041 005 Fail 00044 00001 4 3 00010L 00046 0000 4 -041 013 Fail 00046 00003 4 3 00046L 00056 0000 4 -040 012 Fail 00056 00003 4 3 00026L 00059 0000 2 -040 013 Fail 00059 00003 2 1 00038L 02168 0006 4 204 244 Fail - - 38L - - 021

Totgem 0040 0001 mgkg 1-level 187 (177) 5 00049 (38L) 5 4Totstd= 0087 0002 5-level 166 (154) 1

RESULTS Mean = 000486 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000025 --gt 507 r = 00007Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000084 --gt 1731 R = 00024Remarks 1 Lab rejected (38L)

000 050 100 150 200 250

k-values

4L

12L

10L

46L

26L

38L

Mandels k statistics(Sludge 1 - PBD 100)

-01 00 01 01 02 02 03

Deviation from Mean

4L

12L

10L

46L

26L

38L

Labo

rato

ries

Sludge 1 - PBD 100 -- Mean PARM = 0005 [mgkg]

-100 000 100 200 300

h-values

4L

12L

10L

46L

26L

38L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 100)

Sludge 1-PBD 100

Unit mgkg

Mandels k statistics(Soil 3 - PBD 100)Mandels h statistics(Soil 3 - PBD 100)

Sample Soil 3 NUM

Element PBD 100

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00003 0000 4 -050 000 Fail - - 10L - - NUM46L 00003 0000 4 -050 000 Fail NUM - 46L - - NUM3L 305500 2051 2 150 200 Fail - - 3L - - NUM

26L 00005 0000 2 -050 000 Fail - - 26L - - NUM

Totgem 7638 0513 mgkg 1-level 149 (177) NUM (10L46L3L26L) -1Totstd= 15275 1025 5-level 142 (159) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (10L46L3L26L)

000 050 100 150 200

k-values

10L

46L

3L

26L

Mandels k statistics(Soil 3 - PBD 100)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

10L

46L

3L

26L

Labo

rato

ries

NUM

-100 000 100 200

h-values

10L

46L

3L

26L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 100)

Soil 3-PBD 100

Unit mgkg

Mandels k statistics(Compost 1 - PBD 153)Mandels h statistics(Compost 1 - PBD 153)

Sample Compost 1 NUM

Element PBD 153

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean44L 00053 0001 3 150 157 Fail - - 44L - - NUM46L 00007 0000 4 -044 111 Fail - - 46L - - NUM12L 00005 0000 4 -051 055 Fail - - 12L - - NUM26L 00005 0000 2 -054 001 Fail NUM - 26L - - NUM

Totgem 0002 0000 mgkg 1-level 149 (177) NUM (44L46L12L26L) -1Totstd= 0002 0000 5-level 142 (159) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (44L46L12L26L)

000 050 100 150 200

k-values

44L

46L

12L

26L

Mandels k statistics(Compost 1 - PBD 153)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

44L

46L

12L

26L

Labo

rato

ries

NUM

-100 000 100 200

h-values

44L

46L

12L

26L

Labo

rato

ries

Mandels h statistics(Compost 1 - PBD 153)

Compost 1-PBD 153

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 153)Mandels h statistics(Sludge 1 - PBD 153)

Sample Sludge 1 Sludge 1 - PBD 153 -- Mean PARM = 0004 [mgkg]

Element PBD 153

General calcparmT1= 676738E-02T2= 267609E-04T3= 18T4= 68T5= 19626E-05

n= variabelp= 5

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00024 0000 4 -157 017 00024 00002 4 3 000

12L 00038 0002 4 006 154 00038 00018 4 3 00046L 00039 0000 4 011 026 00039 00003 4 3 00026L 00039 0000 2 018 004 00039 00000 2 1 00064L 00049 0002 4 122 159 00049 00018 4 3 000

Totgem 0004 0001 mgkg 1-level 172 (173) 5 00038 () 5 4Totstd= 0001 0001 5-level 157 (153)

RESULTS Mean = 000378 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000123 --gt 3252 r = 00034Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000142 --gt 3754 R = 00040Remarks none

000 050 100 150 200

k-values

4L

12L

46L

26L

64L

Mandels k statistics(Sludge 1 - PBD 153)

00 00 00 00 00 00 00

Deviation from Mean

4L

12L

46L

26L

64L

Labo

rato

ries

Sludge 1 - PBD 153 -- Mean PARM = 0004 [mgkg]

-200 -100 000 100 200

h-values

4L

12L

46L

26L

64L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 153)

Sludge 1-PBD 153

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 154)Mandels h statistics(Sludge 1 - PBD 154)

Sample Sludge 1 NA

Element PBD 154

General calcparmT1= NAT2= NAT3=T4=T5=

n= variabelp=

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00021 0000 3 -100 021 NA - 4L - - NA

46L 00025 0000 4 115 018 NA - 46L - - NA64L 00021 0001 4 -066 179 - - 64L - - NA12L 00023 0000 4 050 085 - - 12L - - NA

Totgem 0002 0000 mgkg 1-level 149 (167) NA (4L46L64L12L) -1Totstd= 0000 0000 5-level 142 (15) 4

RESULTS Mean = NA mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NAReproducibility var S2R = NAReproducibility std SR = NA --gt NA R = NARemarks 4 Labs rejected (4L46L64L12L)

000 050 100 150 200

k-values

4L

46L

64L

12L

Mandels k statistics(Sludge 1 - PBD 154)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

4L

46L

64L

12L

Labo

rato

ries

NA

-100 000 100 200

h-values

4L

46L

64L

12L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 154)

Sludge 1-PBD 154

Unit mgkg

Mandels k statistics(Soil 3 - PBD 154)Mandels h statistics(Soil 3 - PBD 154)

Sample Soil 3 NUM

Element PBD 154

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

4L 00010 - 1 150 Fail - - 4L - - NUM46L 00001 0000 4 -053 096 Fail - - 46L - - NUM64L 00001 0000 4 -056 105 Fail NUM - 64L - - NUM12L 00002 0000 4 -040 099 Fail - - 12L - - NUM

Totgem 000037 0000 mgkg 1-level 149 (164) NUM (4L46L64L12L) -1Totstd= 000042 0000 5-level 142 (153) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (4L46L64L12L)

000 050 100 150

k-values

4L

46L

64L

12L

Mandels k statistics(Soil 3 - PBD 154)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

4L

46L

64L

12L

Labo

rato

ries

NUM

-100 000 100 200

h-values

4L

46L

64L

12L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 154)

Soil 3-PBD 154

Unit mgkg

Mandels k statistics(Compost 1 - PBD 209)Mandels h statistics(Compost 1 - PBD 209)

Sample Compost 1 NUM

Element PBD 209

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00065 0003 2 -049 032 - - 4L - - NUM

44L 00573 0021 4 150 197 Fail - - 44L - - NUM12L 00078 0001 4 -045 011 - - 12L - - NUM26L 00049 0000 2 -056 000 NUM - 26L - - NUM

Totgem 0019 0006 mgkg 1-level 149 (177) NUM (4L44L12L26L) -1Totstd= 0025 0010 5-level 142 (159) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (4L44L12L26L)

000 050 100 150 200

k-values

4L

44L

12L

26L

Mandels k statistics(Compost 1 - PBD 209)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

4L

44L

12L

26L

Labo

rato

ries

NUM

-100 000 100 200

h-values

4L

44L

12L

26L

Labo

rato

ries

Mandels h statistics(Compost 1 - PBD 209)

Compost 1-PBD 209

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 209)Mandels h statistics(Sludge 1 - PBD 209)

Sample Sludge 1 Sludge 1 - PBD 209 -- Mean PARM = 0249 [mgkg]

Element PBD 209

General calcparmT1= 394542E+00T2= 107296E+00T3= 16T4= 56T5= 19723E-02

n= variabelp= 5

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 01550 0055 4 -112 148 Fail 01550 00551 4 3 -009

46L 02050 0007 2 -053 019 02050 00071 2 1 -00412L 02137 0058 4 -042 155 02137 00576 4 3 -00426L 03149 0021 2 078 057 Fail 03149 00210 2 1 00764L 03577 0007 4 129 020 Fail 03577 00074 4 3 011

Totgem 0249 0030 mgkg 1-level 172 (185) 5 02493 () 5 4Totstd= 0084 0025 5-level 157 (162)

RESULTS Mean = 024926 mgkg

Repeatability variance S2r = 000179Repeatability std Sr = 004234 --gt 1699 r = 01186Between lab variance S2L = 000743Reproducibility var S2R = 000922Reproducibility std SR = 009604 --gt 3853 R = 02689Remarks none

000 050 100 150 200

k-values

4L

46L

12L

26L

64L

Mandels k statistics(Sludge 1 - PBD 209)

-01 -01 00 01 01 02

Deviation from Mean

4L

46L

12L

26L

64L

Labo

rato

ries

Sludge 1 - PBD 209 -- Mean PARM = 0249 [mgkg]

-200 -100 000 100 200

h-values

4L

46L

12L

26L

64L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 209)

Sludge 1-PBD 209

Unit mgkg

Mandels k statistics(Soil 3 - PBD 209)Mandels h statistics(Soil 3 - PBD 209)

Sample Soil 3 Soil 3 - PBD 209 -- Mean PARM = 0258 [mgkg]

Element PBD 209

General calcparmT1= 596398E+00T2= 191917E+00T3= 22T4= 84T5= 13249E-02

n= variabelp= 6

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean26L 01162 0021 2 -108 074 Fail 01162 00207 2 1 -0144L 01303 0031 4 -097 111 Fail 01303 00312 4 3 -013

46L 01975 0036 4 -046 128 Fail 01975 00359 4 3 -00644L 02898 0035 4 024 124 Fail 02898 00346 4 3 00312L 03895 0018 4 100 065 Fail 03895 00181 4 3 01364L 04260 0022 4 127 078 Fail 04260 00219 4 3 017

Totgem 0258 0027 mgkg 1-level 187 (177) 6 02582 () 6 5Totstd= 0132 0008 5-level 166 (154)

RESULTS Mean = 025818 mgkg

Repeatability variance S2r = 000083Repeatability std Sr = 002878 --gt 1115 r = 00806Between lab variance S2L = 001640Reproducibility var S2R = 001723Reproducibility std SR = 013127 --gt 5084 R = 03676Remarks none

000 050 100 150

k-values

26L

4L

46L

44L

12L

64L

Mandels k statistics(Soil 3 - PBD 209)

-02 -01 -01 00 01 01 02 02

Deviation from Mean

26L

4L

46L

44L

12L

64L

Labo

rato

ries

Soil 3 - PBD 209 -- Mean PARM = 0258 [mgkg]

-200 -100 000 100 200

h-values

26L

4L

46L

44L

12L

64L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 209)

Soil 3-PBD 209

Unit mgkg

Mandels k statistics(Compost 1 - Sum PBD)Mandels h statistics(Compost 1 - Sum PBD)

Sample Compost 1 Compost 1 - Sum PBD -- Mean PARM = 0009 [mgkg]

Element Sum PBD

General calcparmT1= 154064E-01T2= 169065E-03T3= 18T4= 68T5= 11354E-04

n= variabelp= 5

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00031 0002 4 -067 016 00031 00016 4 3 -0014L 00055 0005 4 -056 048 00055 00047 4 3 000

46L 00085 0003 4 -042 031 00085 00030 4 3 00026L 00123 0000 2 -024 003 00123 00002 2 1 00012L 00154 0002 4 -011 021 00154 00021 4 3 00144L 00613 0023 4 200 237 Fail - - 44L - - 005

Totgem 0018 0006 mgkg 1-level 187 (177) 5 00089 (44L) 5 4Totstd= 0022 0009 5-level 166 (154) 1

RESULTS Mean = 000893 mgkg

Repeatability variance S2r = 000001Repeatability std Sr = 000296 --gt 3308 r = 00083Between lab variance S2L = 000002Reproducibility var S2R = 000003Reproducibility std SR = 000570 --gt 6374 R = 00159Remarks 1 Lab rejected (44L)

000 050 100 150 200 250

k-values

10L

4L

46L

26L

12L

44L

Mandels k statistics(Compost 1 - Sum PBD)

00 00 00 00 00 00 01 01

Deviation from Mean

10L

4L

46L

26L

12L

44L

Labo

rato

ries

Compost 1 - Sum PBD -- Mean PARM = 0009 [mgkg]

-100 000 100 200

h-values

10L

4L

46L

26L

12L

44L

Labo

rato

ries

Mandels h statistics(Compost 1 - Sum PBD)

Compost 1-Sum PBD

Unit mgkg

Mandels k statistics(Sludge 1 - Sum PBD)Mandels h statistics(Sludge 1 - Sum PBD)

Sample Sludge 1 Sludge 1 - Sum PBD -- Mean PARM = 0256 [mgkg]

Element Sum PBD

General calcparmT1= 531806E+00T2= 162188E+00T3= 22T4= 84T5= 25223E-02

n= variabelp= 6

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00423 0025 4 -156 044 Fail 00423 00252 4 3 -02146L 01808 0118 4 -049 205 - - 46L - - -0074L 01810 0056 4 -049 097 01810 00558 4 3 -007

38L 02168 0006 4 -022 010 02168 00059 4 3 -00412L 02890 0065 4 034 113 02890 00647 4 3 00364L 03958 0008 4 116 014 Fail 03958 00079 4 3 01426L 04094 0034 2 126 059 Fail 04094 00337 2 1 015

Totgem 0245 0044 mgkg 1-level 198 (179) 6 02557 (46L) 6 5Totstd= 0130 0039 5-level 171 (155) 1

RESULTS Mean = 025570 mgkg

Repeatability variance S2r = 000158Repeatability std Sr = 003970 --gt 1553 r = 01112Between lab variance S2L = 001807Reproducibility var S2R = 001964Reproducibility std SR = 014015 --gt 5481 R = 03924Remarks 1 Lab rejected (46L)

000 050 100 150 200 250

k-values

10L

46L

4L

38L

12L

64L

26L

Mandels k statistics(Sludge 1 - Sum PBD)

-03 -02 -02 -01 -01 00 01 01 02 02

Deviation from Mean

10L

46L

4L

38L

12L

64L

26L

Labo

rato

ries

Sludge 1 - Sum PBD -- Mean PARM = 0256 [mgkg]

-200 -100 000 100 200

h-values

10L

46L

4L

38L

12L

64L

26L

Labo

rato

ries

Mandels h statistics(Sludge 1 - Sum PBD)

Sludge 1-Sum PBD

Unit mgkg

Mandels k statistics(Soil 3 - Sum PBD)Mandels h statistics(Soil 3 - Sum PBD)

Sample Soil 3 Soil 3 - Sum PBD -- Mean PARM = 0227 [mgkg]

Element Sum PBD

General calcparmT1= 610980E+00T2= 200876E+00T3= 26T4= 100T5= 13106E-02

n= variabelp= 7

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00028 0001 4 -037 000 Fail 00028 00005 4 3 -02226L 01179 0021 2 -036 003 Fail 01179 00208 2 1 -0114L 01305 0031 4 -036 004 Fail 01305 00308 4 3 -010

46L 02065 0035 4 -036 005 Fail 02065 00350 4 3 -00244L 02923 0037 4 -035 005 Fail 02923 00365 4 3 00712L 04051 0015 4 -034 002 Fail 04051 00149 4 3 01864L 04314 0022 4 -033 003 Fail 04314 00223 4 3 0203L 305500 2051 2 247 283 Fail - - 3L - - 3032

Totgem 4017 0276 mgkg 1-level 206 (181) 7 02266 (3L) 7 6Totstd= 10722 0717 5-level 175 (156) 1

RESULTS Mean = 022663 mgkg

Repeatability variance S2r = 000069Repeatability std Sr = 002626 --gt 1159 r = 00735Between lab variance S2L = 002568Reproducibility var S2R = 002637Reproducibility std SR = 016238 --gt 7165 R = 04547Remarks 1 Lab rejected (3L)

000 050 100 150 200 250 300

k-values

10L

26L

4L

46L

44L

12L

64L

3L

Mandels k statistics(Soil 3 - Sum PBD)

-50 00 50 100 150 200 250 300 350

Deviation from Mean

10L

26L

4L

46L

44L

12L

64L

3L

Labo

rato

ries

Soil 3 - Sum PBD -- Mean PARM = 0227 [mgkg]

-100 000 100 200 300

h-values

10L

26L

4L

46L

44L

12L

64L

3L

Labo

rato

ries

Mandels h statistics(Soil 3 - Sum PBD)

Soil 3-Sum PBD

19

Annex 4

Raw data submitted

Sample Compost1 Sample Compost 1 Sample Compost 1Element PBD 99 Element PBD 100 Element PBD 153

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]4L 00021 10L 00008 44L 000504L 00024 10L 00008 44L 000604L 00014 10L 00007 44L 000504L 00020 10L 00011 46L 00004

10L 00029 46L 00007 46L 0001210L 00027 46L 00012 46L 0000410L 00032 46L 00009 46L 0000946L 00025 46L 00007 12L 0000446L 00052 12L 00008 12L 0000846L 00029 12L 00012 12L 0000446L 00026 12L 00008 12L 0000712L 00026 12L 00014 26L 0000512L 00043 26L 00007 26L 0000512L 00026 26L 0000612L 0004726L 0002626L 00024

Sample Compost 1 Sample Compost 1 Sample Compost 1Element PBD 154 Element PBD 183 Element PBD 196

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]4L 00010 46L 00002 46L 00011

46L 00003 46L 00024 46L 0000846L 00007 46L 00021 12L 0000246L 00003 46L 00003 12L 0000346L 00004 12L 00003 12L 0000112L 00003 12L 00011 12L 0000212L 00005 12L 0000312L 00031 12L 0000312L 00006

Sample Compost 1 Sample Compost 1 Sample Compost 1Element PBD 197 Element PBD 203 Element PBD 209

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00002 46L 00010 4L 0004146L 00023 12L 00002 4L 0008946L 00022 12L 00003 44L 0041012L 00004 12L 00002 44L 0084012L 00006 12L 00002 44L 0064012L 00003 44L 0040012L 00004 12L 00079

12L 0007312L 0006512L 0009326L 0004926L 00049

Sample Compost 1Element PBD 47

LAB PARM [mgkg]26L 0003826L 00039

Element PBD 99 Element PBD 47 Element PBD 209LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]

4L 00170 10L 00210 4L 010004L 00200 10L 00220 4L 018004L 00170 10L 00210 4L 012004L 00190 46L 00300 4L 0220010L 00280 46L 00280 46L 0210010L 00300 46L 00250 46L 0200010L 00290 46L 00260 64L 0351846L 00340 64L 00059 64L 0363846L 00330 64L 00057 64L 0364546L 00300 64L 00062 64L 0350846L 00310 64L 00060 12L 0220964L 00194 12L 00191 12L 0177164L 00154 12L 00187 12L 0292264L 00185 12L 00190 12L 0164664L 00159 12L 00186 26L 0329712L 00242 26L 00666 26L 0300012L 00223 26L 0033212L 0022112L 0022226L 0024626L 00400

Element PBD 203 Element PBD 197 Element PBD 196LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00022 46L 00027 46L 0002446L 00014 46L 00024 46L 0002264L 00036 12L 00161 64L 0005864L 00058 12L 00060 64L 0006512L 00063 12L 00061 12L 0004812L 00034 12L 00036 12L 0002512L 00038 12L 0003212L 00027 12L 00022

Element PBD 183 Element PBD 154 Element PBD 153LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00049 4L 00020 4L 0002246L 00035 4L 00022 4L 0002446L 00036 4L 00020 4L 0002246L 00034 46L 00025 4L 0002664L 00027 46L 00025 46L 0004064L 00023 46L 00025 46L 0004264L 00024 46L 00023 46L 0003564L 00020 64L 00034 46L 0003812L 00230 64L 00023 64L 0007412L 00032 64L 00017 64L 0004712L 00031 64L 00011 64L 0004612L 00030 12L 00030 64L 0003026L 00007 12L 00021 12L 0006526L 00008 12L 00021 12L 00029

12L 00021 12L 0003226L 00015 12L 0002926L 00019 26L 00039

26L 00040

Element PBD 100LAB PARM [mgkg]

4L 000384L 000414L 000374L 00038

38L 0219038L 0220038L 0208038L 0220010L 0004410L 0005010L 0004310L 0004646L 0005746L 0005946L 0005346L 0005312L 0004312L 0004512L 0004312L 0004326L 0006226L 00057

Sample Soil 3 Sample Soil 3 Sample Soil 3Element PBD 99 Element PBD 47 Element PBD 100

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]10L 00016 10L 00011 10L 0000310L 00019 10L 00010 10L 0000410L 00013 10L 00012 10L 0000410L 00019 46L 00007 10L 0000246L 00025 46L 00022 46L 0000246L 00025 46L 00005 46L 0000646L 00008 46L 00007 46L 0000246L 00011 12L 00010 46L 0000264L 00005 12L 00017 3L 29100064L 00005 12L 00010 3L 32000064L 00006 12L 00009 26L 0000564L 00007 26L 00007 26L 0000512L 00012 26L 0000712L 0001312L 0001312L 0001226L 0000526L 00006

Sample Soil 3 Sample Soil 3 Sample Soil 3Element PBD 153 Element PBD 154 Element PBD 196

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]44L 00050 4L 00010 46L 0000744L 00050 46L 00001 46L 0001146L 00002 46L 00002 46L 0000846L 00003 46L 00001 46L 0001146L 00002 46L 00002 64L 0002646L 00002 64L 00001 64L 0002664L 00001 64L 00001 64L 0002964L 00001 64L 00001 64L 0003464L 00001 64L 00002 12L 0004564L 00002 12L 00003 12L 00032

12L 00002 12L 0002212L 00002 12L 0002112L 00002

Sample Soil 3 Sample Soil 3 Sample Soil 3Element PBD 197 Element PBD 203 Element PBD 209

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00006 46L 00011 4L 0091046L 00013 46L 00017 4L 0150046L 00011 46L 00015 4L 0120046L 00013 46L 00018 4L 0160012L 00090 64L 00013 44L 0337012L 00056 64L 00014 44L 0281012L 00033 64L 00016 44L 0287012L 00032 64L 00015 44L 02540

12L 00055 46L 0230012L 00041 46L 0220012L 00027 46L 0150012L 00026 46L 01900

64L 0438164L 0401664L 0414464L 0449812L 0367112L 0397812L 0409112L 03838

Sample Soil 3 26L 0102Element PBD 183 26L 0131

LAB PARM [mgkg]46L 0000746L 0000846L 0005846L 0000764L 0000264L 0000364L 0000364L 0000312L 0001512L 0001112L 0000712L 00007

European Commission EUR 23003 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on polybrominated diphenylethers Author(s) E Sobiecka H van der Sloot D Barcelo B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 68 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07403-5 Abstract Project HORIZONTAL is interdisciplinary aiming at a harmonisation and horizontal standardisation of test procedures in particular for sludge soils and biowastes In the context of this standardization project a series of draft technical specification were designed upon an extensive desk study fine-tuned after expert consultations and finally validated in international intercomparisons exercise This report summarises the work performed within the validation study of the draft standard for the determination of polybrominated diphenylethers (PBDE) in soils sludge and treated bio-waste using gas-chromatography method with mass selective detection (GC-MS) It further explains the underlying statistical concept for the calculation of reproducibility and repeatability from intercomparisons data In addition all single values results of the statistical evaluation as well as background information on the validation materials used are described and explained

The mission of the JRC is to provide customer-driven scientific and technical support for the conception development implementation and monitoring of EU policies As a service of the European Commission the JRC functions as a reference centre of science and technology for the Union Close to the policy-making process it serves the common interest of the Member States while being independent of special interests whether private or national

LB

-NA

-23003-EN

-C

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 99)Mandels h statistics(Sludge 1 - PBD 99)

Sample Sludge 1 Sludge 1 - PBD 99 -- Mean PARM = 0024 [mgkg]

Element PBD 99

General calcparmT1= 448050E-01T2= 112113E-02T3= 19T4= 73T5= 32972E-05

n= variabelp= 5

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean64L 00173 0002 4 -118 041 Fail 00173 00019 4 3 -0014L 00183 0002 4 -104 032 00183 00015 4 3 -001

12L 00227 0001 4 -038 022 00227 00010 4 3 00010L 00290 0001 3 055 021 00290 00010 3 2 00146L 00320 0002 4 100 039 00320 00018 4 3 00126L 00323 0011 2 105 234 - - 26L - - 001

Totgem 0025 0003 mgkg 1-level 187 (177) 5 00239 (26L) 5 4Totstd= 0007 0004 5-level 166 (154) 1

RESULTS Mean = 002385 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000153 --gt 643 r = 00043Between lab variance S2L = 000004Reproducibility var S2R = 000004Reproducibility std SR = 000666 --gt 2791 R = 00186Remarks 1 Lab rejected (26L)

000 050 100 150 200 250

k-values

64L

4L

12L

10L

46L

26L

Mandels k statistics(Sludge 1 - PBD 99)

00 00 00 00 00 00 00 00 00 00

Deviation from Mean

64L

4L

12L

10L

46L

26L

Labo

rato

ries

Sludge 1 - PBD 99 -- Mean PARM = 0024 [mgkg]

-200 -100 000 100 200

h-values

64L

4L

12L

10L

46L

26L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 99)

Sludge 1-PBD 99

Unit mgkg

Mandels k statistics(Soil 3 - PBD 99)Mandels h statistics(Soil 3 - PBD 99)

Sample Soil 3 NUM

Element PBD 99

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00017 0000 4 091 068 - - 10L - - NUM46L 00017 0001 4 100 211 - - 46L - - NUM64L 00005 0000 4 -106 023 NUM - 64L - - NUM12L 00012 0000 4 015 014 - - 12L - - NUM26L 00006 0000 2 -101 012 - - 26L - - NUM

Totgem 0001 0000 mgkg 1-level 172 (173) NUM (10L46L64L12L26L) -1Totstd= 0001 0000 5-level 157 (153) 5

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 5 Labs rejected (10L46L64L12L26L)

000 050 100 150 200 250

k-values

10L

46L

64L

12L

26L

Mandels k statistics(Soil 3 - PBD 99)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

10L

46L

64L

12L

26L

Labo

rato

ries

NUM

-200 -100 000 100 200

h-values

10L

46L

64L

12L

26L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 99)

Soil 3-PBD 99

Unit mgkg

Mandels k statistics(Compost 1 - PBD 100)Mandels h statistics(Compost 1 - PBD 100)

Sample Compost 1 Compost 1 - PBD 100 -- Mean PARM = 0001 [mgkg]

Element PBD 100

General calcparmT1= 124272E-02T2= 113129E-05T3= 14T4= 52T5= 46584E-07

n= variabelp= 4

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean26L 00006 0000 2 -131 037 Fail 00006 00001 2 1 00010L 00009 0000 4 003 083 00009 00002 4 3 00046L 00009 0000 4 016 115 00009 00002 4 3 00012L 00011 0000 4 112 136 Fail 00011 00003 4 3 000

Totgem 0001 0000 mgkg 1-level 149 (167) 4 00009 () 4 3Totstd= 0000 0000 5-level 142 (15)

RESULTS Mean = 000085 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000022 --gt 2531 r = 00006Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000025 --gt 2882 R = 00007Remarks none

000 050 100 150

k-values

26L

10L

46L

12L

Mandels k statistics(Compost 1 - PBD 100)

00 00 00 00 00 00 00 00 00 00 00

Deviation from Mean

26L

10L

46L

12L

Labo

rato

ries

Compost 1 - PBD 100 -- Mean PARM = 0001 [mgkg]

-200 -100 000 100 200

h-values

26L

10L

46L

12L

Labo

rato

ries

Mandels h statistics(Compost 1 - PBD 100)

Compost 1-PBD 100

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 100)Mandels h statistics(Sludge 1 - PBD 100)

Sample Sludge 1 Sludge 1 - PBD 100 -- Mean PARM = 0005 [mgkg]

Element PBD 100

General calcparmT1= 852065E-02T2= 412762E-04T3= 18T4= 68T5= 78914E-07

n= variabelp= 5

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00039 0000 4 -042 007 Fail 00039 00002 4 3 000

12L 00044 0000 4 -041 005 Fail 00044 00001 4 3 00010L 00046 0000 4 -041 013 Fail 00046 00003 4 3 00046L 00056 0000 4 -040 012 Fail 00056 00003 4 3 00026L 00059 0000 2 -040 013 Fail 00059 00003 2 1 00038L 02168 0006 4 204 244 Fail - - 38L - - 021

Totgem 0040 0001 mgkg 1-level 187 (177) 5 00049 (38L) 5 4Totstd= 0087 0002 5-level 166 (154) 1

RESULTS Mean = 000486 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000025 --gt 507 r = 00007Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000084 --gt 1731 R = 00024Remarks 1 Lab rejected (38L)

000 050 100 150 200 250

k-values

4L

12L

10L

46L

26L

38L

Mandels k statistics(Sludge 1 - PBD 100)

-01 00 01 01 02 02 03

Deviation from Mean

4L

12L

10L

46L

26L

38L

Labo

rato

ries

Sludge 1 - PBD 100 -- Mean PARM = 0005 [mgkg]

-100 000 100 200 300

h-values

4L

12L

10L

46L

26L

38L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 100)

Sludge 1-PBD 100

Unit mgkg

Mandels k statistics(Soil 3 - PBD 100)Mandels h statistics(Soil 3 - PBD 100)

Sample Soil 3 NUM

Element PBD 100

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00003 0000 4 -050 000 Fail - - 10L - - NUM46L 00003 0000 4 -050 000 Fail NUM - 46L - - NUM3L 305500 2051 2 150 200 Fail - - 3L - - NUM

26L 00005 0000 2 -050 000 Fail - - 26L - - NUM

Totgem 7638 0513 mgkg 1-level 149 (177) NUM (10L46L3L26L) -1Totstd= 15275 1025 5-level 142 (159) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (10L46L3L26L)

000 050 100 150 200

k-values

10L

46L

3L

26L

Mandels k statistics(Soil 3 - PBD 100)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

10L

46L

3L

26L

Labo

rato

ries

NUM

-100 000 100 200

h-values

10L

46L

3L

26L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 100)

Soil 3-PBD 100

Unit mgkg

Mandels k statistics(Compost 1 - PBD 153)Mandels h statistics(Compost 1 - PBD 153)

Sample Compost 1 NUM

Element PBD 153

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean44L 00053 0001 3 150 157 Fail - - 44L - - NUM46L 00007 0000 4 -044 111 Fail - - 46L - - NUM12L 00005 0000 4 -051 055 Fail - - 12L - - NUM26L 00005 0000 2 -054 001 Fail NUM - 26L - - NUM

Totgem 0002 0000 mgkg 1-level 149 (177) NUM (44L46L12L26L) -1Totstd= 0002 0000 5-level 142 (159) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (44L46L12L26L)

000 050 100 150 200

k-values

44L

46L

12L

26L

Mandels k statistics(Compost 1 - PBD 153)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

44L

46L

12L

26L

Labo

rato

ries

NUM

-100 000 100 200

h-values

44L

46L

12L

26L

Labo

rato

ries

Mandels h statistics(Compost 1 - PBD 153)

Compost 1-PBD 153

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 153)Mandels h statistics(Sludge 1 - PBD 153)

Sample Sludge 1 Sludge 1 - PBD 153 -- Mean PARM = 0004 [mgkg]

Element PBD 153

General calcparmT1= 676738E-02T2= 267609E-04T3= 18T4= 68T5= 19626E-05

n= variabelp= 5

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00024 0000 4 -157 017 00024 00002 4 3 000

12L 00038 0002 4 006 154 00038 00018 4 3 00046L 00039 0000 4 011 026 00039 00003 4 3 00026L 00039 0000 2 018 004 00039 00000 2 1 00064L 00049 0002 4 122 159 00049 00018 4 3 000

Totgem 0004 0001 mgkg 1-level 172 (173) 5 00038 () 5 4Totstd= 0001 0001 5-level 157 (153)

RESULTS Mean = 000378 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000123 --gt 3252 r = 00034Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000142 --gt 3754 R = 00040Remarks none

000 050 100 150 200

k-values

4L

12L

46L

26L

64L

Mandels k statistics(Sludge 1 - PBD 153)

00 00 00 00 00 00 00

Deviation from Mean

4L

12L

46L

26L

64L

Labo

rato

ries

Sludge 1 - PBD 153 -- Mean PARM = 0004 [mgkg]

-200 -100 000 100 200

h-values

4L

12L

46L

26L

64L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 153)

Sludge 1-PBD 153

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 154)Mandels h statistics(Sludge 1 - PBD 154)

Sample Sludge 1 NA

Element PBD 154

General calcparmT1= NAT2= NAT3=T4=T5=

n= variabelp=

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00021 0000 3 -100 021 NA - 4L - - NA

46L 00025 0000 4 115 018 NA - 46L - - NA64L 00021 0001 4 -066 179 - - 64L - - NA12L 00023 0000 4 050 085 - - 12L - - NA

Totgem 0002 0000 mgkg 1-level 149 (167) NA (4L46L64L12L) -1Totstd= 0000 0000 5-level 142 (15) 4

RESULTS Mean = NA mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NAReproducibility var S2R = NAReproducibility std SR = NA --gt NA R = NARemarks 4 Labs rejected (4L46L64L12L)

000 050 100 150 200

k-values

4L

46L

64L

12L

Mandels k statistics(Sludge 1 - PBD 154)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

4L

46L

64L

12L

Labo

rato

ries

NA

-100 000 100 200

h-values

4L

46L

64L

12L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 154)

Sludge 1-PBD 154

Unit mgkg

Mandels k statistics(Soil 3 - PBD 154)Mandels h statistics(Soil 3 - PBD 154)

Sample Soil 3 NUM

Element PBD 154

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

4L 00010 - 1 150 Fail - - 4L - - NUM46L 00001 0000 4 -053 096 Fail - - 46L - - NUM64L 00001 0000 4 -056 105 Fail NUM - 64L - - NUM12L 00002 0000 4 -040 099 Fail - - 12L - - NUM

Totgem 000037 0000 mgkg 1-level 149 (164) NUM (4L46L64L12L) -1Totstd= 000042 0000 5-level 142 (153) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (4L46L64L12L)

000 050 100 150

k-values

4L

46L

64L

12L

Mandels k statistics(Soil 3 - PBD 154)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

4L

46L

64L

12L

Labo

rato

ries

NUM

-100 000 100 200

h-values

4L

46L

64L

12L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 154)

Soil 3-PBD 154

Unit mgkg

Mandels k statistics(Compost 1 - PBD 209)Mandels h statistics(Compost 1 - PBD 209)

Sample Compost 1 NUM

Element PBD 209

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00065 0003 2 -049 032 - - 4L - - NUM

44L 00573 0021 4 150 197 Fail - - 44L - - NUM12L 00078 0001 4 -045 011 - - 12L - - NUM26L 00049 0000 2 -056 000 NUM - 26L - - NUM

Totgem 0019 0006 mgkg 1-level 149 (177) NUM (4L44L12L26L) -1Totstd= 0025 0010 5-level 142 (159) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (4L44L12L26L)

000 050 100 150 200

k-values

4L

44L

12L

26L

Mandels k statistics(Compost 1 - PBD 209)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

4L

44L

12L

26L

Labo

rato

ries

NUM

-100 000 100 200

h-values

4L

44L

12L

26L

Labo

rato

ries

Mandels h statistics(Compost 1 - PBD 209)

Compost 1-PBD 209

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 209)Mandels h statistics(Sludge 1 - PBD 209)

Sample Sludge 1 Sludge 1 - PBD 209 -- Mean PARM = 0249 [mgkg]

Element PBD 209

General calcparmT1= 394542E+00T2= 107296E+00T3= 16T4= 56T5= 19723E-02

n= variabelp= 5

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 01550 0055 4 -112 148 Fail 01550 00551 4 3 -009

46L 02050 0007 2 -053 019 02050 00071 2 1 -00412L 02137 0058 4 -042 155 02137 00576 4 3 -00426L 03149 0021 2 078 057 Fail 03149 00210 2 1 00764L 03577 0007 4 129 020 Fail 03577 00074 4 3 011

Totgem 0249 0030 mgkg 1-level 172 (185) 5 02493 () 5 4Totstd= 0084 0025 5-level 157 (162)

RESULTS Mean = 024926 mgkg

Repeatability variance S2r = 000179Repeatability std Sr = 004234 --gt 1699 r = 01186Between lab variance S2L = 000743Reproducibility var S2R = 000922Reproducibility std SR = 009604 --gt 3853 R = 02689Remarks none

000 050 100 150 200

k-values

4L

46L

12L

26L

64L

Mandels k statistics(Sludge 1 - PBD 209)

-01 -01 00 01 01 02

Deviation from Mean

4L

46L

12L

26L

64L

Labo

rato

ries

Sludge 1 - PBD 209 -- Mean PARM = 0249 [mgkg]

-200 -100 000 100 200

h-values

4L

46L

12L

26L

64L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 209)

Sludge 1-PBD 209

Unit mgkg

Mandels k statistics(Soil 3 - PBD 209)Mandels h statistics(Soil 3 - PBD 209)

Sample Soil 3 Soil 3 - PBD 209 -- Mean PARM = 0258 [mgkg]

Element PBD 209

General calcparmT1= 596398E+00T2= 191917E+00T3= 22T4= 84T5= 13249E-02

n= variabelp= 6

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean26L 01162 0021 2 -108 074 Fail 01162 00207 2 1 -0144L 01303 0031 4 -097 111 Fail 01303 00312 4 3 -013

46L 01975 0036 4 -046 128 Fail 01975 00359 4 3 -00644L 02898 0035 4 024 124 Fail 02898 00346 4 3 00312L 03895 0018 4 100 065 Fail 03895 00181 4 3 01364L 04260 0022 4 127 078 Fail 04260 00219 4 3 017

Totgem 0258 0027 mgkg 1-level 187 (177) 6 02582 () 6 5Totstd= 0132 0008 5-level 166 (154)

RESULTS Mean = 025818 mgkg

Repeatability variance S2r = 000083Repeatability std Sr = 002878 --gt 1115 r = 00806Between lab variance S2L = 001640Reproducibility var S2R = 001723Reproducibility std SR = 013127 --gt 5084 R = 03676Remarks none

000 050 100 150

k-values

26L

4L

46L

44L

12L

64L

Mandels k statistics(Soil 3 - PBD 209)

-02 -01 -01 00 01 01 02 02

Deviation from Mean

26L

4L

46L

44L

12L

64L

Labo

rato

ries

Soil 3 - PBD 209 -- Mean PARM = 0258 [mgkg]

-200 -100 000 100 200

h-values

26L

4L

46L

44L

12L

64L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 209)

Soil 3-PBD 209

Unit mgkg

Mandels k statistics(Compost 1 - Sum PBD)Mandels h statistics(Compost 1 - Sum PBD)

Sample Compost 1 Compost 1 - Sum PBD -- Mean PARM = 0009 [mgkg]

Element Sum PBD

General calcparmT1= 154064E-01T2= 169065E-03T3= 18T4= 68T5= 11354E-04

n= variabelp= 5

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00031 0002 4 -067 016 00031 00016 4 3 -0014L 00055 0005 4 -056 048 00055 00047 4 3 000

46L 00085 0003 4 -042 031 00085 00030 4 3 00026L 00123 0000 2 -024 003 00123 00002 2 1 00012L 00154 0002 4 -011 021 00154 00021 4 3 00144L 00613 0023 4 200 237 Fail - - 44L - - 005

Totgem 0018 0006 mgkg 1-level 187 (177) 5 00089 (44L) 5 4Totstd= 0022 0009 5-level 166 (154) 1

RESULTS Mean = 000893 mgkg

Repeatability variance S2r = 000001Repeatability std Sr = 000296 --gt 3308 r = 00083Between lab variance S2L = 000002Reproducibility var S2R = 000003Reproducibility std SR = 000570 --gt 6374 R = 00159Remarks 1 Lab rejected (44L)

000 050 100 150 200 250

k-values

10L

4L

46L

26L

12L

44L

Mandels k statistics(Compost 1 - Sum PBD)

00 00 00 00 00 00 01 01

Deviation from Mean

10L

4L

46L

26L

12L

44L

Labo

rato

ries

Compost 1 - Sum PBD -- Mean PARM = 0009 [mgkg]

-100 000 100 200

h-values

10L

4L

46L

26L

12L

44L

Labo

rato

ries

Mandels h statistics(Compost 1 - Sum PBD)

Compost 1-Sum PBD

Unit mgkg

Mandels k statistics(Sludge 1 - Sum PBD)Mandels h statistics(Sludge 1 - Sum PBD)

Sample Sludge 1 Sludge 1 - Sum PBD -- Mean PARM = 0256 [mgkg]

Element Sum PBD

General calcparmT1= 531806E+00T2= 162188E+00T3= 22T4= 84T5= 25223E-02

n= variabelp= 6

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00423 0025 4 -156 044 Fail 00423 00252 4 3 -02146L 01808 0118 4 -049 205 - - 46L - - -0074L 01810 0056 4 -049 097 01810 00558 4 3 -007

38L 02168 0006 4 -022 010 02168 00059 4 3 -00412L 02890 0065 4 034 113 02890 00647 4 3 00364L 03958 0008 4 116 014 Fail 03958 00079 4 3 01426L 04094 0034 2 126 059 Fail 04094 00337 2 1 015

Totgem 0245 0044 mgkg 1-level 198 (179) 6 02557 (46L) 6 5Totstd= 0130 0039 5-level 171 (155) 1

RESULTS Mean = 025570 mgkg

Repeatability variance S2r = 000158Repeatability std Sr = 003970 --gt 1553 r = 01112Between lab variance S2L = 001807Reproducibility var S2R = 001964Reproducibility std SR = 014015 --gt 5481 R = 03924Remarks 1 Lab rejected (46L)

000 050 100 150 200 250

k-values

10L

46L

4L

38L

12L

64L

26L

Mandels k statistics(Sludge 1 - Sum PBD)

-03 -02 -02 -01 -01 00 01 01 02 02

Deviation from Mean

10L

46L

4L

38L

12L

64L

26L

Labo

rato

ries

Sludge 1 - Sum PBD -- Mean PARM = 0256 [mgkg]

-200 -100 000 100 200

h-values

10L

46L

4L

38L

12L

64L

26L

Labo

rato

ries

Mandels h statistics(Sludge 1 - Sum PBD)

Sludge 1-Sum PBD

Unit mgkg

Mandels k statistics(Soil 3 - Sum PBD)Mandels h statistics(Soil 3 - Sum PBD)

Sample Soil 3 Soil 3 - Sum PBD -- Mean PARM = 0227 [mgkg]

Element Sum PBD

General calcparmT1= 610980E+00T2= 200876E+00T3= 26T4= 100T5= 13106E-02

n= variabelp= 7

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00028 0001 4 -037 000 Fail 00028 00005 4 3 -02226L 01179 0021 2 -036 003 Fail 01179 00208 2 1 -0114L 01305 0031 4 -036 004 Fail 01305 00308 4 3 -010

46L 02065 0035 4 -036 005 Fail 02065 00350 4 3 -00244L 02923 0037 4 -035 005 Fail 02923 00365 4 3 00712L 04051 0015 4 -034 002 Fail 04051 00149 4 3 01864L 04314 0022 4 -033 003 Fail 04314 00223 4 3 0203L 305500 2051 2 247 283 Fail - - 3L - - 3032

Totgem 4017 0276 mgkg 1-level 206 (181) 7 02266 (3L) 7 6Totstd= 10722 0717 5-level 175 (156) 1

RESULTS Mean = 022663 mgkg

Repeatability variance S2r = 000069Repeatability std Sr = 002626 --gt 1159 r = 00735Between lab variance S2L = 002568Reproducibility var S2R = 002637Reproducibility std SR = 016238 --gt 7165 R = 04547Remarks 1 Lab rejected (3L)

000 050 100 150 200 250 300

k-values

10L

26L

4L

46L

44L

12L

64L

3L

Mandels k statistics(Soil 3 - Sum PBD)

-50 00 50 100 150 200 250 300 350

Deviation from Mean

10L

26L

4L

46L

44L

12L

64L

3L

Labo

rato

ries

Soil 3 - Sum PBD -- Mean PARM = 0227 [mgkg]

-100 000 100 200 300

h-values

10L

26L

4L

46L

44L

12L

64L

3L

Labo

rato

ries

Mandels h statistics(Soil 3 - Sum PBD)

Soil 3-Sum PBD

19

Annex 4

Raw data submitted

Sample Compost1 Sample Compost 1 Sample Compost 1Element PBD 99 Element PBD 100 Element PBD 153

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]4L 00021 10L 00008 44L 000504L 00024 10L 00008 44L 000604L 00014 10L 00007 44L 000504L 00020 10L 00011 46L 00004

10L 00029 46L 00007 46L 0001210L 00027 46L 00012 46L 0000410L 00032 46L 00009 46L 0000946L 00025 46L 00007 12L 0000446L 00052 12L 00008 12L 0000846L 00029 12L 00012 12L 0000446L 00026 12L 00008 12L 0000712L 00026 12L 00014 26L 0000512L 00043 26L 00007 26L 0000512L 00026 26L 0000612L 0004726L 0002626L 00024

Sample Compost 1 Sample Compost 1 Sample Compost 1Element PBD 154 Element PBD 183 Element PBD 196

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]4L 00010 46L 00002 46L 00011

46L 00003 46L 00024 46L 0000846L 00007 46L 00021 12L 0000246L 00003 46L 00003 12L 0000346L 00004 12L 00003 12L 0000112L 00003 12L 00011 12L 0000212L 00005 12L 0000312L 00031 12L 0000312L 00006

Sample Compost 1 Sample Compost 1 Sample Compost 1Element PBD 197 Element PBD 203 Element PBD 209

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00002 46L 00010 4L 0004146L 00023 12L 00002 4L 0008946L 00022 12L 00003 44L 0041012L 00004 12L 00002 44L 0084012L 00006 12L 00002 44L 0064012L 00003 44L 0040012L 00004 12L 00079

12L 0007312L 0006512L 0009326L 0004926L 00049

Sample Compost 1Element PBD 47

LAB PARM [mgkg]26L 0003826L 00039

Element PBD 99 Element PBD 47 Element PBD 209LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]

4L 00170 10L 00210 4L 010004L 00200 10L 00220 4L 018004L 00170 10L 00210 4L 012004L 00190 46L 00300 4L 0220010L 00280 46L 00280 46L 0210010L 00300 46L 00250 46L 0200010L 00290 46L 00260 64L 0351846L 00340 64L 00059 64L 0363846L 00330 64L 00057 64L 0364546L 00300 64L 00062 64L 0350846L 00310 64L 00060 12L 0220964L 00194 12L 00191 12L 0177164L 00154 12L 00187 12L 0292264L 00185 12L 00190 12L 0164664L 00159 12L 00186 26L 0329712L 00242 26L 00666 26L 0300012L 00223 26L 0033212L 0022112L 0022226L 0024626L 00400

Element PBD 203 Element PBD 197 Element PBD 196LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00022 46L 00027 46L 0002446L 00014 46L 00024 46L 0002264L 00036 12L 00161 64L 0005864L 00058 12L 00060 64L 0006512L 00063 12L 00061 12L 0004812L 00034 12L 00036 12L 0002512L 00038 12L 0003212L 00027 12L 00022

Element PBD 183 Element PBD 154 Element PBD 153LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00049 4L 00020 4L 0002246L 00035 4L 00022 4L 0002446L 00036 4L 00020 4L 0002246L 00034 46L 00025 4L 0002664L 00027 46L 00025 46L 0004064L 00023 46L 00025 46L 0004264L 00024 46L 00023 46L 0003564L 00020 64L 00034 46L 0003812L 00230 64L 00023 64L 0007412L 00032 64L 00017 64L 0004712L 00031 64L 00011 64L 0004612L 00030 12L 00030 64L 0003026L 00007 12L 00021 12L 0006526L 00008 12L 00021 12L 00029

12L 00021 12L 0003226L 00015 12L 0002926L 00019 26L 00039

26L 00040

Element PBD 100LAB PARM [mgkg]

4L 000384L 000414L 000374L 00038

38L 0219038L 0220038L 0208038L 0220010L 0004410L 0005010L 0004310L 0004646L 0005746L 0005946L 0005346L 0005312L 0004312L 0004512L 0004312L 0004326L 0006226L 00057

Sample Soil 3 Sample Soil 3 Sample Soil 3Element PBD 99 Element PBD 47 Element PBD 100

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]10L 00016 10L 00011 10L 0000310L 00019 10L 00010 10L 0000410L 00013 10L 00012 10L 0000410L 00019 46L 00007 10L 0000246L 00025 46L 00022 46L 0000246L 00025 46L 00005 46L 0000646L 00008 46L 00007 46L 0000246L 00011 12L 00010 46L 0000264L 00005 12L 00017 3L 29100064L 00005 12L 00010 3L 32000064L 00006 12L 00009 26L 0000564L 00007 26L 00007 26L 0000512L 00012 26L 0000712L 0001312L 0001312L 0001226L 0000526L 00006

Sample Soil 3 Sample Soil 3 Sample Soil 3Element PBD 153 Element PBD 154 Element PBD 196

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]44L 00050 4L 00010 46L 0000744L 00050 46L 00001 46L 0001146L 00002 46L 00002 46L 0000846L 00003 46L 00001 46L 0001146L 00002 46L 00002 64L 0002646L 00002 64L 00001 64L 0002664L 00001 64L 00001 64L 0002964L 00001 64L 00001 64L 0003464L 00001 64L 00002 12L 0004564L 00002 12L 00003 12L 00032

12L 00002 12L 0002212L 00002 12L 0002112L 00002

Sample Soil 3 Sample Soil 3 Sample Soil 3Element PBD 197 Element PBD 203 Element PBD 209

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00006 46L 00011 4L 0091046L 00013 46L 00017 4L 0150046L 00011 46L 00015 4L 0120046L 00013 46L 00018 4L 0160012L 00090 64L 00013 44L 0337012L 00056 64L 00014 44L 0281012L 00033 64L 00016 44L 0287012L 00032 64L 00015 44L 02540

12L 00055 46L 0230012L 00041 46L 0220012L 00027 46L 0150012L 00026 46L 01900

64L 0438164L 0401664L 0414464L 0449812L 0367112L 0397812L 0409112L 03838

Sample Soil 3 26L 0102Element PBD 183 26L 0131

LAB PARM [mgkg]46L 0000746L 0000846L 0005846L 0000764L 0000264L 0000364L 0000364L 0000312L 0001512L 0001112L 0000712L 00007

European Commission EUR 23003 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on polybrominated diphenylethers Author(s) E Sobiecka H van der Sloot D Barcelo B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 68 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07403-5 Abstract Project HORIZONTAL is interdisciplinary aiming at a harmonisation and horizontal standardisation of test procedures in particular for sludge soils and biowastes In the context of this standardization project a series of draft technical specification were designed upon an extensive desk study fine-tuned after expert consultations and finally validated in international intercomparisons exercise This report summarises the work performed within the validation study of the draft standard for the determination of polybrominated diphenylethers (PBDE) in soils sludge and treated bio-waste using gas-chromatography method with mass selective detection (GC-MS) It further explains the underlying statistical concept for the calculation of reproducibility and repeatability from intercomparisons data In addition all single values results of the statistical evaluation as well as background information on the validation materials used are described and explained

The mission of the JRC is to provide customer-driven scientific and technical support for the conception development implementation and monitoring of EU policies As a service of the European Commission the JRC functions as a reference centre of science and technology for the Union Close to the policy-making process it serves the common interest of the Member States while being independent of special interests whether private or national

LB

-NA

-23003-EN

-C

Unit mgkg

Mandels k statistics(Soil 3 - PBD 99)Mandels h statistics(Soil 3 - PBD 99)

Sample Soil 3 NUM

Element PBD 99

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00017 0000 4 091 068 - - 10L - - NUM46L 00017 0001 4 100 211 - - 46L - - NUM64L 00005 0000 4 -106 023 NUM - 64L - - NUM12L 00012 0000 4 015 014 - - 12L - - NUM26L 00006 0000 2 -101 012 - - 26L - - NUM

Totgem 0001 0000 mgkg 1-level 172 (173) NUM (10L46L64L12L26L) -1Totstd= 0001 0000 5-level 157 (153) 5

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 5 Labs rejected (10L46L64L12L26L)

000 050 100 150 200 250

k-values

10L

46L

64L

12L

26L

Mandels k statistics(Soil 3 - PBD 99)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

10L

46L

64L

12L

26L

Labo

rato

ries

NUM

-200 -100 000 100 200

h-values

10L

46L

64L

12L

26L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 99)

Soil 3-PBD 99

Unit mgkg

Mandels k statistics(Compost 1 - PBD 100)Mandels h statistics(Compost 1 - PBD 100)

Sample Compost 1 Compost 1 - PBD 100 -- Mean PARM = 0001 [mgkg]

Element PBD 100

General calcparmT1= 124272E-02T2= 113129E-05T3= 14T4= 52T5= 46584E-07

n= variabelp= 4

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean26L 00006 0000 2 -131 037 Fail 00006 00001 2 1 00010L 00009 0000 4 003 083 00009 00002 4 3 00046L 00009 0000 4 016 115 00009 00002 4 3 00012L 00011 0000 4 112 136 Fail 00011 00003 4 3 000

Totgem 0001 0000 mgkg 1-level 149 (167) 4 00009 () 4 3Totstd= 0000 0000 5-level 142 (15)

RESULTS Mean = 000085 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000022 --gt 2531 r = 00006Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000025 --gt 2882 R = 00007Remarks none

000 050 100 150

k-values

26L

10L

46L

12L

Mandels k statistics(Compost 1 - PBD 100)

00 00 00 00 00 00 00 00 00 00 00

Deviation from Mean

26L

10L

46L

12L

Labo

rato

ries

Compost 1 - PBD 100 -- Mean PARM = 0001 [mgkg]

-200 -100 000 100 200

h-values

26L

10L

46L

12L

Labo

rato

ries

Mandels h statistics(Compost 1 - PBD 100)

Compost 1-PBD 100

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 100)Mandels h statistics(Sludge 1 - PBD 100)

Sample Sludge 1 Sludge 1 - PBD 100 -- Mean PARM = 0005 [mgkg]

Element PBD 100

General calcparmT1= 852065E-02T2= 412762E-04T3= 18T4= 68T5= 78914E-07

n= variabelp= 5

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00039 0000 4 -042 007 Fail 00039 00002 4 3 000

12L 00044 0000 4 -041 005 Fail 00044 00001 4 3 00010L 00046 0000 4 -041 013 Fail 00046 00003 4 3 00046L 00056 0000 4 -040 012 Fail 00056 00003 4 3 00026L 00059 0000 2 -040 013 Fail 00059 00003 2 1 00038L 02168 0006 4 204 244 Fail - - 38L - - 021

Totgem 0040 0001 mgkg 1-level 187 (177) 5 00049 (38L) 5 4Totstd= 0087 0002 5-level 166 (154) 1

RESULTS Mean = 000486 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000025 --gt 507 r = 00007Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000084 --gt 1731 R = 00024Remarks 1 Lab rejected (38L)

000 050 100 150 200 250

k-values

4L

12L

10L

46L

26L

38L

Mandels k statistics(Sludge 1 - PBD 100)

-01 00 01 01 02 02 03

Deviation from Mean

4L

12L

10L

46L

26L

38L

Labo

rato

ries

Sludge 1 - PBD 100 -- Mean PARM = 0005 [mgkg]

-100 000 100 200 300

h-values

4L

12L

10L

46L

26L

38L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 100)

Sludge 1-PBD 100

Unit mgkg

Mandels k statistics(Soil 3 - PBD 100)Mandels h statistics(Soil 3 - PBD 100)

Sample Soil 3 NUM

Element PBD 100

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00003 0000 4 -050 000 Fail - - 10L - - NUM46L 00003 0000 4 -050 000 Fail NUM - 46L - - NUM3L 305500 2051 2 150 200 Fail - - 3L - - NUM

26L 00005 0000 2 -050 000 Fail - - 26L - - NUM

Totgem 7638 0513 mgkg 1-level 149 (177) NUM (10L46L3L26L) -1Totstd= 15275 1025 5-level 142 (159) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (10L46L3L26L)

000 050 100 150 200

k-values

10L

46L

3L

26L

Mandels k statistics(Soil 3 - PBD 100)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

10L

46L

3L

26L

Labo

rato

ries

NUM

-100 000 100 200

h-values

10L

46L

3L

26L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 100)

Soil 3-PBD 100

Unit mgkg

Mandels k statistics(Compost 1 - PBD 153)Mandels h statistics(Compost 1 - PBD 153)

Sample Compost 1 NUM

Element PBD 153

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean44L 00053 0001 3 150 157 Fail - - 44L - - NUM46L 00007 0000 4 -044 111 Fail - - 46L - - NUM12L 00005 0000 4 -051 055 Fail - - 12L - - NUM26L 00005 0000 2 -054 001 Fail NUM - 26L - - NUM

Totgem 0002 0000 mgkg 1-level 149 (177) NUM (44L46L12L26L) -1Totstd= 0002 0000 5-level 142 (159) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (44L46L12L26L)

000 050 100 150 200

k-values

44L

46L

12L

26L

Mandels k statistics(Compost 1 - PBD 153)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

44L

46L

12L

26L

Labo

rato

ries

NUM

-100 000 100 200

h-values

44L

46L

12L

26L

Labo

rato

ries

Mandels h statistics(Compost 1 - PBD 153)

Compost 1-PBD 153

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 153)Mandels h statistics(Sludge 1 - PBD 153)

Sample Sludge 1 Sludge 1 - PBD 153 -- Mean PARM = 0004 [mgkg]

Element PBD 153

General calcparmT1= 676738E-02T2= 267609E-04T3= 18T4= 68T5= 19626E-05

n= variabelp= 5

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00024 0000 4 -157 017 00024 00002 4 3 000

12L 00038 0002 4 006 154 00038 00018 4 3 00046L 00039 0000 4 011 026 00039 00003 4 3 00026L 00039 0000 2 018 004 00039 00000 2 1 00064L 00049 0002 4 122 159 00049 00018 4 3 000

Totgem 0004 0001 mgkg 1-level 172 (173) 5 00038 () 5 4Totstd= 0001 0001 5-level 157 (153)

RESULTS Mean = 000378 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000123 --gt 3252 r = 00034Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000142 --gt 3754 R = 00040Remarks none

000 050 100 150 200

k-values

4L

12L

46L

26L

64L

Mandels k statistics(Sludge 1 - PBD 153)

00 00 00 00 00 00 00

Deviation from Mean

4L

12L

46L

26L

64L

Labo

rato

ries

Sludge 1 - PBD 153 -- Mean PARM = 0004 [mgkg]

-200 -100 000 100 200

h-values

4L

12L

46L

26L

64L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 153)

Sludge 1-PBD 153

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 154)Mandels h statistics(Sludge 1 - PBD 154)

Sample Sludge 1 NA

Element PBD 154

General calcparmT1= NAT2= NAT3=T4=T5=

n= variabelp=

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00021 0000 3 -100 021 NA - 4L - - NA

46L 00025 0000 4 115 018 NA - 46L - - NA64L 00021 0001 4 -066 179 - - 64L - - NA12L 00023 0000 4 050 085 - - 12L - - NA

Totgem 0002 0000 mgkg 1-level 149 (167) NA (4L46L64L12L) -1Totstd= 0000 0000 5-level 142 (15) 4

RESULTS Mean = NA mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NAReproducibility var S2R = NAReproducibility std SR = NA --gt NA R = NARemarks 4 Labs rejected (4L46L64L12L)

000 050 100 150 200

k-values

4L

46L

64L

12L

Mandels k statistics(Sludge 1 - PBD 154)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

4L

46L

64L

12L

Labo

rato

ries

NA

-100 000 100 200

h-values

4L

46L

64L

12L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 154)

Sludge 1-PBD 154

Unit mgkg

Mandels k statistics(Soil 3 - PBD 154)Mandels h statistics(Soil 3 - PBD 154)

Sample Soil 3 NUM

Element PBD 154

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

4L 00010 - 1 150 Fail - - 4L - - NUM46L 00001 0000 4 -053 096 Fail - - 46L - - NUM64L 00001 0000 4 -056 105 Fail NUM - 64L - - NUM12L 00002 0000 4 -040 099 Fail - - 12L - - NUM

Totgem 000037 0000 mgkg 1-level 149 (164) NUM (4L46L64L12L) -1Totstd= 000042 0000 5-level 142 (153) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (4L46L64L12L)

000 050 100 150

k-values

4L

46L

64L

12L

Mandels k statistics(Soil 3 - PBD 154)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

4L

46L

64L

12L

Labo

rato

ries

NUM

-100 000 100 200

h-values

4L

46L

64L

12L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 154)

Soil 3-PBD 154

Unit mgkg

Mandels k statistics(Compost 1 - PBD 209)Mandels h statistics(Compost 1 - PBD 209)

Sample Compost 1 NUM

Element PBD 209

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00065 0003 2 -049 032 - - 4L - - NUM

44L 00573 0021 4 150 197 Fail - - 44L - - NUM12L 00078 0001 4 -045 011 - - 12L - - NUM26L 00049 0000 2 -056 000 NUM - 26L - - NUM

Totgem 0019 0006 mgkg 1-level 149 (177) NUM (4L44L12L26L) -1Totstd= 0025 0010 5-level 142 (159) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (4L44L12L26L)

000 050 100 150 200

k-values

4L

44L

12L

26L

Mandels k statistics(Compost 1 - PBD 209)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

4L

44L

12L

26L

Labo

rato

ries

NUM

-100 000 100 200

h-values

4L

44L

12L

26L

Labo

rato

ries

Mandels h statistics(Compost 1 - PBD 209)

Compost 1-PBD 209

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 209)Mandels h statistics(Sludge 1 - PBD 209)

Sample Sludge 1 Sludge 1 - PBD 209 -- Mean PARM = 0249 [mgkg]

Element PBD 209

General calcparmT1= 394542E+00T2= 107296E+00T3= 16T4= 56T5= 19723E-02

n= variabelp= 5

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 01550 0055 4 -112 148 Fail 01550 00551 4 3 -009

46L 02050 0007 2 -053 019 02050 00071 2 1 -00412L 02137 0058 4 -042 155 02137 00576 4 3 -00426L 03149 0021 2 078 057 Fail 03149 00210 2 1 00764L 03577 0007 4 129 020 Fail 03577 00074 4 3 011

Totgem 0249 0030 mgkg 1-level 172 (185) 5 02493 () 5 4Totstd= 0084 0025 5-level 157 (162)

RESULTS Mean = 024926 mgkg

Repeatability variance S2r = 000179Repeatability std Sr = 004234 --gt 1699 r = 01186Between lab variance S2L = 000743Reproducibility var S2R = 000922Reproducibility std SR = 009604 --gt 3853 R = 02689Remarks none

000 050 100 150 200

k-values

4L

46L

12L

26L

64L

Mandels k statistics(Sludge 1 - PBD 209)

-01 -01 00 01 01 02

Deviation from Mean

4L

46L

12L

26L

64L

Labo

rato

ries

Sludge 1 - PBD 209 -- Mean PARM = 0249 [mgkg]

-200 -100 000 100 200

h-values

4L

46L

12L

26L

64L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 209)

Sludge 1-PBD 209

Unit mgkg

Mandels k statistics(Soil 3 - PBD 209)Mandels h statistics(Soil 3 - PBD 209)

Sample Soil 3 Soil 3 - PBD 209 -- Mean PARM = 0258 [mgkg]

Element PBD 209

General calcparmT1= 596398E+00T2= 191917E+00T3= 22T4= 84T5= 13249E-02

n= variabelp= 6

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean26L 01162 0021 2 -108 074 Fail 01162 00207 2 1 -0144L 01303 0031 4 -097 111 Fail 01303 00312 4 3 -013

46L 01975 0036 4 -046 128 Fail 01975 00359 4 3 -00644L 02898 0035 4 024 124 Fail 02898 00346 4 3 00312L 03895 0018 4 100 065 Fail 03895 00181 4 3 01364L 04260 0022 4 127 078 Fail 04260 00219 4 3 017

Totgem 0258 0027 mgkg 1-level 187 (177) 6 02582 () 6 5Totstd= 0132 0008 5-level 166 (154)

RESULTS Mean = 025818 mgkg

Repeatability variance S2r = 000083Repeatability std Sr = 002878 --gt 1115 r = 00806Between lab variance S2L = 001640Reproducibility var S2R = 001723Reproducibility std SR = 013127 --gt 5084 R = 03676Remarks none

000 050 100 150

k-values

26L

4L

46L

44L

12L

64L

Mandels k statistics(Soil 3 - PBD 209)

-02 -01 -01 00 01 01 02 02

Deviation from Mean

26L

4L

46L

44L

12L

64L

Labo

rato

ries

Soil 3 - PBD 209 -- Mean PARM = 0258 [mgkg]

-200 -100 000 100 200

h-values

26L

4L

46L

44L

12L

64L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 209)

Soil 3-PBD 209

Unit mgkg

Mandels k statistics(Compost 1 - Sum PBD)Mandels h statistics(Compost 1 - Sum PBD)

Sample Compost 1 Compost 1 - Sum PBD -- Mean PARM = 0009 [mgkg]

Element Sum PBD

General calcparmT1= 154064E-01T2= 169065E-03T3= 18T4= 68T5= 11354E-04

n= variabelp= 5

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00031 0002 4 -067 016 00031 00016 4 3 -0014L 00055 0005 4 -056 048 00055 00047 4 3 000

46L 00085 0003 4 -042 031 00085 00030 4 3 00026L 00123 0000 2 -024 003 00123 00002 2 1 00012L 00154 0002 4 -011 021 00154 00021 4 3 00144L 00613 0023 4 200 237 Fail - - 44L - - 005

Totgem 0018 0006 mgkg 1-level 187 (177) 5 00089 (44L) 5 4Totstd= 0022 0009 5-level 166 (154) 1

RESULTS Mean = 000893 mgkg

Repeatability variance S2r = 000001Repeatability std Sr = 000296 --gt 3308 r = 00083Between lab variance S2L = 000002Reproducibility var S2R = 000003Reproducibility std SR = 000570 --gt 6374 R = 00159Remarks 1 Lab rejected (44L)

000 050 100 150 200 250

k-values

10L

4L

46L

26L

12L

44L

Mandels k statistics(Compost 1 - Sum PBD)

00 00 00 00 00 00 01 01

Deviation from Mean

10L

4L

46L

26L

12L

44L

Labo

rato

ries

Compost 1 - Sum PBD -- Mean PARM = 0009 [mgkg]

-100 000 100 200

h-values

10L

4L

46L

26L

12L

44L

Labo

rato

ries

Mandels h statistics(Compost 1 - Sum PBD)

Compost 1-Sum PBD

Unit mgkg

Mandels k statistics(Sludge 1 - Sum PBD)Mandels h statistics(Sludge 1 - Sum PBD)

Sample Sludge 1 Sludge 1 - Sum PBD -- Mean PARM = 0256 [mgkg]

Element Sum PBD

General calcparmT1= 531806E+00T2= 162188E+00T3= 22T4= 84T5= 25223E-02

n= variabelp= 6

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00423 0025 4 -156 044 Fail 00423 00252 4 3 -02146L 01808 0118 4 -049 205 - - 46L - - -0074L 01810 0056 4 -049 097 01810 00558 4 3 -007

38L 02168 0006 4 -022 010 02168 00059 4 3 -00412L 02890 0065 4 034 113 02890 00647 4 3 00364L 03958 0008 4 116 014 Fail 03958 00079 4 3 01426L 04094 0034 2 126 059 Fail 04094 00337 2 1 015

Totgem 0245 0044 mgkg 1-level 198 (179) 6 02557 (46L) 6 5Totstd= 0130 0039 5-level 171 (155) 1

RESULTS Mean = 025570 mgkg

Repeatability variance S2r = 000158Repeatability std Sr = 003970 --gt 1553 r = 01112Between lab variance S2L = 001807Reproducibility var S2R = 001964Reproducibility std SR = 014015 --gt 5481 R = 03924Remarks 1 Lab rejected (46L)

000 050 100 150 200 250

k-values

10L

46L

4L

38L

12L

64L

26L

Mandels k statistics(Sludge 1 - Sum PBD)

-03 -02 -02 -01 -01 00 01 01 02 02

Deviation from Mean

10L

46L

4L

38L

12L

64L

26L

Labo

rato

ries

Sludge 1 - Sum PBD -- Mean PARM = 0256 [mgkg]

-200 -100 000 100 200

h-values

10L

46L

4L

38L

12L

64L

26L

Labo

rato

ries

Mandels h statistics(Sludge 1 - Sum PBD)

Sludge 1-Sum PBD

Unit mgkg

Mandels k statistics(Soil 3 - Sum PBD)Mandels h statistics(Soil 3 - Sum PBD)

Sample Soil 3 Soil 3 - Sum PBD -- Mean PARM = 0227 [mgkg]

Element Sum PBD

General calcparmT1= 610980E+00T2= 200876E+00T3= 26T4= 100T5= 13106E-02

n= variabelp= 7

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00028 0001 4 -037 000 Fail 00028 00005 4 3 -02226L 01179 0021 2 -036 003 Fail 01179 00208 2 1 -0114L 01305 0031 4 -036 004 Fail 01305 00308 4 3 -010

46L 02065 0035 4 -036 005 Fail 02065 00350 4 3 -00244L 02923 0037 4 -035 005 Fail 02923 00365 4 3 00712L 04051 0015 4 -034 002 Fail 04051 00149 4 3 01864L 04314 0022 4 -033 003 Fail 04314 00223 4 3 0203L 305500 2051 2 247 283 Fail - - 3L - - 3032

Totgem 4017 0276 mgkg 1-level 206 (181) 7 02266 (3L) 7 6Totstd= 10722 0717 5-level 175 (156) 1

RESULTS Mean = 022663 mgkg

Repeatability variance S2r = 000069Repeatability std Sr = 002626 --gt 1159 r = 00735Between lab variance S2L = 002568Reproducibility var S2R = 002637Reproducibility std SR = 016238 --gt 7165 R = 04547Remarks 1 Lab rejected (3L)

000 050 100 150 200 250 300

k-values

10L

26L

4L

46L

44L

12L

64L

3L

Mandels k statistics(Soil 3 - Sum PBD)

-50 00 50 100 150 200 250 300 350

Deviation from Mean

10L

26L

4L

46L

44L

12L

64L

3L

Labo

rato

ries

Soil 3 - Sum PBD -- Mean PARM = 0227 [mgkg]

-100 000 100 200 300

h-values

10L

26L

4L

46L

44L

12L

64L

3L

Labo

rato

ries

Mandels h statistics(Soil 3 - Sum PBD)

Soil 3-Sum PBD

19

Annex 4

Raw data submitted

Sample Compost1 Sample Compost 1 Sample Compost 1Element PBD 99 Element PBD 100 Element PBD 153

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]4L 00021 10L 00008 44L 000504L 00024 10L 00008 44L 000604L 00014 10L 00007 44L 000504L 00020 10L 00011 46L 00004

10L 00029 46L 00007 46L 0001210L 00027 46L 00012 46L 0000410L 00032 46L 00009 46L 0000946L 00025 46L 00007 12L 0000446L 00052 12L 00008 12L 0000846L 00029 12L 00012 12L 0000446L 00026 12L 00008 12L 0000712L 00026 12L 00014 26L 0000512L 00043 26L 00007 26L 0000512L 00026 26L 0000612L 0004726L 0002626L 00024

Sample Compost 1 Sample Compost 1 Sample Compost 1Element PBD 154 Element PBD 183 Element PBD 196

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]4L 00010 46L 00002 46L 00011

46L 00003 46L 00024 46L 0000846L 00007 46L 00021 12L 0000246L 00003 46L 00003 12L 0000346L 00004 12L 00003 12L 0000112L 00003 12L 00011 12L 0000212L 00005 12L 0000312L 00031 12L 0000312L 00006

Sample Compost 1 Sample Compost 1 Sample Compost 1Element PBD 197 Element PBD 203 Element PBD 209

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00002 46L 00010 4L 0004146L 00023 12L 00002 4L 0008946L 00022 12L 00003 44L 0041012L 00004 12L 00002 44L 0084012L 00006 12L 00002 44L 0064012L 00003 44L 0040012L 00004 12L 00079

12L 0007312L 0006512L 0009326L 0004926L 00049

Sample Compost 1Element PBD 47

LAB PARM [mgkg]26L 0003826L 00039

Element PBD 99 Element PBD 47 Element PBD 209LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]

4L 00170 10L 00210 4L 010004L 00200 10L 00220 4L 018004L 00170 10L 00210 4L 012004L 00190 46L 00300 4L 0220010L 00280 46L 00280 46L 0210010L 00300 46L 00250 46L 0200010L 00290 46L 00260 64L 0351846L 00340 64L 00059 64L 0363846L 00330 64L 00057 64L 0364546L 00300 64L 00062 64L 0350846L 00310 64L 00060 12L 0220964L 00194 12L 00191 12L 0177164L 00154 12L 00187 12L 0292264L 00185 12L 00190 12L 0164664L 00159 12L 00186 26L 0329712L 00242 26L 00666 26L 0300012L 00223 26L 0033212L 0022112L 0022226L 0024626L 00400

Element PBD 203 Element PBD 197 Element PBD 196LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00022 46L 00027 46L 0002446L 00014 46L 00024 46L 0002264L 00036 12L 00161 64L 0005864L 00058 12L 00060 64L 0006512L 00063 12L 00061 12L 0004812L 00034 12L 00036 12L 0002512L 00038 12L 0003212L 00027 12L 00022

Element PBD 183 Element PBD 154 Element PBD 153LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00049 4L 00020 4L 0002246L 00035 4L 00022 4L 0002446L 00036 4L 00020 4L 0002246L 00034 46L 00025 4L 0002664L 00027 46L 00025 46L 0004064L 00023 46L 00025 46L 0004264L 00024 46L 00023 46L 0003564L 00020 64L 00034 46L 0003812L 00230 64L 00023 64L 0007412L 00032 64L 00017 64L 0004712L 00031 64L 00011 64L 0004612L 00030 12L 00030 64L 0003026L 00007 12L 00021 12L 0006526L 00008 12L 00021 12L 00029

12L 00021 12L 0003226L 00015 12L 0002926L 00019 26L 00039

26L 00040

Element PBD 100LAB PARM [mgkg]

4L 000384L 000414L 000374L 00038

38L 0219038L 0220038L 0208038L 0220010L 0004410L 0005010L 0004310L 0004646L 0005746L 0005946L 0005346L 0005312L 0004312L 0004512L 0004312L 0004326L 0006226L 00057

Sample Soil 3 Sample Soil 3 Sample Soil 3Element PBD 99 Element PBD 47 Element PBD 100

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]10L 00016 10L 00011 10L 0000310L 00019 10L 00010 10L 0000410L 00013 10L 00012 10L 0000410L 00019 46L 00007 10L 0000246L 00025 46L 00022 46L 0000246L 00025 46L 00005 46L 0000646L 00008 46L 00007 46L 0000246L 00011 12L 00010 46L 0000264L 00005 12L 00017 3L 29100064L 00005 12L 00010 3L 32000064L 00006 12L 00009 26L 0000564L 00007 26L 00007 26L 0000512L 00012 26L 0000712L 0001312L 0001312L 0001226L 0000526L 00006

Sample Soil 3 Sample Soil 3 Sample Soil 3Element PBD 153 Element PBD 154 Element PBD 196

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]44L 00050 4L 00010 46L 0000744L 00050 46L 00001 46L 0001146L 00002 46L 00002 46L 0000846L 00003 46L 00001 46L 0001146L 00002 46L 00002 64L 0002646L 00002 64L 00001 64L 0002664L 00001 64L 00001 64L 0002964L 00001 64L 00001 64L 0003464L 00001 64L 00002 12L 0004564L 00002 12L 00003 12L 00032

12L 00002 12L 0002212L 00002 12L 0002112L 00002

Sample Soil 3 Sample Soil 3 Sample Soil 3Element PBD 197 Element PBD 203 Element PBD 209

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00006 46L 00011 4L 0091046L 00013 46L 00017 4L 0150046L 00011 46L 00015 4L 0120046L 00013 46L 00018 4L 0160012L 00090 64L 00013 44L 0337012L 00056 64L 00014 44L 0281012L 00033 64L 00016 44L 0287012L 00032 64L 00015 44L 02540

12L 00055 46L 0230012L 00041 46L 0220012L 00027 46L 0150012L 00026 46L 01900

64L 0438164L 0401664L 0414464L 0449812L 0367112L 0397812L 0409112L 03838

Sample Soil 3 26L 0102Element PBD 183 26L 0131

LAB PARM [mgkg]46L 0000746L 0000846L 0005846L 0000764L 0000264L 0000364L 0000364L 0000312L 0001512L 0001112L 0000712L 00007

European Commission EUR 23003 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on polybrominated diphenylethers Author(s) E Sobiecka H van der Sloot D Barcelo B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 68 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07403-5 Abstract Project HORIZONTAL is interdisciplinary aiming at a harmonisation and horizontal standardisation of test procedures in particular for sludge soils and biowastes In the context of this standardization project a series of draft technical specification were designed upon an extensive desk study fine-tuned after expert consultations and finally validated in international intercomparisons exercise This report summarises the work performed within the validation study of the draft standard for the determination of polybrominated diphenylethers (PBDE) in soils sludge and treated bio-waste using gas-chromatography method with mass selective detection (GC-MS) It further explains the underlying statistical concept for the calculation of reproducibility and repeatability from intercomparisons data In addition all single values results of the statistical evaluation as well as background information on the validation materials used are described and explained

The mission of the JRC is to provide customer-driven scientific and technical support for the conception development implementation and monitoring of EU policies As a service of the European Commission the JRC functions as a reference centre of science and technology for the Union Close to the policy-making process it serves the common interest of the Member States while being independent of special interests whether private or national

LB

-NA

-23003-EN

-C

Unit mgkg

Mandels k statistics(Compost 1 - PBD 100)Mandels h statistics(Compost 1 - PBD 100)

Sample Compost 1 Compost 1 - PBD 100 -- Mean PARM = 0001 [mgkg]

Element PBD 100

General calcparmT1= 124272E-02T2= 113129E-05T3= 14T4= 52T5= 46584E-07

n= variabelp= 4

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean26L 00006 0000 2 -131 037 Fail 00006 00001 2 1 00010L 00009 0000 4 003 083 00009 00002 4 3 00046L 00009 0000 4 016 115 00009 00002 4 3 00012L 00011 0000 4 112 136 Fail 00011 00003 4 3 000

Totgem 0001 0000 mgkg 1-level 149 (167) 4 00009 () 4 3Totstd= 0000 0000 5-level 142 (15)

RESULTS Mean = 000085 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000022 --gt 2531 r = 00006Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000025 --gt 2882 R = 00007Remarks none

000 050 100 150

k-values

26L

10L

46L

12L

Mandels k statistics(Compost 1 - PBD 100)

00 00 00 00 00 00 00 00 00 00 00

Deviation from Mean

26L

10L

46L

12L

Labo

rato

ries

Compost 1 - PBD 100 -- Mean PARM = 0001 [mgkg]

-200 -100 000 100 200

h-values

26L

10L

46L

12L

Labo

rato

ries

Mandels h statistics(Compost 1 - PBD 100)

Compost 1-PBD 100

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 100)Mandels h statistics(Sludge 1 - PBD 100)

Sample Sludge 1 Sludge 1 - PBD 100 -- Mean PARM = 0005 [mgkg]

Element PBD 100

General calcparmT1= 852065E-02T2= 412762E-04T3= 18T4= 68T5= 78914E-07

n= variabelp= 5

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00039 0000 4 -042 007 Fail 00039 00002 4 3 000

12L 00044 0000 4 -041 005 Fail 00044 00001 4 3 00010L 00046 0000 4 -041 013 Fail 00046 00003 4 3 00046L 00056 0000 4 -040 012 Fail 00056 00003 4 3 00026L 00059 0000 2 -040 013 Fail 00059 00003 2 1 00038L 02168 0006 4 204 244 Fail - - 38L - - 021

Totgem 0040 0001 mgkg 1-level 187 (177) 5 00049 (38L) 5 4Totstd= 0087 0002 5-level 166 (154) 1

RESULTS Mean = 000486 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000025 --gt 507 r = 00007Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000084 --gt 1731 R = 00024Remarks 1 Lab rejected (38L)

000 050 100 150 200 250

k-values

4L

12L

10L

46L

26L

38L

Mandels k statistics(Sludge 1 - PBD 100)

-01 00 01 01 02 02 03

Deviation from Mean

4L

12L

10L

46L

26L

38L

Labo

rato

ries

Sludge 1 - PBD 100 -- Mean PARM = 0005 [mgkg]

-100 000 100 200 300

h-values

4L

12L

10L

46L

26L

38L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 100)

Sludge 1-PBD 100

Unit mgkg

Mandels k statistics(Soil 3 - PBD 100)Mandels h statistics(Soil 3 - PBD 100)

Sample Soil 3 NUM

Element PBD 100

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00003 0000 4 -050 000 Fail - - 10L - - NUM46L 00003 0000 4 -050 000 Fail NUM - 46L - - NUM3L 305500 2051 2 150 200 Fail - - 3L - - NUM

26L 00005 0000 2 -050 000 Fail - - 26L - - NUM

Totgem 7638 0513 mgkg 1-level 149 (177) NUM (10L46L3L26L) -1Totstd= 15275 1025 5-level 142 (159) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (10L46L3L26L)

000 050 100 150 200

k-values

10L

46L

3L

26L

Mandels k statistics(Soil 3 - PBD 100)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

10L

46L

3L

26L

Labo

rato

ries

NUM

-100 000 100 200

h-values

10L

46L

3L

26L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 100)

Soil 3-PBD 100

Unit mgkg

Mandels k statistics(Compost 1 - PBD 153)Mandels h statistics(Compost 1 - PBD 153)

Sample Compost 1 NUM

Element PBD 153

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean44L 00053 0001 3 150 157 Fail - - 44L - - NUM46L 00007 0000 4 -044 111 Fail - - 46L - - NUM12L 00005 0000 4 -051 055 Fail - - 12L - - NUM26L 00005 0000 2 -054 001 Fail NUM - 26L - - NUM

Totgem 0002 0000 mgkg 1-level 149 (177) NUM (44L46L12L26L) -1Totstd= 0002 0000 5-level 142 (159) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (44L46L12L26L)

000 050 100 150 200

k-values

44L

46L

12L

26L

Mandels k statistics(Compost 1 - PBD 153)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

44L

46L

12L

26L

Labo

rato

ries

NUM

-100 000 100 200

h-values

44L

46L

12L

26L

Labo

rato

ries

Mandels h statistics(Compost 1 - PBD 153)

Compost 1-PBD 153

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 153)Mandels h statistics(Sludge 1 - PBD 153)

Sample Sludge 1 Sludge 1 - PBD 153 -- Mean PARM = 0004 [mgkg]

Element PBD 153

General calcparmT1= 676738E-02T2= 267609E-04T3= 18T4= 68T5= 19626E-05

n= variabelp= 5

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00024 0000 4 -157 017 00024 00002 4 3 000

12L 00038 0002 4 006 154 00038 00018 4 3 00046L 00039 0000 4 011 026 00039 00003 4 3 00026L 00039 0000 2 018 004 00039 00000 2 1 00064L 00049 0002 4 122 159 00049 00018 4 3 000

Totgem 0004 0001 mgkg 1-level 172 (173) 5 00038 () 5 4Totstd= 0001 0001 5-level 157 (153)

RESULTS Mean = 000378 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000123 --gt 3252 r = 00034Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000142 --gt 3754 R = 00040Remarks none

000 050 100 150 200

k-values

4L

12L

46L

26L

64L

Mandels k statistics(Sludge 1 - PBD 153)

00 00 00 00 00 00 00

Deviation from Mean

4L

12L

46L

26L

64L

Labo

rato

ries

Sludge 1 - PBD 153 -- Mean PARM = 0004 [mgkg]

-200 -100 000 100 200

h-values

4L

12L

46L

26L

64L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 153)

Sludge 1-PBD 153

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 154)Mandels h statistics(Sludge 1 - PBD 154)

Sample Sludge 1 NA

Element PBD 154

General calcparmT1= NAT2= NAT3=T4=T5=

n= variabelp=

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00021 0000 3 -100 021 NA - 4L - - NA

46L 00025 0000 4 115 018 NA - 46L - - NA64L 00021 0001 4 -066 179 - - 64L - - NA12L 00023 0000 4 050 085 - - 12L - - NA

Totgem 0002 0000 mgkg 1-level 149 (167) NA (4L46L64L12L) -1Totstd= 0000 0000 5-level 142 (15) 4

RESULTS Mean = NA mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NAReproducibility var S2R = NAReproducibility std SR = NA --gt NA R = NARemarks 4 Labs rejected (4L46L64L12L)

000 050 100 150 200

k-values

4L

46L

64L

12L

Mandels k statistics(Sludge 1 - PBD 154)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

4L

46L

64L

12L

Labo

rato

ries

NA

-100 000 100 200

h-values

4L

46L

64L

12L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 154)

Sludge 1-PBD 154

Unit mgkg

Mandels k statistics(Soil 3 - PBD 154)Mandels h statistics(Soil 3 - PBD 154)

Sample Soil 3 NUM

Element PBD 154

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

4L 00010 - 1 150 Fail - - 4L - - NUM46L 00001 0000 4 -053 096 Fail - - 46L - - NUM64L 00001 0000 4 -056 105 Fail NUM - 64L - - NUM12L 00002 0000 4 -040 099 Fail - - 12L - - NUM

Totgem 000037 0000 mgkg 1-level 149 (164) NUM (4L46L64L12L) -1Totstd= 000042 0000 5-level 142 (153) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (4L46L64L12L)

000 050 100 150

k-values

4L

46L

64L

12L

Mandels k statistics(Soil 3 - PBD 154)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

4L

46L

64L

12L

Labo

rato

ries

NUM

-100 000 100 200

h-values

4L

46L

64L

12L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 154)

Soil 3-PBD 154

Unit mgkg

Mandels k statistics(Compost 1 - PBD 209)Mandels h statistics(Compost 1 - PBD 209)

Sample Compost 1 NUM

Element PBD 209

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00065 0003 2 -049 032 - - 4L - - NUM

44L 00573 0021 4 150 197 Fail - - 44L - - NUM12L 00078 0001 4 -045 011 - - 12L - - NUM26L 00049 0000 2 -056 000 NUM - 26L - - NUM

Totgem 0019 0006 mgkg 1-level 149 (177) NUM (4L44L12L26L) -1Totstd= 0025 0010 5-level 142 (159) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (4L44L12L26L)

000 050 100 150 200

k-values

4L

44L

12L

26L

Mandels k statistics(Compost 1 - PBD 209)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

4L

44L

12L

26L

Labo

rato

ries

NUM

-100 000 100 200

h-values

4L

44L

12L

26L

Labo

rato

ries

Mandels h statistics(Compost 1 - PBD 209)

Compost 1-PBD 209

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 209)Mandels h statistics(Sludge 1 - PBD 209)

Sample Sludge 1 Sludge 1 - PBD 209 -- Mean PARM = 0249 [mgkg]

Element PBD 209

General calcparmT1= 394542E+00T2= 107296E+00T3= 16T4= 56T5= 19723E-02

n= variabelp= 5

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 01550 0055 4 -112 148 Fail 01550 00551 4 3 -009

46L 02050 0007 2 -053 019 02050 00071 2 1 -00412L 02137 0058 4 -042 155 02137 00576 4 3 -00426L 03149 0021 2 078 057 Fail 03149 00210 2 1 00764L 03577 0007 4 129 020 Fail 03577 00074 4 3 011

Totgem 0249 0030 mgkg 1-level 172 (185) 5 02493 () 5 4Totstd= 0084 0025 5-level 157 (162)

RESULTS Mean = 024926 mgkg

Repeatability variance S2r = 000179Repeatability std Sr = 004234 --gt 1699 r = 01186Between lab variance S2L = 000743Reproducibility var S2R = 000922Reproducibility std SR = 009604 --gt 3853 R = 02689Remarks none

000 050 100 150 200

k-values

4L

46L

12L

26L

64L

Mandels k statistics(Sludge 1 - PBD 209)

-01 -01 00 01 01 02

Deviation from Mean

4L

46L

12L

26L

64L

Labo

rato

ries

Sludge 1 - PBD 209 -- Mean PARM = 0249 [mgkg]

-200 -100 000 100 200

h-values

4L

46L

12L

26L

64L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 209)

Sludge 1-PBD 209

Unit mgkg

Mandels k statistics(Soil 3 - PBD 209)Mandels h statistics(Soil 3 - PBD 209)

Sample Soil 3 Soil 3 - PBD 209 -- Mean PARM = 0258 [mgkg]

Element PBD 209

General calcparmT1= 596398E+00T2= 191917E+00T3= 22T4= 84T5= 13249E-02

n= variabelp= 6

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean26L 01162 0021 2 -108 074 Fail 01162 00207 2 1 -0144L 01303 0031 4 -097 111 Fail 01303 00312 4 3 -013

46L 01975 0036 4 -046 128 Fail 01975 00359 4 3 -00644L 02898 0035 4 024 124 Fail 02898 00346 4 3 00312L 03895 0018 4 100 065 Fail 03895 00181 4 3 01364L 04260 0022 4 127 078 Fail 04260 00219 4 3 017

Totgem 0258 0027 mgkg 1-level 187 (177) 6 02582 () 6 5Totstd= 0132 0008 5-level 166 (154)

RESULTS Mean = 025818 mgkg

Repeatability variance S2r = 000083Repeatability std Sr = 002878 --gt 1115 r = 00806Between lab variance S2L = 001640Reproducibility var S2R = 001723Reproducibility std SR = 013127 --gt 5084 R = 03676Remarks none

000 050 100 150

k-values

26L

4L

46L

44L

12L

64L

Mandels k statistics(Soil 3 - PBD 209)

-02 -01 -01 00 01 01 02 02

Deviation from Mean

26L

4L

46L

44L

12L

64L

Labo

rato

ries

Soil 3 - PBD 209 -- Mean PARM = 0258 [mgkg]

-200 -100 000 100 200

h-values

26L

4L

46L

44L

12L

64L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 209)

Soil 3-PBD 209

Unit mgkg

Mandels k statistics(Compost 1 - Sum PBD)Mandels h statistics(Compost 1 - Sum PBD)

Sample Compost 1 Compost 1 - Sum PBD -- Mean PARM = 0009 [mgkg]

Element Sum PBD

General calcparmT1= 154064E-01T2= 169065E-03T3= 18T4= 68T5= 11354E-04

n= variabelp= 5

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00031 0002 4 -067 016 00031 00016 4 3 -0014L 00055 0005 4 -056 048 00055 00047 4 3 000

46L 00085 0003 4 -042 031 00085 00030 4 3 00026L 00123 0000 2 -024 003 00123 00002 2 1 00012L 00154 0002 4 -011 021 00154 00021 4 3 00144L 00613 0023 4 200 237 Fail - - 44L - - 005

Totgem 0018 0006 mgkg 1-level 187 (177) 5 00089 (44L) 5 4Totstd= 0022 0009 5-level 166 (154) 1

RESULTS Mean = 000893 mgkg

Repeatability variance S2r = 000001Repeatability std Sr = 000296 --gt 3308 r = 00083Between lab variance S2L = 000002Reproducibility var S2R = 000003Reproducibility std SR = 000570 --gt 6374 R = 00159Remarks 1 Lab rejected (44L)

000 050 100 150 200 250

k-values

10L

4L

46L

26L

12L

44L

Mandels k statistics(Compost 1 - Sum PBD)

00 00 00 00 00 00 01 01

Deviation from Mean

10L

4L

46L

26L

12L

44L

Labo

rato

ries

Compost 1 - Sum PBD -- Mean PARM = 0009 [mgkg]

-100 000 100 200

h-values

10L

4L

46L

26L

12L

44L

Labo

rato

ries

Mandels h statistics(Compost 1 - Sum PBD)

Compost 1-Sum PBD

Unit mgkg

Mandels k statistics(Sludge 1 - Sum PBD)Mandels h statistics(Sludge 1 - Sum PBD)

Sample Sludge 1 Sludge 1 - Sum PBD -- Mean PARM = 0256 [mgkg]

Element Sum PBD

General calcparmT1= 531806E+00T2= 162188E+00T3= 22T4= 84T5= 25223E-02

n= variabelp= 6

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00423 0025 4 -156 044 Fail 00423 00252 4 3 -02146L 01808 0118 4 -049 205 - - 46L - - -0074L 01810 0056 4 -049 097 01810 00558 4 3 -007

38L 02168 0006 4 -022 010 02168 00059 4 3 -00412L 02890 0065 4 034 113 02890 00647 4 3 00364L 03958 0008 4 116 014 Fail 03958 00079 4 3 01426L 04094 0034 2 126 059 Fail 04094 00337 2 1 015

Totgem 0245 0044 mgkg 1-level 198 (179) 6 02557 (46L) 6 5Totstd= 0130 0039 5-level 171 (155) 1

RESULTS Mean = 025570 mgkg

Repeatability variance S2r = 000158Repeatability std Sr = 003970 --gt 1553 r = 01112Between lab variance S2L = 001807Reproducibility var S2R = 001964Reproducibility std SR = 014015 --gt 5481 R = 03924Remarks 1 Lab rejected (46L)

000 050 100 150 200 250

k-values

10L

46L

4L

38L

12L

64L

26L

Mandels k statistics(Sludge 1 - Sum PBD)

-03 -02 -02 -01 -01 00 01 01 02 02

Deviation from Mean

10L

46L

4L

38L

12L

64L

26L

Labo

rato

ries

Sludge 1 - Sum PBD -- Mean PARM = 0256 [mgkg]

-200 -100 000 100 200

h-values

10L

46L

4L

38L

12L

64L

26L

Labo

rato

ries

Mandels h statistics(Sludge 1 - Sum PBD)

Sludge 1-Sum PBD

Unit mgkg

Mandels k statistics(Soil 3 - Sum PBD)Mandels h statistics(Soil 3 - Sum PBD)

Sample Soil 3 Soil 3 - Sum PBD -- Mean PARM = 0227 [mgkg]

Element Sum PBD

General calcparmT1= 610980E+00T2= 200876E+00T3= 26T4= 100T5= 13106E-02

n= variabelp= 7

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00028 0001 4 -037 000 Fail 00028 00005 4 3 -02226L 01179 0021 2 -036 003 Fail 01179 00208 2 1 -0114L 01305 0031 4 -036 004 Fail 01305 00308 4 3 -010

46L 02065 0035 4 -036 005 Fail 02065 00350 4 3 -00244L 02923 0037 4 -035 005 Fail 02923 00365 4 3 00712L 04051 0015 4 -034 002 Fail 04051 00149 4 3 01864L 04314 0022 4 -033 003 Fail 04314 00223 4 3 0203L 305500 2051 2 247 283 Fail - - 3L - - 3032

Totgem 4017 0276 mgkg 1-level 206 (181) 7 02266 (3L) 7 6Totstd= 10722 0717 5-level 175 (156) 1

RESULTS Mean = 022663 mgkg

Repeatability variance S2r = 000069Repeatability std Sr = 002626 --gt 1159 r = 00735Between lab variance S2L = 002568Reproducibility var S2R = 002637Reproducibility std SR = 016238 --gt 7165 R = 04547Remarks 1 Lab rejected (3L)

000 050 100 150 200 250 300

k-values

10L

26L

4L

46L

44L

12L

64L

3L

Mandels k statistics(Soil 3 - Sum PBD)

-50 00 50 100 150 200 250 300 350

Deviation from Mean

10L

26L

4L

46L

44L

12L

64L

3L

Labo

rato

ries

Soil 3 - Sum PBD -- Mean PARM = 0227 [mgkg]

-100 000 100 200 300

h-values

10L

26L

4L

46L

44L

12L

64L

3L

Labo

rato

ries

Mandels h statistics(Soil 3 - Sum PBD)

Soil 3-Sum PBD

19

Annex 4

Raw data submitted

Sample Compost1 Sample Compost 1 Sample Compost 1Element PBD 99 Element PBD 100 Element PBD 153

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]4L 00021 10L 00008 44L 000504L 00024 10L 00008 44L 000604L 00014 10L 00007 44L 000504L 00020 10L 00011 46L 00004

10L 00029 46L 00007 46L 0001210L 00027 46L 00012 46L 0000410L 00032 46L 00009 46L 0000946L 00025 46L 00007 12L 0000446L 00052 12L 00008 12L 0000846L 00029 12L 00012 12L 0000446L 00026 12L 00008 12L 0000712L 00026 12L 00014 26L 0000512L 00043 26L 00007 26L 0000512L 00026 26L 0000612L 0004726L 0002626L 00024

Sample Compost 1 Sample Compost 1 Sample Compost 1Element PBD 154 Element PBD 183 Element PBD 196

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]4L 00010 46L 00002 46L 00011

46L 00003 46L 00024 46L 0000846L 00007 46L 00021 12L 0000246L 00003 46L 00003 12L 0000346L 00004 12L 00003 12L 0000112L 00003 12L 00011 12L 0000212L 00005 12L 0000312L 00031 12L 0000312L 00006

Sample Compost 1 Sample Compost 1 Sample Compost 1Element PBD 197 Element PBD 203 Element PBD 209

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00002 46L 00010 4L 0004146L 00023 12L 00002 4L 0008946L 00022 12L 00003 44L 0041012L 00004 12L 00002 44L 0084012L 00006 12L 00002 44L 0064012L 00003 44L 0040012L 00004 12L 00079

12L 0007312L 0006512L 0009326L 0004926L 00049

Sample Compost 1Element PBD 47

LAB PARM [mgkg]26L 0003826L 00039

Element PBD 99 Element PBD 47 Element PBD 209LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]

4L 00170 10L 00210 4L 010004L 00200 10L 00220 4L 018004L 00170 10L 00210 4L 012004L 00190 46L 00300 4L 0220010L 00280 46L 00280 46L 0210010L 00300 46L 00250 46L 0200010L 00290 46L 00260 64L 0351846L 00340 64L 00059 64L 0363846L 00330 64L 00057 64L 0364546L 00300 64L 00062 64L 0350846L 00310 64L 00060 12L 0220964L 00194 12L 00191 12L 0177164L 00154 12L 00187 12L 0292264L 00185 12L 00190 12L 0164664L 00159 12L 00186 26L 0329712L 00242 26L 00666 26L 0300012L 00223 26L 0033212L 0022112L 0022226L 0024626L 00400

Element PBD 203 Element PBD 197 Element PBD 196LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00022 46L 00027 46L 0002446L 00014 46L 00024 46L 0002264L 00036 12L 00161 64L 0005864L 00058 12L 00060 64L 0006512L 00063 12L 00061 12L 0004812L 00034 12L 00036 12L 0002512L 00038 12L 0003212L 00027 12L 00022

Element PBD 183 Element PBD 154 Element PBD 153LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00049 4L 00020 4L 0002246L 00035 4L 00022 4L 0002446L 00036 4L 00020 4L 0002246L 00034 46L 00025 4L 0002664L 00027 46L 00025 46L 0004064L 00023 46L 00025 46L 0004264L 00024 46L 00023 46L 0003564L 00020 64L 00034 46L 0003812L 00230 64L 00023 64L 0007412L 00032 64L 00017 64L 0004712L 00031 64L 00011 64L 0004612L 00030 12L 00030 64L 0003026L 00007 12L 00021 12L 0006526L 00008 12L 00021 12L 00029

12L 00021 12L 0003226L 00015 12L 0002926L 00019 26L 00039

26L 00040

Element PBD 100LAB PARM [mgkg]

4L 000384L 000414L 000374L 00038

38L 0219038L 0220038L 0208038L 0220010L 0004410L 0005010L 0004310L 0004646L 0005746L 0005946L 0005346L 0005312L 0004312L 0004512L 0004312L 0004326L 0006226L 00057

Sample Soil 3 Sample Soil 3 Sample Soil 3Element PBD 99 Element PBD 47 Element PBD 100

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]10L 00016 10L 00011 10L 0000310L 00019 10L 00010 10L 0000410L 00013 10L 00012 10L 0000410L 00019 46L 00007 10L 0000246L 00025 46L 00022 46L 0000246L 00025 46L 00005 46L 0000646L 00008 46L 00007 46L 0000246L 00011 12L 00010 46L 0000264L 00005 12L 00017 3L 29100064L 00005 12L 00010 3L 32000064L 00006 12L 00009 26L 0000564L 00007 26L 00007 26L 0000512L 00012 26L 0000712L 0001312L 0001312L 0001226L 0000526L 00006

Sample Soil 3 Sample Soil 3 Sample Soil 3Element PBD 153 Element PBD 154 Element PBD 196

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]44L 00050 4L 00010 46L 0000744L 00050 46L 00001 46L 0001146L 00002 46L 00002 46L 0000846L 00003 46L 00001 46L 0001146L 00002 46L 00002 64L 0002646L 00002 64L 00001 64L 0002664L 00001 64L 00001 64L 0002964L 00001 64L 00001 64L 0003464L 00001 64L 00002 12L 0004564L 00002 12L 00003 12L 00032

12L 00002 12L 0002212L 00002 12L 0002112L 00002

Sample Soil 3 Sample Soil 3 Sample Soil 3Element PBD 197 Element PBD 203 Element PBD 209

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00006 46L 00011 4L 0091046L 00013 46L 00017 4L 0150046L 00011 46L 00015 4L 0120046L 00013 46L 00018 4L 0160012L 00090 64L 00013 44L 0337012L 00056 64L 00014 44L 0281012L 00033 64L 00016 44L 0287012L 00032 64L 00015 44L 02540

12L 00055 46L 0230012L 00041 46L 0220012L 00027 46L 0150012L 00026 46L 01900

64L 0438164L 0401664L 0414464L 0449812L 0367112L 0397812L 0409112L 03838

Sample Soil 3 26L 0102Element PBD 183 26L 0131

LAB PARM [mgkg]46L 0000746L 0000846L 0005846L 0000764L 0000264L 0000364L 0000364L 0000312L 0001512L 0001112L 0000712L 00007

European Commission EUR 23003 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on polybrominated diphenylethers Author(s) E Sobiecka H van der Sloot D Barcelo B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 68 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07403-5 Abstract Project HORIZONTAL is interdisciplinary aiming at a harmonisation and horizontal standardisation of test procedures in particular for sludge soils and biowastes In the context of this standardization project a series of draft technical specification were designed upon an extensive desk study fine-tuned after expert consultations and finally validated in international intercomparisons exercise This report summarises the work performed within the validation study of the draft standard for the determination of polybrominated diphenylethers (PBDE) in soils sludge and treated bio-waste using gas-chromatography method with mass selective detection (GC-MS) It further explains the underlying statistical concept for the calculation of reproducibility and repeatability from intercomparisons data In addition all single values results of the statistical evaluation as well as background information on the validation materials used are described and explained

The mission of the JRC is to provide customer-driven scientific and technical support for the conception development implementation and monitoring of EU policies As a service of the European Commission the JRC functions as a reference centre of science and technology for the Union Close to the policy-making process it serves the common interest of the Member States while being independent of special interests whether private or national

LB

-NA

-23003-EN

-C

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 100)Mandels h statistics(Sludge 1 - PBD 100)

Sample Sludge 1 Sludge 1 - PBD 100 -- Mean PARM = 0005 [mgkg]

Element PBD 100

General calcparmT1= 852065E-02T2= 412762E-04T3= 18T4= 68T5= 78914E-07

n= variabelp= 5

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00039 0000 4 -042 007 Fail 00039 00002 4 3 000

12L 00044 0000 4 -041 005 Fail 00044 00001 4 3 00010L 00046 0000 4 -041 013 Fail 00046 00003 4 3 00046L 00056 0000 4 -040 012 Fail 00056 00003 4 3 00026L 00059 0000 2 -040 013 Fail 00059 00003 2 1 00038L 02168 0006 4 204 244 Fail - - 38L - - 021

Totgem 0040 0001 mgkg 1-level 187 (177) 5 00049 (38L) 5 4Totstd= 0087 0002 5-level 166 (154) 1

RESULTS Mean = 000486 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000025 --gt 507 r = 00007Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000084 --gt 1731 R = 00024Remarks 1 Lab rejected (38L)

000 050 100 150 200 250

k-values

4L

12L

10L

46L

26L

38L

Mandels k statistics(Sludge 1 - PBD 100)

-01 00 01 01 02 02 03

Deviation from Mean

4L

12L

10L

46L

26L

38L

Labo

rato

ries

Sludge 1 - PBD 100 -- Mean PARM = 0005 [mgkg]

-100 000 100 200 300

h-values

4L

12L

10L

46L

26L

38L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 100)

Sludge 1-PBD 100

Unit mgkg

Mandels k statistics(Soil 3 - PBD 100)Mandels h statistics(Soil 3 - PBD 100)

Sample Soil 3 NUM

Element PBD 100

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00003 0000 4 -050 000 Fail - - 10L - - NUM46L 00003 0000 4 -050 000 Fail NUM - 46L - - NUM3L 305500 2051 2 150 200 Fail - - 3L - - NUM

26L 00005 0000 2 -050 000 Fail - - 26L - - NUM

Totgem 7638 0513 mgkg 1-level 149 (177) NUM (10L46L3L26L) -1Totstd= 15275 1025 5-level 142 (159) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (10L46L3L26L)

000 050 100 150 200

k-values

10L

46L

3L

26L

Mandels k statistics(Soil 3 - PBD 100)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

10L

46L

3L

26L

Labo

rato

ries

NUM

-100 000 100 200

h-values

10L

46L

3L

26L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 100)

Soil 3-PBD 100

Unit mgkg

Mandels k statistics(Compost 1 - PBD 153)Mandels h statistics(Compost 1 - PBD 153)

Sample Compost 1 NUM

Element PBD 153

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean44L 00053 0001 3 150 157 Fail - - 44L - - NUM46L 00007 0000 4 -044 111 Fail - - 46L - - NUM12L 00005 0000 4 -051 055 Fail - - 12L - - NUM26L 00005 0000 2 -054 001 Fail NUM - 26L - - NUM

Totgem 0002 0000 mgkg 1-level 149 (177) NUM (44L46L12L26L) -1Totstd= 0002 0000 5-level 142 (159) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (44L46L12L26L)

000 050 100 150 200

k-values

44L

46L

12L

26L

Mandels k statistics(Compost 1 - PBD 153)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

44L

46L

12L

26L

Labo

rato

ries

NUM

-100 000 100 200

h-values

44L

46L

12L

26L

Labo

rato

ries

Mandels h statistics(Compost 1 - PBD 153)

Compost 1-PBD 153

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 153)Mandels h statistics(Sludge 1 - PBD 153)

Sample Sludge 1 Sludge 1 - PBD 153 -- Mean PARM = 0004 [mgkg]

Element PBD 153

General calcparmT1= 676738E-02T2= 267609E-04T3= 18T4= 68T5= 19626E-05

n= variabelp= 5

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00024 0000 4 -157 017 00024 00002 4 3 000

12L 00038 0002 4 006 154 00038 00018 4 3 00046L 00039 0000 4 011 026 00039 00003 4 3 00026L 00039 0000 2 018 004 00039 00000 2 1 00064L 00049 0002 4 122 159 00049 00018 4 3 000

Totgem 0004 0001 mgkg 1-level 172 (173) 5 00038 () 5 4Totstd= 0001 0001 5-level 157 (153)

RESULTS Mean = 000378 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000123 --gt 3252 r = 00034Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000142 --gt 3754 R = 00040Remarks none

000 050 100 150 200

k-values

4L

12L

46L

26L

64L

Mandels k statistics(Sludge 1 - PBD 153)

00 00 00 00 00 00 00

Deviation from Mean

4L

12L

46L

26L

64L

Labo

rato

ries

Sludge 1 - PBD 153 -- Mean PARM = 0004 [mgkg]

-200 -100 000 100 200

h-values

4L

12L

46L

26L

64L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 153)

Sludge 1-PBD 153

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 154)Mandels h statistics(Sludge 1 - PBD 154)

Sample Sludge 1 NA

Element PBD 154

General calcparmT1= NAT2= NAT3=T4=T5=

n= variabelp=

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00021 0000 3 -100 021 NA - 4L - - NA

46L 00025 0000 4 115 018 NA - 46L - - NA64L 00021 0001 4 -066 179 - - 64L - - NA12L 00023 0000 4 050 085 - - 12L - - NA

Totgem 0002 0000 mgkg 1-level 149 (167) NA (4L46L64L12L) -1Totstd= 0000 0000 5-level 142 (15) 4

RESULTS Mean = NA mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NAReproducibility var S2R = NAReproducibility std SR = NA --gt NA R = NARemarks 4 Labs rejected (4L46L64L12L)

000 050 100 150 200

k-values

4L

46L

64L

12L

Mandels k statistics(Sludge 1 - PBD 154)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

4L

46L

64L

12L

Labo

rato

ries

NA

-100 000 100 200

h-values

4L

46L

64L

12L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 154)

Sludge 1-PBD 154

Unit mgkg

Mandels k statistics(Soil 3 - PBD 154)Mandels h statistics(Soil 3 - PBD 154)

Sample Soil 3 NUM

Element PBD 154

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

4L 00010 - 1 150 Fail - - 4L - - NUM46L 00001 0000 4 -053 096 Fail - - 46L - - NUM64L 00001 0000 4 -056 105 Fail NUM - 64L - - NUM12L 00002 0000 4 -040 099 Fail - - 12L - - NUM

Totgem 000037 0000 mgkg 1-level 149 (164) NUM (4L46L64L12L) -1Totstd= 000042 0000 5-level 142 (153) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (4L46L64L12L)

000 050 100 150

k-values

4L

46L

64L

12L

Mandels k statistics(Soil 3 - PBD 154)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

4L

46L

64L

12L

Labo

rato

ries

NUM

-100 000 100 200

h-values

4L

46L

64L

12L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 154)

Soil 3-PBD 154

Unit mgkg

Mandels k statistics(Compost 1 - PBD 209)Mandels h statistics(Compost 1 - PBD 209)

Sample Compost 1 NUM

Element PBD 209

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00065 0003 2 -049 032 - - 4L - - NUM

44L 00573 0021 4 150 197 Fail - - 44L - - NUM12L 00078 0001 4 -045 011 - - 12L - - NUM26L 00049 0000 2 -056 000 NUM - 26L - - NUM

Totgem 0019 0006 mgkg 1-level 149 (177) NUM (4L44L12L26L) -1Totstd= 0025 0010 5-level 142 (159) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (4L44L12L26L)

000 050 100 150 200

k-values

4L

44L

12L

26L

Mandels k statistics(Compost 1 - PBD 209)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

4L

44L

12L

26L

Labo

rato

ries

NUM

-100 000 100 200

h-values

4L

44L

12L

26L

Labo

rato

ries

Mandels h statistics(Compost 1 - PBD 209)

Compost 1-PBD 209

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 209)Mandels h statistics(Sludge 1 - PBD 209)

Sample Sludge 1 Sludge 1 - PBD 209 -- Mean PARM = 0249 [mgkg]

Element PBD 209

General calcparmT1= 394542E+00T2= 107296E+00T3= 16T4= 56T5= 19723E-02

n= variabelp= 5

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 01550 0055 4 -112 148 Fail 01550 00551 4 3 -009

46L 02050 0007 2 -053 019 02050 00071 2 1 -00412L 02137 0058 4 -042 155 02137 00576 4 3 -00426L 03149 0021 2 078 057 Fail 03149 00210 2 1 00764L 03577 0007 4 129 020 Fail 03577 00074 4 3 011

Totgem 0249 0030 mgkg 1-level 172 (185) 5 02493 () 5 4Totstd= 0084 0025 5-level 157 (162)

RESULTS Mean = 024926 mgkg

Repeatability variance S2r = 000179Repeatability std Sr = 004234 --gt 1699 r = 01186Between lab variance S2L = 000743Reproducibility var S2R = 000922Reproducibility std SR = 009604 --gt 3853 R = 02689Remarks none

000 050 100 150 200

k-values

4L

46L

12L

26L

64L

Mandels k statistics(Sludge 1 - PBD 209)

-01 -01 00 01 01 02

Deviation from Mean

4L

46L

12L

26L

64L

Labo

rato

ries

Sludge 1 - PBD 209 -- Mean PARM = 0249 [mgkg]

-200 -100 000 100 200

h-values

4L

46L

12L

26L

64L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 209)

Sludge 1-PBD 209

Unit mgkg

Mandels k statistics(Soil 3 - PBD 209)Mandels h statistics(Soil 3 - PBD 209)

Sample Soil 3 Soil 3 - PBD 209 -- Mean PARM = 0258 [mgkg]

Element PBD 209

General calcparmT1= 596398E+00T2= 191917E+00T3= 22T4= 84T5= 13249E-02

n= variabelp= 6

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean26L 01162 0021 2 -108 074 Fail 01162 00207 2 1 -0144L 01303 0031 4 -097 111 Fail 01303 00312 4 3 -013

46L 01975 0036 4 -046 128 Fail 01975 00359 4 3 -00644L 02898 0035 4 024 124 Fail 02898 00346 4 3 00312L 03895 0018 4 100 065 Fail 03895 00181 4 3 01364L 04260 0022 4 127 078 Fail 04260 00219 4 3 017

Totgem 0258 0027 mgkg 1-level 187 (177) 6 02582 () 6 5Totstd= 0132 0008 5-level 166 (154)

RESULTS Mean = 025818 mgkg

Repeatability variance S2r = 000083Repeatability std Sr = 002878 --gt 1115 r = 00806Between lab variance S2L = 001640Reproducibility var S2R = 001723Reproducibility std SR = 013127 --gt 5084 R = 03676Remarks none

000 050 100 150

k-values

26L

4L

46L

44L

12L

64L

Mandels k statistics(Soil 3 - PBD 209)

-02 -01 -01 00 01 01 02 02

Deviation from Mean

26L

4L

46L

44L

12L

64L

Labo

rato

ries

Soil 3 - PBD 209 -- Mean PARM = 0258 [mgkg]

-200 -100 000 100 200

h-values

26L

4L

46L

44L

12L

64L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 209)

Soil 3-PBD 209

Unit mgkg

Mandels k statistics(Compost 1 - Sum PBD)Mandels h statistics(Compost 1 - Sum PBD)

Sample Compost 1 Compost 1 - Sum PBD -- Mean PARM = 0009 [mgkg]

Element Sum PBD

General calcparmT1= 154064E-01T2= 169065E-03T3= 18T4= 68T5= 11354E-04

n= variabelp= 5

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00031 0002 4 -067 016 00031 00016 4 3 -0014L 00055 0005 4 -056 048 00055 00047 4 3 000

46L 00085 0003 4 -042 031 00085 00030 4 3 00026L 00123 0000 2 -024 003 00123 00002 2 1 00012L 00154 0002 4 -011 021 00154 00021 4 3 00144L 00613 0023 4 200 237 Fail - - 44L - - 005

Totgem 0018 0006 mgkg 1-level 187 (177) 5 00089 (44L) 5 4Totstd= 0022 0009 5-level 166 (154) 1

RESULTS Mean = 000893 mgkg

Repeatability variance S2r = 000001Repeatability std Sr = 000296 --gt 3308 r = 00083Between lab variance S2L = 000002Reproducibility var S2R = 000003Reproducibility std SR = 000570 --gt 6374 R = 00159Remarks 1 Lab rejected (44L)

000 050 100 150 200 250

k-values

10L

4L

46L

26L

12L

44L

Mandels k statistics(Compost 1 - Sum PBD)

00 00 00 00 00 00 01 01

Deviation from Mean

10L

4L

46L

26L

12L

44L

Labo

rato

ries

Compost 1 - Sum PBD -- Mean PARM = 0009 [mgkg]

-100 000 100 200

h-values

10L

4L

46L

26L

12L

44L

Labo

rato

ries

Mandels h statistics(Compost 1 - Sum PBD)

Compost 1-Sum PBD

Unit mgkg

Mandels k statistics(Sludge 1 - Sum PBD)Mandels h statistics(Sludge 1 - Sum PBD)

Sample Sludge 1 Sludge 1 - Sum PBD -- Mean PARM = 0256 [mgkg]

Element Sum PBD

General calcparmT1= 531806E+00T2= 162188E+00T3= 22T4= 84T5= 25223E-02

n= variabelp= 6

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00423 0025 4 -156 044 Fail 00423 00252 4 3 -02146L 01808 0118 4 -049 205 - - 46L - - -0074L 01810 0056 4 -049 097 01810 00558 4 3 -007

38L 02168 0006 4 -022 010 02168 00059 4 3 -00412L 02890 0065 4 034 113 02890 00647 4 3 00364L 03958 0008 4 116 014 Fail 03958 00079 4 3 01426L 04094 0034 2 126 059 Fail 04094 00337 2 1 015

Totgem 0245 0044 mgkg 1-level 198 (179) 6 02557 (46L) 6 5Totstd= 0130 0039 5-level 171 (155) 1

RESULTS Mean = 025570 mgkg

Repeatability variance S2r = 000158Repeatability std Sr = 003970 --gt 1553 r = 01112Between lab variance S2L = 001807Reproducibility var S2R = 001964Reproducibility std SR = 014015 --gt 5481 R = 03924Remarks 1 Lab rejected (46L)

000 050 100 150 200 250

k-values

10L

46L

4L

38L

12L

64L

26L

Mandels k statistics(Sludge 1 - Sum PBD)

-03 -02 -02 -01 -01 00 01 01 02 02

Deviation from Mean

10L

46L

4L

38L

12L

64L

26L

Labo

rato

ries

Sludge 1 - Sum PBD -- Mean PARM = 0256 [mgkg]

-200 -100 000 100 200

h-values

10L

46L

4L

38L

12L

64L

26L

Labo

rato

ries

Mandels h statistics(Sludge 1 - Sum PBD)

Sludge 1-Sum PBD

Unit mgkg

Mandels k statistics(Soil 3 - Sum PBD)Mandels h statistics(Soil 3 - Sum PBD)

Sample Soil 3 Soil 3 - Sum PBD -- Mean PARM = 0227 [mgkg]

Element Sum PBD

General calcparmT1= 610980E+00T2= 200876E+00T3= 26T4= 100T5= 13106E-02

n= variabelp= 7

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00028 0001 4 -037 000 Fail 00028 00005 4 3 -02226L 01179 0021 2 -036 003 Fail 01179 00208 2 1 -0114L 01305 0031 4 -036 004 Fail 01305 00308 4 3 -010

46L 02065 0035 4 -036 005 Fail 02065 00350 4 3 -00244L 02923 0037 4 -035 005 Fail 02923 00365 4 3 00712L 04051 0015 4 -034 002 Fail 04051 00149 4 3 01864L 04314 0022 4 -033 003 Fail 04314 00223 4 3 0203L 305500 2051 2 247 283 Fail - - 3L - - 3032

Totgem 4017 0276 mgkg 1-level 206 (181) 7 02266 (3L) 7 6Totstd= 10722 0717 5-level 175 (156) 1

RESULTS Mean = 022663 mgkg

Repeatability variance S2r = 000069Repeatability std Sr = 002626 --gt 1159 r = 00735Between lab variance S2L = 002568Reproducibility var S2R = 002637Reproducibility std SR = 016238 --gt 7165 R = 04547Remarks 1 Lab rejected (3L)

000 050 100 150 200 250 300

k-values

10L

26L

4L

46L

44L

12L

64L

3L

Mandels k statistics(Soil 3 - Sum PBD)

-50 00 50 100 150 200 250 300 350

Deviation from Mean

10L

26L

4L

46L

44L

12L

64L

3L

Labo

rato

ries

Soil 3 - Sum PBD -- Mean PARM = 0227 [mgkg]

-100 000 100 200 300

h-values

10L

26L

4L

46L

44L

12L

64L

3L

Labo

rato

ries

Mandels h statistics(Soil 3 - Sum PBD)

Soil 3-Sum PBD

19

Annex 4

Raw data submitted

Sample Compost1 Sample Compost 1 Sample Compost 1Element PBD 99 Element PBD 100 Element PBD 153

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]4L 00021 10L 00008 44L 000504L 00024 10L 00008 44L 000604L 00014 10L 00007 44L 000504L 00020 10L 00011 46L 00004

10L 00029 46L 00007 46L 0001210L 00027 46L 00012 46L 0000410L 00032 46L 00009 46L 0000946L 00025 46L 00007 12L 0000446L 00052 12L 00008 12L 0000846L 00029 12L 00012 12L 0000446L 00026 12L 00008 12L 0000712L 00026 12L 00014 26L 0000512L 00043 26L 00007 26L 0000512L 00026 26L 0000612L 0004726L 0002626L 00024

Sample Compost 1 Sample Compost 1 Sample Compost 1Element PBD 154 Element PBD 183 Element PBD 196

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]4L 00010 46L 00002 46L 00011

46L 00003 46L 00024 46L 0000846L 00007 46L 00021 12L 0000246L 00003 46L 00003 12L 0000346L 00004 12L 00003 12L 0000112L 00003 12L 00011 12L 0000212L 00005 12L 0000312L 00031 12L 0000312L 00006

Sample Compost 1 Sample Compost 1 Sample Compost 1Element PBD 197 Element PBD 203 Element PBD 209

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00002 46L 00010 4L 0004146L 00023 12L 00002 4L 0008946L 00022 12L 00003 44L 0041012L 00004 12L 00002 44L 0084012L 00006 12L 00002 44L 0064012L 00003 44L 0040012L 00004 12L 00079

12L 0007312L 0006512L 0009326L 0004926L 00049

Sample Compost 1Element PBD 47

LAB PARM [mgkg]26L 0003826L 00039

Element PBD 99 Element PBD 47 Element PBD 209LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]

4L 00170 10L 00210 4L 010004L 00200 10L 00220 4L 018004L 00170 10L 00210 4L 012004L 00190 46L 00300 4L 0220010L 00280 46L 00280 46L 0210010L 00300 46L 00250 46L 0200010L 00290 46L 00260 64L 0351846L 00340 64L 00059 64L 0363846L 00330 64L 00057 64L 0364546L 00300 64L 00062 64L 0350846L 00310 64L 00060 12L 0220964L 00194 12L 00191 12L 0177164L 00154 12L 00187 12L 0292264L 00185 12L 00190 12L 0164664L 00159 12L 00186 26L 0329712L 00242 26L 00666 26L 0300012L 00223 26L 0033212L 0022112L 0022226L 0024626L 00400

Element PBD 203 Element PBD 197 Element PBD 196LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00022 46L 00027 46L 0002446L 00014 46L 00024 46L 0002264L 00036 12L 00161 64L 0005864L 00058 12L 00060 64L 0006512L 00063 12L 00061 12L 0004812L 00034 12L 00036 12L 0002512L 00038 12L 0003212L 00027 12L 00022

Element PBD 183 Element PBD 154 Element PBD 153LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00049 4L 00020 4L 0002246L 00035 4L 00022 4L 0002446L 00036 4L 00020 4L 0002246L 00034 46L 00025 4L 0002664L 00027 46L 00025 46L 0004064L 00023 46L 00025 46L 0004264L 00024 46L 00023 46L 0003564L 00020 64L 00034 46L 0003812L 00230 64L 00023 64L 0007412L 00032 64L 00017 64L 0004712L 00031 64L 00011 64L 0004612L 00030 12L 00030 64L 0003026L 00007 12L 00021 12L 0006526L 00008 12L 00021 12L 00029

12L 00021 12L 0003226L 00015 12L 0002926L 00019 26L 00039

26L 00040

Element PBD 100LAB PARM [mgkg]

4L 000384L 000414L 000374L 00038

38L 0219038L 0220038L 0208038L 0220010L 0004410L 0005010L 0004310L 0004646L 0005746L 0005946L 0005346L 0005312L 0004312L 0004512L 0004312L 0004326L 0006226L 00057

Sample Soil 3 Sample Soil 3 Sample Soil 3Element PBD 99 Element PBD 47 Element PBD 100

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]10L 00016 10L 00011 10L 0000310L 00019 10L 00010 10L 0000410L 00013 10L 00012 10L 0000410L 00019 46L 00007 10L 0000246L 00025 46L 00022 46L 0000246L 00025 46L 00005 46L 0000646L 00008 46L 00007 46L 0000246L 00011 12L 00010 46L 0000264L 00005 12L 00017 3L 29100064L 00005 12L 00010 3L 32000064L 00006 12L 00009 26L 0000564L 00007 26L 00007 26L 0000512L 00012 26L 0000712L 0001312L 0001312L 0001226L 0000526L 00006

Sample Soil 3 Sample Soil 3 Sample Soil 3Element PBD 153 Element PBD 154 Element PBD 196

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]44L 00050 4L 00010 46L 0000744L 00050 46L 00001 46L 0001146L 00002 46L 00002 46L 0000846L 00003 46L 00001 46L 0001146L 00002 46L 00002 64L 0002646L 00002 64L 00001 64L 0002664L 00001 64L 00001 64L 0002964L 00001 64L 00001 64L 0003464L 00001 64L 00002 12L 0004564L 00002 12L 00003 12L 00032

12L 00002 12L 0002212L 00002 12L 0002112L 00002

Sample Soil 3 Sample Soil 3 Sample Soil 3Element PBD 197 Element PBD 203 Element PBD 209

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00006 46L 00011 4L 0091046L 00013 46L 00017 4L 0150046L 00011 46L 00015 4L 0120046L 00013 46L 00018 4L 0160012L 00090 64L 00013 44L 0337012L 00056 64L 00014 44L 0281012L 00033 64L 00016 44L 0287012L 00032 64L 00015 44L 02540

12L 00055 46L 0230012L 00041 46L 0220012L 00027 46L 0150012L 00026 46L 01900

64L 0438164L 0401664L 0414464L 0449812L 0367112L 0397812L 0409112L 03838

Sample Soil 3 26L 0102Element PBD 183 26L 0131

LAB PARM [mgkg]46L 0000746L 0000846L 0005846L 0000764L 0000264L 0000364L 0000364L 0000312L 0001512L 0001112L 0000712L 00007

European Commission EUR 23003 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on polybrominated diphenylethers Author(s) E Sobiecka H van der Sloot D Barcelo B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 68 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07403-5 Abstract Project HORIZONTAL is interdisciplinary aiming at a harmonisation and horizontal standardisation of test procedures in particular for sludge soils and biowastes In the context of this standardization project a series of draft technical specification were designed upon an extensive desk study fine-tuned after expert consultations and finally validated in international intercomparisons exercise This report summarises the work performed within the validation study of the draft standard for the determination of polybrominated diphenylethers (PBDE) in soils sludge and treated bio-waste using gas-chromatography method with mass selective detection (GC-MS) It further explains the underlying statistical concept for the calculation of reproducibility and repeatability from intercomparisons data In addition all single values results of the statistical evaluation as well as background information on the validation materials used are described and explained

The mission of the JRC is to provide customer-driven scientific and technical support for the conception development implementation and monitoring of EU policies As a service of the European Commission the JRC functions as a reference centre of science and technology for the Union Close to the policy-making process it serves the common interest of the Member States while being independent of special interests whether private or national

LB

-NA

-23003-EN

-C

Unit mgkg

Mandels k statistics(Soil 3 - PBD 100)Mandels h statistics(Soil 3 - PBD 100)

Sample Soil 3 NUM

Element PBD 100

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00003 0000 4 -050 000 Fail - - 10L - - NUM46L 00003 0000 4 -050 000 Fail NUM - 46L - - NUM3L 305500 2051 2 150 200 Fail - - 3L - - NUM

26L 00005 0000 2 -050 000 Fail - - 26L - - NUM

Totgem 7638 0513 mgkg 1-level 149 (177) NUM (10L46L3L26L) -1Totstd= 15275 1025 5-level 142 (159) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (10L46L3L26L)

000 050 100 150 200

k-values

10L

46L

3L

26L

Mandels k statistics(Soil 3 - PBD 100)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

10L

46L

3L

26L

Labo

rato

ries

NUM

-100 000 100 200

h-values

10L

46L

3L

26L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 100)

Soil 3-PBD 100

Unit mgkg

Mandels k statistics(Compost 1 - PBD 153)Mandels h statistics(Compost 1 - PBD 153)

Sample Compost 1 NUM

Element PBD 153

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean44L 00053 0001 3 150 157 Fail - - 44L - - NUM46L 00007 0000 4 -044 111 Fail - - 46L - - NUM12L 00005 0000 4 -051 055 Fail - - 12L - - NUM26L 00005 0000 2 -054 001 Fail NUM - 26L - - NUM

Totgem 0002 0000 mgkg 1-level 149 (177) NUM (44L46L12L26L) -1Totstd= 0002 0000 5-level 142 (159) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (44L46L12L26L)

000 050 100 150 200

k-values

44L

46L

12L

26L

Mandels k statistics(Compost 1 - PBD 153)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

44L

46L

12L

26L

Labo

rato

ries

NUM

-100 000 100 200

h-values

44L

46L

12L

26L

Labo

rato

ries

Mandels h statistics(Compost 1 - PBD 153)

Compost 1-PBD 153

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 153)Mandels h statistics(Sludge 1 - PBD 153)

Sample Sludge 1 Sludge 1 - PBD 153 -- Mean PARM = 0004 [mgkg]

Element PBD 153

General calcparmT1= 676738E-02T2= 267609E-04T3= 18T4= 68T5= 19626E-05

n= variabelp= 5

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00024 0000 4 -157 017 00024 00002 4 3 000

12L 00038 0002 4 006 154 00038 00018 4 3 00046L 00039 0000 4 011 026 00039 00003 4 3 00026L 00039 0000 2 018 004 00039 00000 2 1 00064L 00049 0002 4 122 159 00049 00018 4 3 000

Totgem 0004 0001 mgkg 1-level 172 (173) 5 00038 () 5 4Totstd= 0001 0001 5-level 157 (153)

RESULTS Mean = 000378 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000123 --gt 3252 r = 00034Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000142 --gt 3754 R = 00040Remarks none

000 050 100 150 200

k-values

4L

12L

46L

26L

64L

Mandels k statistics(Sludge 1 - PBD 153)

00 00 00 00 00 00 00

Deviation from Mean

4L

12L

46L

26L

64L

Labo

rato

ries

Sludge 1 - PBD 153 -- Mean PARM = 0004 [mgkg]

-200 -100 000 100 200

h-values

4L

12L

46L

26L

64L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 153)

Sludge 1-PBD 153

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 154)Mandels h statistics(Sludge 1 - PBD 154)

Sample Sludge 1 NA

Element PBD 154

General calcparmT1= NAT2= NAT3=T4=T5=

n= variabelp=

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00021 0000 3 -100 021 NA - 4L - - NA

46L 00025 0000 4 115 018 NA - 46L - - NA64L 00021 0001 4 -066 179 - - 64L - - NA12L 00023 0000 4 050 085 - - 12L - - NA

Totgem 0002 0000 mgkg 1-level 149 (167) NA (4L46L64L12L) -1Totstd= 0000 0000 5-level 142 (15) 4

RESULTS Mean = NA mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NAReproducibility var S2R = NAReproducibility std SR = NA --gt NA R = NARemarks 4 Labs rejected (4L46L64L12L)

000 050 100 150 200

k-values

4L

46L

64L

12L

Mandels k statistics(Sludge 1 - PBD 154)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

4L

46L

64L

12L

Labo

rato

ries

NA

-100 000 100 200

h-values

4L

46L

64L

12L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 154)

Sludge 1-PBD 154

Unit mgkg

Mandels k statistics(Soil 3 - PBD 154)Mandels h statistics(Soil 3 - PBD 154)

Sample Soil 3 NUM

Element PBD 154

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

4L 00010 - 1 150 Fail - - 4L - - NUM46L 00001 0000 4 -053 096 Fail - - 46L - - NUM64L 00001 0000 4 -056 105 Fail NUM - 64L - - NUM12L 00002 0000 4 -040 099 Fail - - 12L - - NUM

Totgem 000037 0000 mgkg 1-level 149 (164) NUM (4L46L64L12L) -1Totstd= 000042 0000 5-level 142 (153) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (4L46L64L12L)

000 050 100 150

k-values

4L

46L

64L

12L

Mandels k statistics(Soil 3 - PBD 154)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

4L

46L

64L

12L

Labo

rato

ries

NUM

-100 000 100 200

h-values

4L

46L

64L

12L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 154)

Soil 3-PBD 154

Unit mgkg

Mandels k statistics(Compost 1 - PBD 209)Mandels h statistics(Compost 1 - PBD 209)

Sample Compost 1 NUM

Element PBD 209

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00065 0003 2 -049 032 - - 4L - - NUM

44L 00573 0021 4 150 197 Fail - - 44L - - NUM12L 00078 0001 4 -045 011 - - 12L - - NUM26L 00049 0000 2 -056 000 NUM - 26L - - NUM

Totgem 0019 0006 mgkg 1-level 149 (177) NUM (4L44L12L26L) -1Totstd= 0025 0010 5-level 142 (159) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (4L44L12L26L)

000 050 100 150 200

k-values

4L

44L

12L

26L

Mandels k statistics(Compost 1 - PBD 209)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

4L

44L

12L

26L

Labo

rato

ries

NUM

-100 000 100 200

h-values

4L

44L

12L

26L

Labo

rato

ries

Mandels h statistics(Compost 1 - PBD 209)

Compost 1-PBD 209

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 209)Mandels h statistics(Sludge 1 - PBD 209)

Sample Sludge 1 Sludge 1 - PBD 209 -- Mean PARM = 0249 [mgkg]

Element PBD 209

General calcparmT1= 394542E+00T2= 107296E+00T3= 16T4= 56T5= 19723E-02

n= variabelp= 5

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 01550 0055 4 -112 148 Fail 01550 00551 4 3 -009

46L 02050 0007 2 -053 019 02050 00071 2 1 -00412L 02137 0058 4 -042 155 02137 00576 4 3 -00426L 03149 0021 2 078 057 Fail 03149 00210 2 1 00764L 03577 0007 4 129 020 Fail 03577 00074 4 3 011

Totgem 0249 0030 mgkg 1-level 172 (185) 5 02493 () 5 4Totstd= 0084 0025 5-level 157 (162)

RESULTS Mean = 024926 mgkg

Repeatability variance S2r = 000179Repeatability std Sr = 004234 --gt 1699 r = 01186Between lab variance S2L = 000743Reproducibility var S2R = 000922Reproducibility std SR = 009604 --gt 3853 R = 02689Remarks none

000 050 100 150 200

k-values

4L

46L

12L

26L

64L

Mandels k statistics(Sludge 1 - PBD 209)

-01 -01 00 01 01 02

Deviation from Mean

4L

46L

12L

26L

64L

Labo

rato

ries

Sludge 1 - PBD 209 -- Mean PARM = 0249 [mgkg]

-200 -100 000 100 200

h-values

4L

46L

12L

26L

64L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 209)

Sludge 1-PBD 209

Unit mgkg

Mandels k statistics(Soil 3 - PBD 209)Mandels h statistics(Soil 3 - PBD 209)

Sample Soil 3 Soil 3 - PBD 209 -- Mean PARM = 0258 [mgkg]

Element PBD 209

General calcparmT1= 596398E+00T2= 191917E+00T3= 22T4= 84T5= 13249E-02

n= variabelp= 6

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean26L 01162 0021 2 -108 074 Fail 01162 00207 2 1 -0144L 01303 0031 4 -097 111 Fail 01303 00312 4 3 -013

46L 01975 0036 4 -046 128 Fail 01975 00359 4 3 -00644L 02898 0035 4 024 124 Fail 02898 00346 4 3 00312L 03895 0018 4 100 065 Fail 03895 00181 4 3 01364L 04260 0022 4 127 078 Fail 04260 00219 4 3 017

Totgem 0258 0027 mgkg 1-level 187 (177) 6 02582 () 6 5Totstd= 0132 0008 5-level 166 (154)

RESULTS Mean = 025818 mgkg

Repeatability variance S2r = 000083Repeatability std Sr = 002878 --gt 1115 r = 00806Between lab variance S2L = 001640Reproducibility var S2R = 001723Reproducibility std SR = 013127 --gt 5084 R = 03676Remarks none

000 050 100 150

k-values

26L

4L

46L

44L

12L

64L

Mandels k statistics(Soil 3 - PBD 209)

-02 -01 -01 00 01 01 02 02

Deviation from Mean

26L

4L

46L

44L

12L

64L

Labo

rato

ries

Soil 3 - PBD 209 -- Mean PARM = 0258 [mgkg]

-200 -100 000 100 200

h-values

26L

4L

46L

44L

12L

64L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 209)

Soil 3-PBD 209

Unit mgkg

Mandels k statistics(Compost 1 - Sum PBD)Mandels h statistics(Compost 1 - Sum PBD)

Sample Compost 1 Compost 1 - Sum PBD -- Mean PARM = 0009 [mgkg]

Element Sum PBD

General calcparmT1= 154064E-01T2= 169065E-03T3= 18T4= 68T5= 11354E-04

n= variabelp= 5

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00031 0002 4 -067 016 00031 00016 4 3 -0014L 00055 0005 4 -056 048 00055 00047 4 3 000

46L 00085 0003 4 -042 031 00085 00030 4 3 00026L 00123 0000 2 -024 003 00123 00002 2 1 00012L 00154 0002 4 -011 021 00154 00021 4 3 00144L 00613 0023 4 200 237 Fail - - 44L - - 005

Totgem 0018 0006 mgkg 1-level 187 (177) 5 00089 (44L) 5 4Totstd= 0022 0009 5-level 166 (154) 1

RESULTS Mean = 000893 mgkg

Repeatability variance S2r = 000001Repeatability std Sr = 000296 --gt 3308 r = 00083Between lab variance S2L = 000002Reproducibility var S2R = 000003Reproducibility std SR = 000570 --gt 6374 R = 00159Remarks 1 Lab rejected (44L)

000 050 100 150 200 250

k-values

10L

4L

46L

26L

12L

44L

Mandels k statistics(Compost 1 - Sum PBD)

00 00 00 00 00 00 01 01

Deviation from Mean

10L

4L

46L

26L

12L

44L

Labo

rato

ries

Compost 1 - Sum PBD -- Mean PARM = 0009 [mgkg]

-100 000 100 200

h-values

10L

4L

46L

26L

12L

44L

Labo

rato

ries

Mandels h statistics(Compost 1 - Sum PBD)

Compost 1-Sum PBD

Unit mgkg

Mandels k statistics(Sludge 1 - Sum PBD)Mandels h statistics(Sludge 1 - Sum PBD)

Sample Sludge 1 Sludge 1 - Sum PBD -- Mean PARM = 0256 [mgkg]

Element Sum PBD

General calcparmT1= 531806E+00T2= 162188E+00T3= 22T4= 84T5= 25223E-02

n= variabelp= 6

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00423 0025 4 -156 044 Fail 00423 00252 4 3 -02146L 01808 0118 4 -049 205 - - 46L - - -0074L 01810 0056 4 -049 097 01810 00558 4 3 -007

38L 02168 0006 4 -022 010 02168 00059 4 3 -00412L 02890 0065 4 034 113 02890 00647 4 3 00364L 03958 0008 4 116 014 Fail 03958 00079 4 3 01426L 04094 0034 2 126 059 Fail 04094 00337 2 1 015

Totgem 0245 0044 mgkg 1-level 198 (179) 6 02557 (46L) 6 5Totstd= 0130 0039 5-level 171 (155) 1

RESULTS Mean = 025570 mgkg

Repeatability variance S2r = 000158Repeatability std Sr = 003970 --gt 1553 r = 01112Between lab variance S2L = 001807Reproducibility var S2R = 001964Reproducibility std SR = 014015 --gt 5481 R = 03924Remarks 1 Lab rejected (46L)

000 050 100 150 200 250

k-values

10L

46L

4L

38L

12L

64L

26L

Mandels k statistics(Sludge 1 - Sum PBD)

-03 -02 -02 -01 -01 00 01 01 02 02

Deviation from Mean

10L

46L

4L

38L

12L

64L

26L

Labo

rato

ries

Sludge 1 - Sum PBD -- Mean PARM = 0256 [mgkg]

-200 -100 000 100 200

h-values

10L

46L

4L

38L

12L

64L

26L

Labo

rato

ries

Mandels h statistics(Sludge 1 - Sum PBD)

Sludge 1-Sum PBD

Unit mgkg

Mandels k statistics(Soil 3 - Sum PBD)Mandels h statistics(Soil 3 - Sum PBD)

Sample Soil 3 Soil 3 - Sum PBD -- Mean PARM = 0227 [mgkg]

Element Sum PBD

General calcparmT1= 610980E+00T2= 200876E+00T3= 26T4= 100T5= 13106E-02

n= variabelp= 7

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00028 0001 4 -037 000 Fail 00028 00005 4 3 -02226L 01179 0021 2 -036 003 Fail 01179 00208 2 1 -0114L 01305 0031 4 -036 004 Fail 01305 00308 4 3 -010

46L 02065 0035 4 -036 005 Fail 02065 00350 4 3 -00244L 02923 0037 4 -035 005 Fail 02923 00365 4 3 00712L 04051 0015 4 -034 002 Fail 04051 00149 4 3 01864L 04314 0022 4 -033 003 Fail 04314 00223 4 3 0203L 305500 2051 2 247 283 Fail - - 3L - - 3032

Totgem 4017 0276 mgkg 1-level 206 (181) 7 02266 (3L) 7 6Totstd= 10722 0717 5-level 175 (156) 1

RESULTS Mean = 022663 mgkg

Repeatability variance S2r = 000069Repeatability std Sr = 002626 --gt 1159 r = 00735Between lab variance S2L = 002568Reproducibility var S2R = 002637Reproducibility std SR = 016238 --gt 7165 R = 04547Remarks 1 Lab rejected (3L)

000 050 100 150 200 250 300

k-values

10L

26L

4L

46L

44L

12L

64L

3L

Mandels k statistics(Soil 3 - Sum PBD)

-50 00 50 100 150 200 250 300 350

Deviation from Mean

10L

26L

4L

46L

44L

12L

64L

3L

Labo

rato

ries

Soil 3 - Sum PBD -- Mean PARM = 0227 [mgkg]

-100 000 100 200 300

h-values

10L

26L

4L

46L

44L

12L

64L

3L

Labo

rato

ries

Mandels h statistics(Soil 3 - Sum PBD)

Soil 3-Sum PBD

19

Annex 4

Raw data submitted

Sample Compost1 Sample Compost 1 Sample Compost 1Element PBD 99 Element PBD 100 Element PBD 153

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]4L 00021 10L 00008 44L 000504L 00024 10L 00008 44L 000604L 00014 10L 00007 44L 000504L 00020 10L 00011 46L 00004

10L 00029 46L 00007 46L 0001210L 00027 46L 00012 46L 0000410L 00032 46L 00009 46L 0000946L 00025 46L 00007 12L 0000446L 00052 12L 00008 12L 0000846L 00029 12L 00012 12L 0000446L 00026 12L 00008 12L 0000712L 00026 12L 00014 26L 0000512L 00043 26L 00007 26L 0000512L 00026 26L 0000612L 0004726L 0002626L 00024

Sample Compost 1 Sample Compost 1 Sample Compost 1Element PBD 154 Element PBD 183 Element PBD 196

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]4L 00010 46L 00002 46L 00011

46L 00003 46L 00024 46L 0000846L 00007 46L 00021 12L 0000246L 00003 46L 00003 12L 0000346L 00004 12L 00003 12L 0000112L 00003 12L 00011 12L 0000212L 00005 12L 0000312L 00031 12L 0000312L 00006

Sample Compost 1 Sample Compost 1 Sample Compost 1Element PBD 197 Element PBD 203 Element PBD 209

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00002 46L 00010 4L 0004146L 00023 12L 00002 4L 0008946L 00022 12L 00003 44L 0041012L 00004 12L 00002 44L 0084012L 00006 12L 00002 44L 0064012L 00003 44L 0040012L 00004 12L 00079

12L 0007312L 0006512L 0009326L 0004926L 00049

Sample Compost 1Element PBD 47

LAB PARM [mgkg]26L 0003826L 00039

Element PBD 99 Element PBD 47 Element PBD 209LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]

4L 00170 10L 00210 4L 010004L 00200 10L 00220 4L 018004L 00170 10L 00210 4L 012004L 00190 46L 00300 4L 0220010L 00280 46L 00280 46L 0210010L 00300 46L 00250 46L 0200010L 00290 46L 00260 64L 0351846L 00340 64L 00059 64L 0363846L 00330 64L 00057 64L 0364546L 00300 64L 00062 64L 0350846L 00310 64L 00060 12L 0220964L 00194 12L 00191 12L 0177164L 00154 12L 00187 12L 0292264L 00185 12L 00190 12L 0164664L 00159 12L 00186 26L 0329712L 00242 26L 00666 26L 0300012L 00223 26L 0033212L 0022112L 0022226L 0024626L 00400

Element PBD 203 Element PBD 197 Element PBD 196LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00022 46L 00027 46L 0002446L 00014 46L 00024 46L 0002264L 00036 12L 00161 64L 0005864L 00058 12L 00060 64L 0006512L 00063 12L 00061 12L 0004812L 00034 12L 00036 12L 0002512L 00038 12L 0003212L 00027 12L 00022

Element PBD 183 Element PBD 154 Element PBD 153LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00049 4L 00020 4L 0002246L 00035 4L 00022 4L 0002446L 00036 4L 00020 4L 0002246L 00034 46L 00025 4L 0002664L 00027 46L 00025 46L 0004064L 00023 46L 00025 46L 0004264L 00024 46L 00023 46L 0003564L 00020 64L 00034 46L 0003812L 00230 64L 00023 64L 0007412L 00032 64L 00017 64L 0004712L 00031 64L 00011 64L 0004612L 00030 12L 00030 64L 0003026L 00007 12L 00021 12L 0006526L 00008 12L 00021 12L 00029

12L 00021 12L 0003226L 00015 12L 0002926L 00019 26L 00039

26L 00040

Element PBD 100LAB PARM [mgkg]

4L 000384L 000414L 000374L 00038

38L 0219038L 0220038L 0208038L 0220010L 0004410L 0005010L 0004310L 0004646L 0005746L 0005946L 0005346L 0005312L 0004312L 0004512L 0004312L 0004326L 0006226L 00057

Sample Soil 3 Sample Soil 3 Sample Soil 3Element PBD 99 Element PBD 47 Element PBD 100

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]10L 00016 10L 00011 10L 0000310L 00019 10L 00010 10L 0000410L 00013 10L 00012 10L 0000410L 00019 46L 00007 10L 0000246L 00025 46L 00022 46L 0000246L 00025 46L 00005 46L 0000646L 00008 46L 00007 46L 0000246L 00011 12L 00010 46L 0000264L 00005 12L 00017 3L 29100064L 00005 12L 00010 3L 32000064L 00006 12L 00009 26L 0000564L 00007 26L 00007 26L 0000512L 00012 26L 0000712L 0001312L 0001312L 0001226L 0000526L 00006

Sample Soil 3 Sample Soil 3 Sample Soil 3Element PBD 153 Element PBD 154 Element PBD 196

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]44L 00050 4L 00010 46L 0000744L 00050 46L 00001 46L 0001146L 00002 46L 00002 46L 0000846L 00003 46L 00001 46L 0001146L 00002 46L 00002 64L 0002646L 00002 64L 00001 64L 0002664L 00001 64L 00001 64L 0002964L 00001 64L 00001 64L 0003464L 00001 64L 00002 12L 0004564L 00002 12L 00003 12L 00032

12L 00002 12L 0002212L 00002 12L 0002112L 00002

Sample Soil 3 Sample Soil 3 Sample Soil 3Element PBD 197 Element PBD 203 Element PBD 209

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00006 46L 00011 4L 0091046L 00013 46L 00017 4L 0150046L 00011 46L 00015 4L 0120046L 00013 46L 00018 4L 0160012L 00090 64L 00013 44L 0337012L 00056 64L 00014 44L 0281012L 00033 64L 00016 44L 0287012L 00032 64L 00015 44L 02540

12L 00055 46L 0230012L 00041 46L 0220012L 00027 46L 0150012L 00026 46L 01900

64L 0438164L 0401664L 0414464L 0449812L 0367112L 0397812L 0409112L 03838

Sample Soil 3 26L 0102Element PBD 183 26L 0131

LAB PARM [mgkg]46L 0000746L 0000846L 0005846L 0000764L 0000264L 0000364L 0000364L 0000312L 0001512L 0001112L 0000712L 00007

European Commission EUR 23003 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on polybrominated diphenylethers Author(s) E Sobiecka H van der Sloot D Barcelo B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 68 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07403-5 Abstract Project HORIZONTAL is interdisciplinary aiming at a harmonisation and horizontal standardisation of test procedures in particular for sludge soils and biowastes In the context of this standardization project a series of draft technical specification were designed upon an extensive desk study fine-tuned after expert consultations and finally validated in international intercomparisons exercise This report summarises the work performed within the validation study of the draft standard for the determination of polybrominated diphenylethers (PBDE) in soils sludge and treated bio-waste using gas-chromatography method with mass selective detection (GC-MS) It further explains the underlying statistical concept for the calculation of reproducibility and repeatability from intercomparisons data In addition all single values results of the statistical evaluation as well as background information on the validation materials used are described and explained

The mission of the JRC is to provide customer-driven scientific and technical support for the conception development implementation and monitoring of EU policies As a service of the European Commission the JRC functions as a reference centre of science and technology for the Union Close to the policy-making process it serves the common interest of the Member States while being independent of special interests whether private or national

LB

-NA

-23003-EN

-C

Unit mgkg

Mandels k statistics(Compost 1 - PBD 153)Mandels h statistics(Compost 1 - PBD 153)

Sample Compost 1 NUM

Element PBD 153

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean44L 00053 0001 3 150 157 Fail - - 44L - - NUM46L 00007 0000 4 -044 111 Fail - - 46L - - NUM12L 00005 0000 4 -051 055 Fail - - 12L - - NUM26L 00005 0000 2 -054 001 Fail NUM - 26L - - NUM

Totgem 0002 0000 mgkg 1-level 149 (177) NUM (44L46L12L26L) -1Totstd= 0002 0000 5-level 142 (159) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (44L46L12L26L)

000 050 100 150 200

k-values

44L

46L

12L

26L

Mandels k statistics(Compost 1 - PBD 153)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

44L

46L

12L

26L

Labo

rato

ries

NUM

-100 000 100 200

h-values

44L

46L

12L

26L

Labo

rato

ries

Mandels h statistics(Compost 1 - PBD 153)

Compost 1-PBD 153

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 153)Mandels h statistics(Sludge 1 - PBD 153)

Sample Sludge 1 Sludge 1 - PBD 153 -- Mean PARM = 0004 [mgkg]

Element PBD 153

General calcparmT1= 676738E-02T2= 267609E-04T3= 18T4= 68T5= 19626E-05

n= variabelp= 5

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00024 0000 4 -157 017 00024 00002 4 3 000

12L 00038 0002 4 006 154 00038 00018 4 3 00046L 00039 0000 4 011 026 00039 00003 4 3 00026L 00039 0000 2 018 004 00039 00000 2 1 00064L 00049 0002 4 122 159 00049 00018 4 3 000

Totgem 0004 0001 mgkg 1-level 172 (173) 5 00038 () 5 4Totstd= 0001 0001 5-level 157 (153)

RESULTS Mean = 000378 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000123 --gt 3252 r = 00034Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000142 --gt 3754 R = 00040Remarks none

000 050 100 150 200

k-values

4L

12L

46L

26L

64L

Mandels k statistics(Sludge 1 - PBD 153)

00 00 00 00 00 00 00

Deviation from Mean

4L

12L

46L

26L

64L

Labo

rato

ries

Sludge 1 - PBD 153 -- Mean PARM = 0004 [mgkg]

-200 -100 000 100 200

h-values

4L

12L

46L

26L

64L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 153)

Sludge 1-PBD 153

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 154)Mandels h statistics(Sludge 1 - PBD 154)

Sample Sludge 1 NA

Element PBD 154

General calcparmT1= NAT2= NAT3=T4=T5=

n= variabelp=

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00021 0000 3 -100 021 NA - 4L - - NA

46L 00025 0000 4 115 018 NA - 46L - - NA64L 00021 0001 4 -066 179 - - 64L - - NA12L 00023 0000 4 050 085 - - 12L - - NA

Totgem 0002 0000 mgkg 1-level 149 (167) NA (4L46L64L12L) -1Totstd= 0000 0000 5-level 142 (15) 4

RESULTS Mean = NA mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NAReproducibility var S2R = NAReproducibility std SR = NA --gt NA R = NARemarks 4 Labs rejected (4L46L64L12L)

000 050 100 150 200

k-values

4L

46L

64L

12L

Mandels k statistics(Sludge 1 - PBD 154)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

4L

46L

64L

12L

Labo

rato

ries

NA

-100 000 100 200

h-values

4L

46L

64L

12L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 154)

Sludge 1-PBD 154

Unit mgkg

Mandels k statistics(Soil 3 - PBD 154)Mandels h statistics(Soil 3 - PBD 154)

Sample Soil 3 NUM

Element PBD 154

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

4L 00010 - 1 150 Fail - - 4L - - NUM46L 00001 0000 4 -053 096 Fail - - 46L - - NUM64L 00001 0000 4 -056 105 Fail NUM - 64L - - NUM12L 00002 0000 4 -040 099 Fail - - 12L - - NUM

Totgem 000037 0000 mgkg 1-level 149 (164) NUM (4L46L64L12L) -1Totstd= 000042 0000 5-level 142 (153) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (4L46L64L12L)

000 050 100 150

k-values

4L

46L

64L

12L

Mandels k statistics(Soil 3 - PBD 154)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

4L

46L

64L

12L

Labo

rato

ries

NUM

-100 000 100 200

h-values

4L

46L

64L

12L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 154)

Soil 3-PBD 154

Unit mgkg

Mandels k statistics(Compost 1 - PBD 209)Mandels h statistics(Compost 1 - PBD 209)

Sample Compost 1 NUM

Element PBD 209

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00065 0003 2 -049 032 - - 4L - - NUM

44L 00573 0021 4 150 197 Fail - - 44L - - NUM12L 00078 0001 4 -045 011 - - 12L - - NUM26L 00049 0000 2 -056 000 NUM - 26L - - NUM

Totgem 0019 0006 mgkg 1-level 149 (177) NUM (4L44L12L26L) -1Totstd= 0025 0010 5-level 142 (159) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (4L44L12L26L)

000 050 100 150 200

k-values

4L

44L

12L

26L

Mandels k statistics(Compost 1 - PBD 209)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

4L

44L

12L

26L

Labo

rato

ries

NUM

-100 000 100 200

h-values

4L

44L

12L

26L

Labo

rato

ries

Mandels h statistics(Compost 1 - PBD 209)

Compost 1-PBD 209

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 209)Mandels h statistics(Sludge 1 - PBD 209)

Sample Sludge 1 Sludge 1 - PBD 209 -- Mean PARM = 0249 [mgkg]

Element PBD 209

General calcparmT1= 394542E+00T2= 107296E+00T3= 16T4= 56T5= 19723E-02

n= variabelp= 5

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 01550 0055 4 -112 148 Fail 01550 00551 4 3 -009

46L 02050 0007 2 -053 019 02050 00071 2 1 -00412L 02137 0058 4 -042 155 02137 00576 4 3 -00426L 03149 0021 2 078 057 Fail 03149 00210 2 1 00764L 03577 0007 4 129 020 Fail 03577 00074 4 3 011

Totgem 0249 0030 mgkg 1-level 172 (185) 5 02493 () 5 4Totstd= 0084 0025 5-level 157 (162)

RESULTS Mean = 024926 mgkg

Repeatability variance S2r = 000179Repeatability std Sr = 004234 --gt 1699 r = 01186Between lab variance S2L = 000743Reproducibility var S2R = 000922Reproducibility std SR = 009604 --gt 3853 R = 02689Remarks none

000 050 100 150 200

k-values

4L

46L

12L

26L

64L

Mandels k statistics(Sludge 1 - PBD 209)

-01 -01 00 01 01 02

Deviation from Mean

4L

46L

12L

26L

64L

Labo

rato

ries

Sludge 1 - PBD 209 -- Mean PARM = 0249 [mgkg]

-200 -100 000 100 200

h-values

4L

46L

12L

26L

64L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 209)

Sludge 1-PBD 209

Unit mgkg

Mandels k statistics(Soil 3 - PBD 209)Mandels h statistics(Soil 3 - PBD 209)

Sample Soil 3 Soil 3 - PBD 209 -- Mean PARM = 0258 [mgkg]

Element PBD 209

General calcparmT1= 596398E+00T2= 191917E+00T3= 22T4= 84T5= 13249E-02

n= variabelp= 6

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean26L 01162 0021 2 -108 074 Fail 01162 00207 2 1 -0144L 01303 0031 4 -097 111 Fail 01303 00312 4 3 -013

46L 01975 0036 4 -046 128 Fail 01975 00359 4 3 -00644L 02898 0035 4 024 124 Fail 02898 00346 4 3 00312L 03895 0018 4 100 065 Fail 03895 00181 4 3 01364L 04260 0022 4 127 078 Fail 04260 00219 4 3 017

Totgem 0258 0027 mgkg 1-level 187 (177) 6 02582 () 6 5Totstd= 0132 0008 5-level 166 (154)

RESULTS Mean = 025818 mgkg

Repeatability variance S2r = 000083Repeatability std Sr = 002878 --gt 1115 r = 00806Between lab variance S2L = 001640Reproducibility var S2R = 001723Reproducibility std SR = 013127 --gt 5084 R = 03676Remarks none

000 050 100 150

k-values

26L

4L

46L

44L

12L

64L

Mandels k statistics(Soil 3 - PBD 209)

-02 -01 -01 00 01 01 02 02

Deviation from Mean

26L

4L

46L

44L

12L

64L

Labo

rato

ries

Soil 3 - PBD 209 -- Mean PARM = 0258 [mgkg]

-200 -100 000 100 200

h-values

26L

4L

46L

44L

12L

64L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 209)

Soil 3-PBD 209

Unit mgkg

Mandels k statistics(Compost 1 - Sum PBD)Mandels h statistics(Compost 1 - Sum PBD)

Sample Compost 1 Compost 1 - Sum PBD -- Mean PARM = 0009 [mgkg]

Element Sum PBD

General calcparmT1= 154064E-01T2= 169065E-03T3= 18T4= 68T5= 11354E-04

n= variabelp= 5

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00031 0002 4 -067 016 00031 00016 4 3 -0014L 00055 0005 4 -056 048 00055 00047 4 3 000

46L 00085 0003 4 -042 031 00085 00030 4 3 00026L 00123 0000 2 -024 003 00123 00002 2 1 00012L 00154 0002 4 -011 021 00154 00021 4 3 00144L 00613 0023 4 200 237 Fail - - 44L - - 005

Totgem 0018 0006 mgkg 1-level 187 (177) 5 00089 (44L) 5 4Totstd= 0022 0009 5-level 166 (154) 1

RESULTS Mean = 000893 mgkg

Repeatability variance S2r = 000001Repeatability std Sr = 000296 --gt 3308 r = 00083Between lab variance S2L = 000002Reproducibility var S2R = 000003Reproducibility std SR = 000570 --gt 6374 R = 00159Remarks 1 Lab rejected (44L)

000 050 100 150 200 250

k-values

10L

4L

46L

26L

12L

44L

Mandels k statistics(Compost 1 - Sum PBD)

00 00 00 00 00 00 01 01

Deviation from Mean

10L

4L

46L

26L

12L

44L

Labo

rato

ries

Compost 1 - Sum PBD -- Mean PARM = 0009 [mgkg]

-100 000 100 200

h-values

10L

4L

46L

26L

12L

44L

Labo

rato

ries

Mandels h statistics(Compost 1 - Sum PBD)

Compost 1-Sum PBD

Unit mgkg

Mandels k statistics(Sludge 1 - Sum PBD)Mandels h statistics(Sludge 1 - Sum PBD)

Sample Sludge 1 Sludge 1 - Sum PBD -- Mean PARM = 0256 [mgkg]

Element Sum PBD

General calcparmT1= 531806E+00T2= 162188E+00T3= 22T4= 84T5= 25223E-02

n= variabelp= 6

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00423 0025 4 -156 044 Fail 00423 00252 4 3 -02146L 01808 0118 4 -049 205 - - 46L - - -0074L 01810 0056 4 -049 097 01810 00558 4 3 -007

38L 02168 0006 4 -022 010 02168 00059 4 3 -00412L 02890 0065 4 034 113 02890 00647 4 3 00364L 03958 0008 4 116 014 Fail 03958 00079 4 3 01426L 04094 0034 2 126 059 Fail 04094 00337 2 1 015

Totgem 0245 0044 mgkg 1-level 198 (179) 6 02557 (46L) 6 5Totstd= 0130 0039 5-level 171 (155) 1

RESULTS Mean = 025570 mgkg

Repeatability variance S2r = 000158Repeatability std Sr = 003970 --gt 1553 r = 01112Between lab variance S2L = 001807Reproducibility var S2R = 001964Reproducibility std SR = 014015 --gt 5481 R = 03924Remarks 1 Lab rejected (46L)

000 050 100 150 200 250

k-values

10L

46L

4L

38L

12L

64L

26L

Mandels k statistics(Sludge 1 - Sum PBD)

-03 -02 -02 -01 -01 00 01 01 02 02

Deviation from Mean

10L

46L

4L

38L

12L

64L

26L

Labo

rato

ries

Sludge 1 - Sum PBD -- Mean PARM = 0256 [mgkg]

-200 -100 000 100 200

h-values

10L

46L

4L

38L

12L

64L

26L

Labo

rato

ries

Mandels h statistics(Sludge 1 - Sum PBD)

Sludge 1-Sum PBD

Unit mgkg

Mandels k statistics(Soil 3 - Sum PBD)Mandels h statistics(Soil 3 - Sum PBD)

Sample Soil 3 Soil 3 - Sum PBD -- Mean PARM = 0227 [mgkg]

Element Sum PBD

General calcparmT1= 610980E+00T2= 200876E+00T3= 26T4= 100T5= 13106E-02

n= variabelp= 7

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00028 0001 4 -037 000 Fail 00028 00005 4 3 -02226L 01179 0021 2 -036 003 Fail 01179 00208 2 1 -0114L 01305 0031 4 -036 004 Fail 01305 00308 4 3 -010

46L 02065 0035 4 -036 005 Fail 02065 00350 4 3 -00244L 02923 0037 4 -035 005 Fail 02923 00365 4 3 00712L 04051 0015 4 -034 002 Fail 04051 00149 4 3 01864L 04314 0022 4 -033 003 Fail 04314 00223 4 3 0203L 305500 2051 2 247 283 Fail - - 3L - - 3032

Totgem 4017 0276 mgkg 1-level 206 (181) 7 02266 (3L) 7 6Totstd= 10722 0717 5-level 175 (156) 1

RESULTS Mean = 022663 mgkg

Repeatability variance S2r = 000069Repeatability std Sr = 002626 --gt 1159 r = 00735Between lab variance S2L = 002568Reproducibility var S2R = 002637Reproducibility std SR = 016238 --gt 7165 R = 04547Remarks 1 Lab rejected (3L)

000 050 100 150 200 250 300

k-values

10L

26L

4L

46L

44L

12L

64L

3L

Mandels k statistics(Soil 3 - Sum PBD)

-50 00 50 100 150 200 250 300 350

Deviation from Mean

10L

26L

4L

46L

44L

12L

64L

3L

Labo

rato

ries

Soil 3 - Sum PBD -- Mean PARM = 0227 [mgkg]

-100 000 100 200 300

h-values

10L

26L

4L

46L

44L

12L

64L

3L

Labo

rato

ries

Mandels h statistics(Soil 3 - Sum PBD)

Soil 3-Sum PBD

19

Annex 4

Raw data submitted

Sample Compost1 Sample Compost 1 Sample Compost 1Element PBD 99 Element PBD 100 Element PBD 153

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]4L 00021 10L 00008 44L 000504L 00024 10L 00008 44L 000604L 00014 10L 00007 44L 000504L 00020 10L 00011 46L 00004

10L 00029 46L 00007 46L 0001210L 00027 46L 00012 46L 0000410L 00032 46L 00009 46L 0000946L 00025 46L 00007 12L 0000446L 00052 12L 00008 12L 0000846L 00029 12L 00012 12L 0000446L 00026 12L 00008 12L 0000712L 00026 12L 00014 26L 0000512L 00043 26L 00007 26L 0000512L 00026 26L 0000612L 0004726L 0002626L 00024

Sample Compost 1 Sample Compost 1 Sample Compost 1Element PBD 154 Element PBD 183 Element PBD 196

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]4L 00010 46L 00002 46L 00011

46L 00003 46L 00024 46L 0000846L 00007 46L 00021 12L 0000246L 00003 46L 00003 12L 0000346L 00004 12L 00003 12L 0000112L 00003 12L 00011 12L 0000212L 00005 12L 0000312L 00031 12L 0000312L 00006

Sample Compost 1 Sample Compost 1 Sample Compost 1Element PBD 197 Element PBD 203 Element PBD 209

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00002 46L 00010 4L 0004146L 00023 12L 00002 4L 0008946L 00022 12L 00003 44L 0041012L 00004 12L 00002 44L 0084012L 00006 12L 00002 44L 0064012L 00003 44L 0040012L 00004 12L 00079

12L 0007312L 0006512L 0009326L 0004926L 00049

Sample Compost 1Element PBD 47

LAB PARM [mgkg]26L 0003826L 00039

Element PBD 99 Element PBD 47 Element PBD 209LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]

4L 00170 10L 00210 4L 010004L 00200 10L 00220 4L 018004L 00170 10L 00210 4L 012004L 00190 46L 00300 4L 0220010L 00280 46L 00280 46L 0210010L 00300 46L 00250 46L 0200010L 00290 46L 00260 64L 0351846L 00340 64L 00059 64L 0363846L 00330 64L 00057 64L 0364546L 00300 64L 00062 64L 0350846L 00310 64L 00060 12L 0220964L 00194 12L 00191 12L 0177164L 00154 12L 00187 12L 0292264L 00185 12L 00190 12L 0164664L 00159 12L 00186 26L 0329712L 00242 26L 00666 26L 0300012L 00223 26L 0033212L 0022112L 0022226L 0024626L 00400

Element PBD 203 Element PBD 197 Element PBD 196LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00022 46L 00027 46L 0002446L 00014 46L 00024 46L 0002264L 00036 12L 00161 64L 0005864L 00058 12L 00060 64L 0006512L 00063 12L 00061 12L 0004812L 00034 12L 00036 12L 0002512L 00038 12L 0003212L 00027 12L 00022

Element PBD 183 Element PBD 154 Element PBD 153LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00049 4L 00020 4L 0002246L 00035 4L 00022 4L 0002446L 00036 4L 00020 4L 0002246L 00034 46L 00025 4L 0002664L 00027 46L 00025 46L 0004064L 00023 46L 00025 46L 0004264L 00024 46L 00023 46L 0003564L 00020 64L 00034 46L 0003812L 00230 64L 00023 64L 0007412L 00032 64L 00017 64L 0004712L 00031 64L 00011 64L 0004612L 00030 12L 00030 64L 0003026L 00007 12L 00021 12L 0006526L 00008 12L 00021 12L 00029

12L 00021 12L 0003226L 00015 12L 0002926L 00019 26L 00039

26L 00040

Element PBD 100LAB PARM [mgkg]

4L 000384L 000414L 000374L 00038

38L 0219038L 0220038L 0208038L 0220010L 0004410L 0005010L 0004310L 0004646L 0005746L 0005946L 0005346L 0005312L 0004312L 0004512L 0004312L 0004326L 0006226L 00057

Sample Soil 3 Sample Soil 3 Sample Soil 3Element PBD 99 Element PBD 47 Element PBD 100

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]10L 00016 10L 00011 10L 0000310L 00019 10L 00010 10L 0000410L 00013 10L 00012 10L 0000410L 00019 46L 00007 10L 0000246L 00025 46L 00022 46L 0000246L 00025 46L 00005 46L 0000646L 00008 46L 00007 46L 0000246L 00011 12L 00010 46L 0000264L 00005 12L 00017 3L 29100064L 00005 12L 00010 3L 32000064L 00006 12L 00009 26L 0000564L 00007 26L 00007 26L 0000512L 00012 26L 0000712L 0001312L 0001312L 0001226L 0000526L 00006

Sample Soil 3 Sample Soil 3 Sample Soil 3Element PBD 153 Element PBD 154 Element PBD 196

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]44L 00050 4L 00010 46L 0000744L 00050 46L 00001 46L 0001146L 00002 46L 00002 46L 0000846L 00003 46L 00001 46L 0001146L 00002 46L 00002 64L 0002646L 00002 64L 00001 64L 0002664L 00001 64L 00001 64L 0002964L 00001 64L 00001 64L 0003464L 00001 64L 00002 12L 0004564L 00002 12L 00003 12L 00032

12L 00002 12L 0002212L 00002 12L 0002112L 00002

Sample Soil 3 Sample Soil 3 Sample Soil 3Element PBD 197 Element PBD 203 Element PBD 209

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00006 46L 00011 4L 0091046L 00013 46L 00017 4L 0150046L 00011 46L 00015 4L 0120046L 00013 46L 00018 4L 0160012L 00090 64L 00013 44L 0337012L 00056 64L 00014 44L 0281012L 00033 64L 00016 44L 0287012L 00032 64L 00015 44L 02540

12L 00055 46L 0230012L 00041 46L 0220012L 00027 46L 0150012L 00026 46L 01900

64L 0438164L 0401664L 0414464L 0449812L 0367112L 0397812L 0409112L 03838

Sample Soil 3 26L 0102Element PBD 183 26L 0131

LAB PARM [mgkg]46L 0000746L 0000846L 0005846L 0000764L 0000264L 0000364L 0000364L 0000312L 0001512L 0001112L 0000712L 00007

European Commission EUR 23003 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on polybrominated diphenylethers Author(s) E Sobiecka H van der Sloot D Barcelo B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 68 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07403-5 Abstract Project HORIZONTAL is interdisciplinary aiming at a harmonisation and horizontal standardisation of test procedures in particular for sludge soils and biowastes In the context of this standardization project a series of draft technical specification were designed upon an extensive desk study fine-tuned after expert consultations and finally validated in international intercomparisons exercise This report summarises the work performed within the validation study of the draft standard for the determination of polybrominated diphenylethers (PBDE) in soils sludge and treated bio-waste using gas-chromatography method with mass selective detection (GC-MS) It further explains the underlying statistical concept for the calculation of reproducibility and repeatability from intercomparisons data In addition all single values results of the statistical evaluation as well as background information on the validation materials used are described and explained

The mission of the JRC is to provide customer-driven scientific and technical support for the conception development implementation and monitoring of EU policies As a service of the European Commission the JRC functions as a reference centre of science and technology for the Union Close to the policy-making process it serves the common interest of the Member States while being independent of special interests whether private or national

LB

-NA

-23003-EN

-C

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 153)Mandels h statistics(Sludge 1 - PBD 153)

Sample Sludge 1 Sludge 1 - PBD 153 -- Mean PARM = 0004 [mgkg]

Element PBD 153

General calcparmT1= 676738E-02T2= 267609E-04T3= 18T4= 68T5= 19626E-05

n= variabelp= 5

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00024 0000 4 -157 017 00024 00002 4 3 000

12L 00038 0002 4 006 154 00038 00018 4 3 00046L 00039 0000 4 011 026 00039 00003 4 3 00026L 00039 0000 2 018 004 00039 00000 2 1 00064L 00049 0002 4 122 159 00049 00018 4 3 000

Totgem 0004 0001 mgkg 1-level 172 (173) 5 00038 () 5 4Totstd= 0001 0001 5-level 157 (153)

RESULTS Mean = 000378 mgkg

Repeatability variance S2r = 000000Repeatability std Sr = 000123 --gt 3252 r = 00034Between lab variance S2L = 000000Reproducibility var S2R = 000000Reproducibility std SR = 000142 --gt 3754 R = 00040Remarks none

000 050 100 150 200

k-values

4L

12L

46L

26L

64L

Mandels k statistics(Sludge 1 - PBD 153)

00 00 00 00 00 00 00

Deviation from Mean

4L

12L

46L

26L

64L

Labo

rato

ries

Sludge 1 - PBD 153 -- Mean PARM = 0004 [mgkg]

-200 -100 000 100 200

h-values

4L

12L

46L

26L

64L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 153)

Sludge 1-PBD 153

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 154)Mandels h statistics(Sludge 1 - PBD 154)

Sample Sludge 1 NA

Element PBD 154

General calcparmT1= NAT2= NAT3=T4=T5=

n= variabelp=

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00021 0000 3 -100 021 NA - 4L - - NA

46L 00025 0000 4 115 018 NA - 46L - - NA64L 00021 0001 4 -066 179 - - 64L - - NA12L 00023 0000 4 050 085 - - 12L - - NA

Totgem 0002 0000 mgkg 1-level 149 (167) NA (4L46L64L12L) -1Totstd= 0000 0000 5-level 142 (15) 4

RESULTS Mean = NA mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NAReproducibility var S2R = NAReproducibility std SR = NA --gt NA R = NARemarks 4 Labs rejected (4L46L64L12L)

000 050 100 150 200

k-values

4L

46L

64L

12L

Mandels k statistics(Sludge 1 - PBD 154)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

4L

46L

64L

12L

Labo

rato

ries

NA

-100 000 100 200

h-values

4L

46L

64L

12L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 154)

Sludge 1-PBD 154

Unit mgkg

Mandels k statistics(Soil 3 - PBD 154)Mandels h statistics(Soil 3 - PBD 154)

Sample Soil 3 NUM

Element PBD 154

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

4L 00010 - 1 150 Fail - - 4L - - NUM46L 00001 0000 4 -053 096 Fail - - 46L - - NUM64L 00001 0000 4 -056 105 Fail NUM - 64L - - NUM12L 00002 0000 4 -040 099 Fail - - 12L - - NUM

Totgem 000037 0000 mgkg 1-level 149 (164) NUM (4L46L64L12L) -1Totstd= 000042 0000 5-level 142 (153) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (4L46L64L12L)

000 050 100 150

k-values

4L

46L

64L

12L

Mandels k statistics(Soil 3 - PBD 154)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

4L

46L

64L

12L

Labo

rato

ries

NUM

-100 000 100 200

h-values

4L

46L

64L

12L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 154)

Soil 3-PBD 154

Unit mgkg

Mandels k statistics(Compost 1 - PBD 209)Mandels h statistics(Compost 1 - PBD 209)

Sample Compost 1 NUM

Element PBD 209

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00065 0003 2 -049 032 - - 4L - - NUM

44L 00573 0021 4 150 197 Fail - - 44L - - NUM12L 00078 0001 4 -045 011 - - 12L - - NUM26L 00049 0000 2 -056 000 NUM - 26L - - NUM

Totgem 0019 0006 mgkg 1-level 149 (177) NUM (4L44L12L26L) -1Totstd= 0025 0010 5-level 142 (159) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (4L44L12L26L)

000 050 100 150 200

k-values

4L

44L

12L

26L

Mandels k statistics(Compost 1 - PBD 209)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

4L

44L

12L

26L

Labo

rato

ries

NUM

-100 000 100 200

h-values

4L

44L

12L

26L

Labo

rato

ries

Mandels h statistics(Compost 1 - PBD 209)

Compost 1-PBD 209

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 209)Mandels h statistics(Sludge 1 - PBD 209)

Sample Sludge 1 Sludge 1 - PBD 209 -- Mean PARM = 0249 [mgkg]

Element PBD 209

General calcparmT1= 394542E+00T2= 107296E+00T3= 16T4= 56T5= 19723E-02

n= variabelp= 5

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 01550 0055 4 -112 148 Fail 01550 00551 4 3 -009

46L 02050 0007 2 -053 019 02050 00071 2 1 -00412L 02137 0058 4 -042 155 02137 00576 4 3 -00426L 03149 0021 2 078 057 Fail 03149 00210 2 1 00764L 03577 0007 4 129 020 Fail 03577 00074 4 3 011

Totgem 0249 0030 mgkg 1-level 172 (185) 5 02493 () 5 4Totstd= 0084 0025 5-level 157 (162)

RESULTS Mean = 024926 mgkg

Repeatability variance S2r = 000179Repeatability std Sr = 004234 --gt 1699 r = 01186Between lab variance S2L = 000743Reproducibility var S2R = 000922Reproducibility std SR = 009604 --gt 3853 R = 02689Remarks none

000 050 100 150 200

k-values

4L

46L

12L

26L

64L

Mandels k statistics(Sludge 1 - PBD 209)

-01 -01 00 01 01 02

Deviation from Mean

4L

46L

12L

26L

64L

Labo

rato

ries

Sludge 1 - PBD 209 -- Mean PARM = 0249 [mgkg]

-200 -100 000 100 200

h-values

4L

46L

12L

26L

64L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 209)

Sludge 1-PBD 209

Unit mgkg

Mandels k statistics(Soil 3 - PBD 209)Mandels h statistics(Soil 3 - PBD 209)

Sample Soil 3 Soil 3 - PBD 209 -- Mean PARM = 0258 [mgkg]

Element PBD 209

General calcparmT1= 596398E+00T2= 191917E+00T3= 22T4= 84T5= 13249E-02

n= variabelp= 6

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean26L 01162 0021 2 -108 074 Fail 01162 00207 2 1 -0144L 01303 0031 4 -097 111 Fail 01303 00312 4 3 -013

46L 01975 0036 4 -046 128 Fail 01975 00359 4 3 -00644L 02898 0035 4 024 124 Fail 02898 00346 4 3 00312L 03895 0018 4 100 065 Fail 03895 00181 4 3 01364L 04260 0022 4 127 078 Fail 04260 00219 4 3 017

Totgem 0258 0027 mgkg 1-level 187 (177) 6 02582 () 6 5Totstd= 0132 0008 5-level 166 (154)

RESULTS Mean = 025818 mgkg

Repeatability variance S2r = 000083Repeatability std Sr = 002878 --gt 1115 r = 00806Between lab variance S2L = 001640Reproducibility var S2R = 001723Reproducibility std SR = 013127 --gt 5084 R = 03676Remarks none

000 050 100 150

k-values

26L

4L

46L

44L

12L

64L

Mandels k statistics(Soil 3 - PBD 209)

-02 -01 -01 00 01 01 02 02

Deviation from Mean

26L

4L

46L

44L

12L

64L

Labo

rato

ries

Soil 3 - PBD 209 -- Mean PARM = 0258 [mgkg]

-200 -100 000 100 200

h-values

26L

4L

46L

44L

12L

64L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 209)

Soil 3-PBD 209

Unit mgkg

Mandels k statistics(Compost 1 - Sum PBD)Mandels h statistics(Compost 1 - Sum PBD)

Sample Compost 1 Compost 1 - Sum PBD -- Mean PARM = 0009 [mgkg]

Element Sum PBD

General calcparmT1= 154064E-01T2= 169065E-03T3= 18T4= 68T5= 11354E-04

n= variabelp= 5

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00031 0002 4 -067 016 00031 00016 4 3 -0014L 00055 0005 4 -056 048 00055 00047 4 3 000

46L 00085 0003 4 -042 031 00085 00030 4 3 00026L 00123 0000 2 -024 003 00123 00002 2 1 00012L 00154 0002 4 -011 021 00154 00021 4 3 00144L 00613 0023 4 200 237 Fail - - 44L - - 005

Totgem 0018 0006 mgkg 1-level 187 (177) 5 00089 (44L) 5 4Totstd= 0022 0009 5-level 166 (154) 1

RESULTS Mean = 000893 mgkg

Repeatability variance S2r = 000001Repeatability std Sr = 000296 --gt 3308 r = 00083Between lab variance S2L = 000002Reproducibility var S2R = 000003Reproducibility std SR = 000570 --gt 6374 R = 00159Remarks 1 Lab rejected (44L)

000 050 100 150 200 250

k-values

10L

4L

46L

26L

12L

44L

Mandels k statistics(Compost 1 - Sum PBD)

00 00 00 00 00 00 01 01

Deviation from Mean

10L

4L

46L

26L

12L

44L

Labo

rato

ries

Compost 1 - Sum PBD -- Mean PARM = 0009 [mgkg]

-100 000 100 200

h-values

10L

4L

46L

26L

12L

44L

Labo

rato

ries

Mandels h statistics(Compost 1 - Sum PBD)

Compost 1-Sum PBD

Unit mgkg

Mandels k statistics(Sludge 1 - Sum PBD)Mandels h statistics(Sludge 1 - Sum PBD)

Sample Sludge 1 Sludge 1 - Sum PBD -- Mean PARM = 0256 [mgkg]

Element Sum PBD

General calcparmT1= 531806E+00T2= 162188E+00T3= 22T4= 84T5= 25223E-02

n= variabelp= 6

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00423 0025 4 -156 044 Fail 00423 00252 4 3 -02146L 01808 0118 4 -049 205 - - 46L - - -0074L 01810 0056 4 -049 097 01810 00558 4 3 -007

38L 02168 0006 4 -022 010 02168 00059 4 3 -00412L 02890 0065 4 034 113 02890 00647 4 3 00364L 03958 0008 4 116 014 Fail 03958 00079 4 3 01426L 04094 0034 2 126 059 Fail 04094 00337 2 1 015

Totgem 0245 0044 mgkg 1-level 198 (179) 6 02557 (46L) 6 5Totstd= 0130 0039 5-level 171 (155) 1

RESULTS Mean = 025570 mgkg

Repeatability variance S2r = 000158Repeatability std Sr = 003970 --gt 1553 r = 01112Between lab variance S2L = 001807Reproducibility var S2R = 001964Reproducibility std SR = 014015 --gt 5481 R = 03924Remarks 1 Lab rejected (46L)

000 050 100 150 200 250

k-values

10L

46L

4L

38L

12L

64L

26L

Mandels k statistics(Sludge 1 - Sum PBD)

-03 -02 -02 -01 -01 00 01 01 02 02

Deviation from Mean

10L

46L

4L

38L

12L

64L

26L

Labo

rato

ries

Sludge 1 - Sum PBD -- Mean PARM = 0256 [mgkg]

-200 -100 000 100 200

h-values

10L

46L

4L

38L

12L

64L

26L

Labo

rato

ries

Mandels h statistics(Sludge 1 - Sum PBD)

Sludge 1-Sum PBD

Unit mgkg

Mandels k statistics(Soil 3 - Sum PBD)Mandels h statistics(Soil 3 - Sum PBD)

Sample Soil 3 Soil 3 - Sum PBD -- Mean PARM = 0227 [mgkg]

Element Sum PBD

General calcparmT1= 610980E+00T2= 200876E+00T3= 26T4= 100T5= 13106E-02

n= variabelp= 7

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00028 0001 4 -037 000 Fail 00028 00005 4 3 -02226L 01179 0021 2 -036 003 Fail 01179 00208 2 1 -0114L 01305 0031 4 -036 004 Fail 01305 00308 4 3 -010

46L 02065 0035 4 -036 005 Fail 02065 00350 4 3 -00244L 02923 0037 4 -035 005 Fail 02923 00365 4 3 00712L 04051 0015 4 -034 002 Fail 04051 00149 4 3 01864L 04314 0022 4 -033 003 Fail 04314 00223 4 3 0203L 305500 2051 2 247 283 Fail - - 3L - - 3032

Totgem 4017 0276 mgkg 1-level 206 (181) 7 02266 (3L) 7 6Totstd= 10722 0717 5-level 175 (156) 1

RESULTS Mean = 022663 mgkg

Repeatability variance S2r = 000069Repeatability std Sr = 002626 --gt 1159 r = 00735Between lab variance S2L = 002568Reproducibility var S2R = 002637Reproducibility std SR = 016238 --gt 7165 R = 04547Remarks 1 Lab rejected (3L)

000 050 100 150 200 250 300

k-values

10L

26L

4L

46L

44L

12L

64L

3L

Mandels k statistics(Soil 3 - Sum PBD)

-50 00 50 100 150 200 250 300 350

Deviation from Mean

10L

26L

4L

46L

44L

12L

64L

3L

Labo

rato

ries

Soil 3 - Sum PBD -- Mean PARM = 0227 [mgkg]

-100 000 100 200 300

h-values

10L

26L

4L

46L

44L

12L

64L

3L

Labo

rato

ries

Mandels h statistics(Soil 3 - Sum PBD)

Soil 3-Sum PBD

19

Annex 4

Raw data submitted

Sample Compost1 Sample Compost 1 Sample Compost 1Element PBD 99 Element PBD 100 Element PBD 153

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]4L 00021 10L 00008 44L 000504L 00024 10L 00008 44L 000604L 00014 10L 00007 44L 000504L 00020 10L 00011 46L 00004

10L 00029 46L 00007 46L 0001210L 00027 46L 00012 46L 0000410L 00032 46L 00009 46L 0000946L 00025 46L 00007 12L 0000446L 00052 12L 00008 12L 0000846L 00029 12L 00012 12L 0000446L 00026 12L 00008 12L 0000712L 00026 12L 00014 26L 0000512L 00043 26L 00007 26L 0000512L 00026 26L 0000612L 0004726L 0002626L 00024

Sample Compost 1 Sample Compost 1 Sample Compost 1Element PBD 154 Element PBD 183 Element PBD 196

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]4L 00010 46L 00002 46L 00011

46L 00003 46L 00024 46L 0000846L 00007 46L 00021 12L 0000246L 00003 46L 00003 12L 0000346L 00004 12L 00003 12L 0000112L 00003 12L 00011 12L 0000212L 00005 12L 0000312L 00031 12L 0000312L 00006

Sample Compost 1 Sample Compost 1 Sample Compost 1Element PBD 197 Element PBD 203 Element PBD 209

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00002 46L 00010 4L 0004146L 00023 12L 00002 4L 0008946L 00022 12L 00003 44L 0041012L 00004 12L 00002 44L 0084012L 00006 12L 00002 44L 0064012L 00003 44L 0040012L 00004 12L 00079

12L 0007312L 0006512L 0009326L 0004926L 00049

Sample Compost 1Element PBD 47

LAB PARM [mgkg]26L 0003826L 00039

Element PBD 99 Element PBD 47 Element PBD 209LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]

4L 00170 10L 00210 4L 010004L 00200 10L 00220 4L 018004L 00170 10L 00210 4L 012004L 00190 46L 00300 4L 0220010L 00280 46L 00280 46L 0210010L 00300 46L 00250 46L 0200010L 00290 46L 00260 64L 0351846L 00340 64L 00059 64L 0363846L 00330 64L 00057 64L 0364546L 00300 64L 00062 64L 0350846L 00310 64L 00060 12L 0220964L 00194 12L 00191 12L 0177164L 00154 12L 00187 12L 0292264L 00185 12L 00190 12L 0164664L 00159 12L 00186 26L 0329712L 00242 26L 00666 26L 0300012L 00223 26L 0033212L 0022112L 0022226L 0024626L 00400

Element PBD 203 Element PBD 197 Element PBD 196LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00022 46L 00027 46L 0002446L 00014 46L 00024 46L 0002264L 00036 12L 00161 64L 0005864L 00058 12L 00060 64L 0006512L 00063 12L 00061 12L 0004812L 00034 12L 00036 12L 0002512L 00038 12L 0003212L 00027 12L 00022

Element PBD 183 Element PBD 154 Element PBD 153LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00049 4L 00020 4L 0002246L 00035 4L 00022 4L 0002446L 00036 4L 00020 4L 0002246L 00034 46L 00025 4L 0002664L 00027 46L 00025 46L 0004064L 00023 46L 00025 46L 0004264L 00024 46L 00023 46L 0003564L 00020 64L 00034 46L 0003812L 00230 64L 00023 64L 0007412L 00032 64L 00017 64L 0004712L 00031 64L 00011 64L 0004612L 00030 12L 00030 64L 0003026L 00007 12L 00021 12L 0006526L 00008 12L 00021 12L 00029

12L 00021 12L 0003226L 00015 12L 0002926L 00019 26L 00039

26L 00040

Element PBD 100LAB PARM [mgkg]

4L 000384L 000414L 000374L 00038

38L 0219038L 0220038L 0208038L 0220010L 0004410L 0005010L 0004310L 0004646L 0005746L 0005946L 0005346L 0005312L 0004312L 0004512L 0004312L 0004326L 0006226L 00057

Sample Soil 3 Sample Soil 3 Sample Soil 3Element PBD 99 Element PBD 47 Element PBD 100

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]10L 00016 10L 00011 10L 0000310L 00019 10L 00010 10L 0000410L 00013 10L 00012 10L 0000410L 00019 46L 00007 10L 0000246L 00025 46L 00022 46L 0000246L 00025 46L 00005 46L 0000646L 00008 46L 00007 46L 0000246L 00011 12L 00010 46L 0000264L 00005 12L 00017 3L 29100064L 00005 12L 00010 3L 32000064L 00006 12L 00009 26L 0000564L 00007 26L 00007 26L 0000512L 00012 26L 0000712L 0001312L 0001312L 0001226L 0000526L 00006

Sample Soil 3 Sample Soil 3 Sample Soil 3Element PBD 153 Element PBD 154 Element PBD 196

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]44L 00050 4L 00010 46L 0000744L 00050 46L 00001 46L 0001146L 00002 46L 00002 46L 0000846L 00003 46L 00001 46L 0001146L 00002 46L 00002 64L 0002646L 00002 64L 00001 64L 0002664L 00001 64L 00001 64L 0002964L 00001 64L 00001 64L 0003464L 00001 64L 00002 12L 0004564L 00002 12L 00003 12L 00032

12L 00002 12L 0002212L 00002 12L 0002112L 00002

Sample Soil 3 Sample Soil 3 Sample Soil 3Element PBD 197 Element PBD 203 Element PBD 209

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00006 46L 00011 4L 0091046L 00013 46L 00017 4L 0150046L 00011 46L 00015 4L 0120046L 00013 46L 00018 4L 0160012L 00090 64L 00013 44L 0337012L 00056 64L 00014 44L 0281012L 00033 64L 00016 44L 0287012L 00032 64L 00015 44L 02540

12L 00055 46L 0230012L 00041 46L 0220012L 00027 46L 0150012L 00026 46L 01900

64L 0438164L 0401664L 0414464L 0449812L 0367112L 0397812L 0409112L 03838

Sample Soil 3 26L 0102Element PBD 183 26L 0131

LAB PARM [mgkg]46L 0000746L 0000846L 0005846L 0000764L 0000264L 0000364L 0000364L 0000312L 0001512L 0001112L 0000712L 00007

European Commission EUR 23003 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on polybrominated diphenylethers Author(s) E Sobiecka H van der Sloot D Barcelo B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 68 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07403-5 Abstract Project HORIZONTAL is interdisciplinary aiming at a harmonisation and horizontal standardisation of test procedures in particular for sludge soils and biowastes In the context of this standardization project a series of draft technical specification were designed upon an extensive desk study fine-tuned after expert consultations and finally validated in international intercomparisons exercise This report summarises the work performed within the validation study of the draft standard for the determination of polybrominated diphenylethers (PBDE) in soils sludge and treated bio-waste using gas-chromatography method with mass selective detection (GC-MS) It further explains the underlying statistical concept for the calculation of reproducibility and repeatability from intercomparisons data In addition all single values results of the statistical evaluation as well as background information on the validation materials used are described and explained

The mission of the JRC is to provide customer-driven scientific and technical support for the conception development implementation and monitoring of EU policies As a service of the European Commission the JRC functions as a reference centre of science and technology for the Union Close to the policy-making process it serves the common interest of the Member States while being independent of special interests whether private or national

LB

-NA

-23003-EN

-C

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 154)Mandels h statistics(Sludge 1 - PBD 154)

Sample Sludge 1 NA

Element PBD 154

General calcparmT1= NAT2= NAT3=T4=T5=

n= variabelp=

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00021 0000 3 -100 021 NA - 4L - - NA

46L 00025 0000 4 115 018 NA - 46L - - NA64L 00021 0001 4 -066 179 - - 64L - - NA12L 00023 0000 4 050 085 - - 12L - - NA

Totgem 0002 0000 mgkg 1-level 149 (167) NA (4L46L64L12L) -1Totstd= 0000 0000 5-level 142 (15) 4

RESULTS Mean = NA mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NAReproducibility var S2R = NAReproducibility std SR = NA --gt NA R = NARemarks 4 Labs rejected (4L46L64L12L)

000 050 100 150 200

k-values

4L

46L

64L

12L

Mandels k statistics(Sludge 1 - PBD 154)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

4L

46L

64L

12L

Labo

rato

ries

NA

-100 000 100 200

h-values

4L

46L

64L

12L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 154)

Sludge 1-PBD 154

Unit mgkg

Mandels k statistics(Soil 3 - PBD 154)Mandels h statistics(Soil 3 - PBD 154)

Sample Soil 3 NUM

Element PBD 154

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

4L 00010 - 1 150 Fail - - 4L - - NUM46L 00001 0000 4 -053 096 Fail - - 46L - - NUM64L 00001 0000 4 -056 105 Fail NUM - 64L - - NUM12L 00002 0000 4 -040 099 Fail - - 12L - - NUM

Totgem 000037 0000 mgkg 1-level 149 (164) NUM (4L46L64L12L) -1Totstd= 000042 0000 5-level 142 (153) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (4L46L64L12L)

000 050 100 150

k-values

4L

46L

64L

12L

Mandels k statistics(Soil 3 - PBD 154)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

4L

46L

64L

12L

Labo

rato

ries

NUM

-100 000 100 200

h-values

4L

46L

64L

12L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 154)

Soil 3-PBD 154

Unit mgkg

Mandels k statistics(Compost 1 - PBD 209)Mandels h statistics(Compost 1 - PBD 209)

Sample Compost 1 NUM

Element PBD 209

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00065 0003 2 -049 032 - - 4L - - NUM

44L 00573 0021 4 150 197 Fail - - 44L - - NUM12L 00078 0001 4 -045 011 - - 12L - - NUM26L 00049 0000 2 -056 000 NUM - 26L - - NUM

Totgem 0019 0006 mgkg 1-level 149 (177) NUM (4L44L12L26L) -1Totstd= 0025 0010 5-level 142 (159) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (4L44L12L26L)

000 050 100 150 200

k-values

4L

44L

12L

26L

Mandels k statistics(Compost 1 - PBD 209)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

4L

44L

12L

26L

Labo

rato

ries

NUM

-100 000 100 200

h-values

4L

44L

12L

26L

Labo

rato

ries

Mandels h statistics(Compost 1 - PBD 209)

Compost 1-PBD 209

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 209)Mandels h statistics(Sludge 1 - PBD 209)

Sample Sludge 1 Sludge 1 - PBD 209 -- Mean PARM = 0249 [mgkg]

Element PBD 209

General calcparmT1= 394542E+00T2= 107296E+00T3= 16T4= 56T5= 19723E-02

n= variabelp= 5

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 01550 0055 4 -112 148 Fail 01550 00551 4 3 -009

46L 02050 0007 2 -053 019 02050 00071 2 1 -00412L 02137 0058 4 -042 155 02137 00576 4 3 -00426L 03149 0021 2 078 057 Fail 03149 00210 2 1 00764L 03577 0007 4 129 020 Fail 03577 00074 4 3 011

Totgem 0249 0030 mgkg 1-level 172 (185) 5 02493 () 5 4Totstd= 0084 0025 5-level 157 (162)

RESULTS Mean = 024926 mgkg

Repeatability variance S2r = 000179Repeatability std Sr = 004234 --gt 1699 r = 01186Between lab variance S2L = 000743Reproducibility var S2R = 000922Reproducibility std SR = 009604 --gt 3853 R = 02689Remarks none

000 050 100 150 200

k-values

4L

46L

12L

26L

64L

Mandels k statistics(Sludge 1 - PBD 209)

-01 -01 00 01 01 02

Deviation from Mean

4L

46L

12L

26L

64L

Labo

rato

ries

Sludge 1 - PBD 209 -- Mean PARM = 0249 [mgkg]

-200 -100 000 100 200

h-values

4L

46L

12L

26L

64L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 209)

Sludge 1-PBD 209

Unit mgkg

Mandels k statistics(Soil 3 - PBD 209)Mandels h statistics(Soil 3 - PBD 209)

Sample Soil 3 Soil 3 - PBD 209 -- Mean PARM = 0258 [mgkg]

Element PBD 209

General calcparmT1= 596398E+00T2= 191917E+00T3= 22T4= 84T5= 13249E-02

n= variabelp= 6

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean26L 01162 0021 2 -108 074 Fail 01162 00207 2 1 -0144L 01303 0031 4 -097 111 Fail 01303 00312 4 3 -013

46L 01975 0036 4 -046 128 Fail 01975 00359 4 3 -00644L 02898 0035 4 024 124 Fail 02898 00346 4 3 00312L 03895 0018 4 100 065 Fail 03895 00181 4 3 01364L 04260 0022 4 127 078 Fail 04260 00219 4 3 017

Totgem 0258 0027 mgkg 1-level 187 (177) 6 02582 () 6 5Totstd= 0132 0008 5-level 166 (154)

RESULTS Mean = 025818 mgkg

Repeatability variance S2r = 000083Repeatability std Sr = 002878 --gt 1115 r = 00806Between lab variance S2L = 001640Reproducibility var S2R = 001723Reproducibility std SR = 013127 --gt 5084 R = 03676Remarks none

000 050 100 150

k-values

26L

4L

46L

44L

12L

64L

Mandels k statistics(Soil 3 - PBD 209)

-02 -01 -01 00 01 01 02 02

Deviation from Mean

26L

4L

46L

44L

12L

64L

Labo

rato

ries

Soil 3 - PBD 209 -- Mean PARM = 0258 [mgkg]

-200 -100 000 100 200

h-values

26L

4L

46L

44L

12L

64L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 209)

Soil 3-PBD 209

Unit mgkg

Mandels k statistics(Compost 1 - Sum PBD)Mandels h statistics(Compost 1 - Sum PBD)

Sample Compost 1 Compost 1 - Sum PBD -- Mean PARM = 0009 [mgkg]

Element Sum PBD

General calcparmT1= 154064E-01T2= 169065E-03T3= 18T4= 68T5= 11354E-04

n= variabelp= 5

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00031 0002 4 -067 016 00031 00016 4 3 -0014L 00055 0005 4 -056 048 00055 00047 4 3 000

46L 00085 0003 4 -042 031 00085 00030 4 3 00026L 00123 0000 2 -024 003 00123 00002 2 1 00012L 00154 0002 4 -011 021 00154 00021 4 3 00144L 00613 0023 4 200 237 Fail - - 44L - - 005

Totgem 0018 0006 mgkg 1-level 187 (177) 5 00089 (44L) 5 4Totstd= 0022 0009 5-level 166 (154) 1

RESULTS Mean = 000893 mgkg

Repeatability variance S2r = 000001Repeatability std Sr = 000296 --gt 3308 r = 00083Between lab variance S2L = 000002Reproducibility var S2R = 000003Reproducibility std SR = 000570 --gt 6374 R = 00159Remarks 1 Lab rejected (44L)

000 050 100 150 200 250

k-values

10L

4L

46L

26L

12L

44L

Mandels k statistics(Compost 1 - Sum PBD)

00 00 00 00 00 00 01 01

Deviation from Mean

10L

4L

46L

26L

12L

44L

Labo

rato

ries

Compost 1 - Sum PBD -- Mean PARM = 0009 [mgkg]

-100 000 100 200

h-values

10L

4L

46L

26L

12L

44L

Labo

rato

ries

Mandels h statistics(Compost 1 - Sum PBD)

Compost 1-Sum PBD

Unit mgkg

Mandels k statistics(Sludge 1 - Sum PBD)Mandels h statistics(Sludge 1 - Sum PBD)

Sample Sludge 1 Sludge 1 - Sum PBD -- Mean PARM = 0256 [mgkg]

Element Sum PBD

General calcparmT1= 531806E+00T2= 162188E+00T3= 22T4= 84T5= 25223E-02

n= variabelp= 6

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00423 0025 4 -156 044 Fail 00423 00252 4 3 -02146L 01808 0118 4 -049 205 - - 46L - - -0074L 01810 0056 4 -049 097 01810 00558 4 3 -007

38L 02168 0006 4 -022 010 02168 00059 4 3 -00412L 02890 0065 4 034 113 02890 00647 4 3 00364L 03958 0008 4 116 014 Fail 03958 00079 4 3 01426L 04094 0034 2 126 059 Fail 04094 00337 2 1 015

Totgem 0245 0044 mgkg 1-level 198 (179) 6 02557 (46L) 6 5Totstd= 0130 0039 5-level 171 (155) 1

RESULTS Mean = 025570 mgkg

Repeatability variance S2r = 000158Repeatability std Sr = 003970 --gt 1553 r = 01112Between lab variance S2L = 001807Reproducibility var S2R = 001964Reproducibility std SR = 014015 --gt 5481 R = 03924Remarks 1 Lab rejected (46L)

000 050 100 150 200 250

k-values

10L

46L

4L

38L

12L

64L

26L

Mandels k statistics(Sludge 1 - Sum PBD)

-03 -02 -02 -01 -01 00 01 01 02 02

Deviation from Mean

10L

46L

4L

38L

12L

64L

26L

Labo

rato

ries

Sludge 1 - Sum PBD -- Mean PARM = 0256 [mgkg]

-200 -100 000 100 200

h-values

10L

46L

4L

38L

12L

64L

26L

Labo

rato

ries

Mandels h statistics(Sludge 1 - Sum PBD)

Sludge 1-Sum PBD

Unit mgkg

Mandels k statistics(Soil 3 - Sum PBD)Mandels h statistics(Soil 3 - Sum PBD)

Sample Soil 3 Soil 3 - Sum PBD -- Mean PARM = 0227 [mgkg]

Element Sum PBD

General calcparmT1= 610980E+00T2= 200876E+00T3= 26T4= 100T5= 13106E-02

n= variabelp= 7

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00028 0001 4 -037 000 Fail 00028 00005 4 3 -02226L 01179 0021 2 -036 003 Fail 01179 00208 2 1 -0114L 01305 0031 4 -036 004 Fail 01305 00308 4 3 -010

46L 02065 0035 4 -036 005 Fail 02065 00350 4 3 -00244L 02923 0037 4 -035 005 Fail 02923 00365 4 3 00712L 04051 0015 4 -034 002 Fail 04051 00149 4 3 01864L 04314 0022 4 -033 003 Fail 04314 00223 4 3 0203L 305500 2051 2 247 283 Fail - - 3L - - 3032

Totgem 4017 0276 mgkg 1-level 206 (181) 7 02266 (3L) 7 6Totstd= 10722 0717 5-level 175 (156) 1

RESULTS Mean = 022663 mgkg

Repeatability variance S2r = 000069Repeatability std Sr = 002626 --gt 1159 r = 00735Between lab variance S2L = 002568Reproducibility var S2R = 002637Reproducibility std SR = 016238 --gt 7165 R = 04547Remarks 1 Lab rejected (3L)

000 050 100 150 200 250 300

k-values

10L

26L

4L

46L

44L

12L

64L

3L

Mandels k statistics(Soil 3 - Sum PBD)

-50 00 50 100 150 200 250 300 350

Deviation from Mean

10L

26L

4L

46L

44L

12L

64L

3L

Labo

rato

ries

Soil 3 - Sum PBD -- Mean PARM = 0227 [mgkg]

-100 000 100 200 300

h-values

10L

26L

4L

46L

44L

12L

64L

3L

Labo

rato

ries

Mandels h statistics(Soil 3 - Sum PBD)

Soil 3-Sum PBD

19

Annex 4

Raw data submitted

Sample Compost1 Sample Compost 1 Sample Compost 1Element PBD 99 Element PBD 100 Element PBD 153

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]4L 00021 10L 00008 44L 000504L 00024 10L 00008 44L 000604L 00014 10L 00007 44L 000504L 00020 10L 00011 46L 00004

10L 00029 46L 00007 46L 0001210L 00027 46L 00012 46L 0000410L 00032 46L 00009 46L 0000946L 00025 46L 00007 12L 0000446L 00052 12L 00008 12L 0000846L 00029 12L 00012 12L 0000446L 00026 12L 00008 12L 0000712L 00026 12L 00014 26L 0000512L 00043 26L 00007 26L 0000512L 00026 26L 0000612L 0004726L 0002626L 00024

Sample Compost 1 Sample Compost 1 Sample Compost 1Element PBD 154 Element PBD 183 Element PBD 196

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]4L 00010 46L 00002 46L 00011

46L 00003 46L 00024 46L 0000846L 00007 46L 00021 12L 0000246L 00003 46L 00003 12L 0000346L 00004 12L 00003 12L 0000112L 00003 12L 00011 12L 0000212L 00005 12L 0000312L 00031 12L 0000312L 00006

Sample Compost 1 Sample Compost 1 Sample Compost 1Element PBD 197 Element PBD 203 Element PBD 209

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00002 46L 00010 4L 0004146L 00023 12L 00002 4L 0008946L 00022 12L 00003 44L 0041012L 00004 12L 00002 44L 0084012L 00006 12L 00002 44L 0064012L 00003 44L 0040012L 00004 12L 00079

12L 0007312L 0006512L 0009326L 0004926L 00049

Sample Compost 1Element PBD 47

LAB PARM [mgkg]26L 0003826L 00039

Element PBD 99 Element PBD 47 Element PBD 209LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]

4L 00170 10L 00210 4L 010004L 00200 10L 00220 4L 018004L 00170 10L 00210 4L 012004L 00190 46L 00300 4L 0220010L 00280 46L 00280 46L 0210010L 00300 46L 00250 46L 0200010L 00290 46L 00260 64L 0351846L 00340 64L 00059 64L 0363846L 00330 64L 00057 64L 0364546L 00300 64L 00062 64L 0350846L 00310 64L 00060 12L 0220964L 00194 12L 00191 12L 0177164L 00154 12L 00187 12L 0292264L 00185 12L 00190 12L 0164664L 00159 12L 00186 26L 0329712L 00242 26L 00666 26L 0300012L 00223 26L 0033212L 0022112L 0022226L 0024626L 00400

Element PBD 203 Element PBD 197 Element PBD 196LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00022 46L 00027 46L 0002446L 00014 46L 00024 46L 0002264L 00036 12L 00161 64L 0005864L 00058 12L 00060 64L 0006512L 00063 12L 00061 12L 0004812L 00034 12L 00036 12L 0002512L 00038 12L 0003212L 00027 12L 00022

Element PBD 183 Element PBD 154 Element PBD 153LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00049 4L 00020 4L 0002246L 00035 4L 00022 4L 0002446L 00036 4L 00020 4L 0002246L 00034 46L 00025 4L 0002664L 00027 46L 00025 46L 0004064L 00023 46L 00025 46L 0004264L 00024 46L 00023 46L 0003564L 00020 64L 00034 46L 0003812L 00230 64L 00023 64L 0007412L 00032 64L 00017 64L 0004712L 00031 64L 00011 64L 0004612L 00030 12L 00030 64L 0003026L 00007 12L 00021 12L 0006526L 00008 12L 00021 12L 00029

12L 00021 12L 0003226L 00015 12L 0002926L 00019 26L 00039

26L 00040

Element PBD 100LAB PARM [mgkg]

4L 000384L 000414L 000374L 00038

38L 0219038L 0220038L 0208038L 0220010L 0004410L 0005010L 0004310L 0004646L 0005746L 0005946L 0005346L 0005312L 0004312L 0004512L 0004312L 0004326L 0006226L 00057

Sample Soil 3 Sample Soil 3 Sample Soil 3Element PBD 99 Element PBD 47 Element PBD 100

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]10L 00016 10L 00011 10L 0000310L 00019 10L 00010 10L 0000410L 00013 10L 00012 10L 0000410L 00019 46L 00007 10L 0000246L 00025 46L 00022 46L 0000246L 00025 46L 00005 46L 0000646L 00008 46L 00007 46L 0000246L 00011 12L 00010 46L 0000264L 00005 12L 00017 3L 29100064L 00005 12L 00010 3L 32000064L 00006 12L 00009 26L 0000564L 00007 26L 00007 26L 0000512L 00012 26L 0000712L 0001312L 0001312L 0001226L 0000526L 00006

Sample Soil 3 Sample Soil 3 Sample Soil 3Element PBD 153 Element PBD 154 Element PBD 196

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]44L 00050 4L 00010 46L 0000744L 00050 46L 00001 46L 0001146L 00002 46L 00002 46L 0000846L 00003 46L 00001 46L 0001146L 00002 46L 00002 64L 0002646L 00002 64L 00001 64L 0002664L 00001 64L 00001 64L 0002964L 00001 64L 00001 64L 0003464L 00001 64L 00002 12L 0004564L 00002 12L 00003 12L 00032

12L 00002 12L 0002212L 00002 12L 0002112L 00002

Sample Soil 3 Sample Soil 3 Sample Soil 3Element PBD 197 Element PBD 203 Element PBD 209

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00006 46L 00011 4L 0091046L 00013 46L 00017 4L 0150046L 00011 46L 00015 4L 0120046L 00013 46L 00018 4L 0160012L 00090 64L 00013 44L 0337012L 00056 64L 00014 44L 0281012L 00033 64L 00016 44L 0287012L 00032 64L 00015 44L 02540

12L 00055 46L 0230012L 00041 46L 0220012L 00027 46L 0150012L 00026 46L 01900

64L 0438164L 0401664L 0414464L 0449812L 0367112L 0397812L 0409112L 03838

Sample Soil 3 26L 0102Element PBD 183 26L 0131

LAB PARM [mgkg]46L 0000746L 0000846L 0005846L 0000764L 0000264L 0000364L 0000364L 0000312L 0001512L 0001112L 0000712L 00007

European Commission EUR 23003 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on polybrominated diphenylethers Author(s) E Sobiecka H van der Sloot D Barcelo B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 68 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07403-5 Abstract Project HORIZONTAL is interdisciplinary aiming at a harmonisation and horizontal standardisation of test procedures in particular for sludge soils and biowastes In the context of this standardization project a series of draft technical specification were designed upon an extensive desk study fine-tuned after expert consultations and finally validated in international intercomparisons exercise This report summarises the work performed within the validation study of the draft standard for the determination of polybrominated diphenylethers (PBDE) in soils sludge and treated bio-waste using gas-chromatography method with mass selective detection (GC-MS) It further explains the underlying statistical concept for the calculation of reproducibility and repeatability from intercomparisons data In addition all single values results of the statistical evaluation as well as background information on the validation materials used are described and explained

The mission of the JRC is to provide customer-driven scientific and technical support for the conception development implementation and monitoring of EU policies As a service of the European Commission the JRC functions as a reference centre of science and technology for the Union Close to the policy-making process it serves the common interest of the Member States while being independent of special interests whether private or national

LB

-NA

-23003-EN

-C

Unit mgkg

Mandels k statistics(Soil 3 - PBD 154)Mandels h statistics(Soil 3 - PBD 154)

Sample Soil 3 NUM

Element PBD 154

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

4L 00010 - 1 150 Fail - - 4L - - NUM46L 00001 0000 4 -053 096 Fail - - 46L - - NUM64L 00001 0000 4 -056 105 Fail NUM - 64L - - NUM12L 00002 0000 4 -040 099 Fail - - 12L - - NUM

Totgem 000037 0000 mgkg 1-level 149 (164) NUM (4L46L64L12L) -1Totstd= 000042 0000 5-level 142 (153) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (4L46L64L12L)

000 050 100 150

k-values

4L

46L

64L

12L

Mandels k statistics(Soil 3 - PBD 154)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

4L

46L

64L

12L

Labo

rato

ries

NUM

-100 000 100 200

h-values

4L

46L

64L

12L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 154)

Soil 3-PBD 154

Unit mgkg

Mandels k statistics(Compost 1 - PBD 209)Mandels h statistics(Compost 1 - PBD 209)

Sample Compost 1 NUM

Element PBD 209

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00065 0003 2 -049 032 - - 4L - - NUM

44L 00573 0021 4 150 197 Fail - - 44L - - NUM12L 00078 0001 4 -045 011 - - 12L - - NUM26L 00049 0000 2 -056 000 NUM - 26L - - NUM

Totgem 0019 0006 mgkg 1-level 149 (177) NUM (4L44L12L26L) -1Totstd= 0025 0010 5-level 142 (159) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (4L44L12L26L)

000 050 100 150 200

k-values

4L

44L

12L

26L

Mandels k statistics(Compost 1 - PBD 209)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

4L

44L

12L

26L

Labo

rato

ries

NUM

-100 000 100 200

h-values

4L

44L

12L

26L

Labo

rato

ries

Mandels h statistics(Compost 1 - PBD 209)

Compost 1-PBD 209

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 209)Mandels h statistics(Sludge 1 - PBD 209)

Sample Sludge 1 Sludge 1 - PBD 209 -- Mean PARM = 0249 [mgkg]

Element PBD 209

General calcparmT1= 394542E+00T2= 107296E+00T3= 16T4= 56T5= 19723E-02

n= variabelp= 5

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 01550 0055 4 -112 148 Fail 01550 00551 4 3 -009

46L 02050 0007 2 -053 019 02050 00071 2 1 -00412L 02137 0058 4 -042 155 02137 00576 4 3 -00426L 03149 0021 2 078 057 Fail 03149 00210 2 1 00764L 03577 0007 4 129 020 Fail 03577 00074 4 3 011

Totgem 0249 0030 mgkg 1-level 172 (185) 5 02493 () 5 4Totstd= 0084 0025 5-level 157 (162)

RESULTS Mean = 024926 mgkg

Repeatability variance S2r = 000179Repeatability std Sr = 004234 --gt 1699 r = 01186Between lab variance S2L = 000743Reproducibility var S2R = 000922Reproducibility std SR = 009604 --gt 3853 R = 02689Remarks none

000 050 100 150 200

k-values

4L

46L

12L

26L

64L

Mandels k statistics(Sludge 1 - PBD 209)

-01 -01 00 01 01 02

Deviation from Mean

4L

46L

12L

26L

64L

Labo

rato

ries

Sludge 1 - PBD 209 -- Mean PARM = 0249 [mgkg]

-200 -100 000 100 200

h-values

4L

46L

12L

26L

64L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 209)

Sludge 1-PBD 209

Unit mgkg

Mandels k statistics(Soil 3 - PBD 209)Mandels h statistics(Soil 3 - PBD 209)

Sample Soil 3 Soil 3 - PBD 209 -- Mean PARM = 0258 [mgkg]

Element PBD 209

General calcparmT1= 596398E+00T2= 191917E+00T3= 22T4= 84T5= 13249E-02

n= variabelp= 6

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean26L 01162 0021 2 -108 074 Fail 01162 00207 2 1 -0144L 01303 0031 4 -097 111 Fail 01303 00312 4 3 -013

46L 01975 0036 4 -046 128 Fail 01975 00359 4 3 -00644L 02898 0035 4 024 124 Fail 02898 00346 4 3 00312L 03895 0018 4 100 065 Fail 03895 00181 4 3 01364L 04260 0022 4 127 078 Fail 04260 00219 4 3 017

Totgem 0258 0027 mgkg 1-level 187 (177) 6 02582 () 6 5Totstd= 0132 0008 5-level 166 (154)

RESULTS Mean = 025818 mgkg

Repeatability variance S2r = 000083Repeatability std Sr = 002878 --gt 1115 r = 00806Between lab variance S2L = 001640Reproducibility var S2R = 001723Reproducibility std SR = 013127 --gt 5084 R = 03676Remarks none

000 050 100 150

k-values

26L

4L

46L

44L

12L

64L

Mandels k statistics(Soil 3 - PBD 209)

-02 -01 -01 00 01 01 02 02

Deviation from Mean

26L

4L

46L

44L

12L

64L

Labo

rato

ries

Soil 3 - PBD 209 -- Mean PARM = 0258 [mgkg]

-200 -100 000 100 200

h-values

26L

4L

46L

44L

12L

64L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 209)

Soil 3-PBD 209

Unit mgkg

Mandels k statistics(Compost 1 - Sum PBD)Mandels h statistics(Compost 1 - Sum PBD)

Sample Compost 1 Compost 1 - Sum PBD -- Mean PARM = 0009 [mgkg]

Element Sum PBD

General calcparmT1= 154064E-01T2= 169065E-03T3= 18T4= 68T5= 11354E-04

n= variabelp= 5

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00031 0002 4 -067 016 00031 00016 4 3 -0014L 00055 0005 4 -056 048 00055 00047 4 3 000

46L 00085 0003 4 -042 031 00085 00030 4 3 00026L 00123 0000 2 -024 003 00123 00002 2 1 00012L 00154 0002 4 -011 021 00154 00021 4 3 00144L 00613 0023 4 200 237 Fail - - 44L - - 005

Totgem 0018 0006 mgkg 1-level 187 (177) 5 00089 (44L) 5 4Totstd= 0022 0009 5-level 166 (154) 1

RESULTS Mean = 000893 mgkg

Repeatability variance S2r = 000001Repeatability std Sr = 000296 --gt 3308 r = 00083Between lab variance S2L = 000002Reproducibility var S2R = 000003Reproducibility std SR = 000570 --gt 6374 R = 00159Remarks 1 Lab rejected (44L)

000 050 100 150 200 250

k-values

10L

4L

46L

26L

12L

44L

Mandels k statistics(Compost 1 - Sum PBD)

00 00 00 00 00 00 01 01

Deviation from Mean

10L

4L

46L

26L

12L

44L

Labo

rato

ries

Compost 1 - Sum PBD -- Mean PARM = 0009 [mgkg]

-100 000 100 200

h-values

10L

4L

46L

26L

12L

44L

Labo

rato

ries

Mandels h statistics(Compost 1 - Sum PBD)

Compost 1-Sum PBD

Unit mgkg

Mandels k statistics(Sludge 1 - Sum PBD)Mandels h statistics(Sludge 1 - Sum PBD)

Sample Sludge 1 Sludge 1 - Sum PBD -- Mean PARM = 0256 [mgkg]

Element Sum PBD

General calcparmT1= 531806E+00T2= 162188E+00T3= 22T4= 84T5= 25223E-02

n= variabelp= 6

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00423 0025 4 -156 044 Fail 00423 00252 4 3 -02146L 01808 0118 4 -049 205 - - 46L - - -0074L 01810 0056 4 -049 097 01810 00558 4 3 -007

38L 02168 0006 4 -022 010 02168 00059 4 3 -00412L 02890 0065 4 034 113 02890 00647 4 3 00364L 03958 0008 4 116 014 Fail 03958 00079 4 3 01426L 04094 0034 2 126 059 Fail 04094 00337 2 1 015

Totgem 0245 0044 mgkg 1-level 198 (179) 6 02557 (46L) 6 5Totstd= 0130 0039 5-level 171 (155) 1

RESULTS Mean = 025570 mgkg

Repeatability variance S2r = 000158Repeatability std Sr = 003970 --gt 1553 r = 01112Between lab variance S2L = 001807Reproducibility var S2R = 001964Reproducibility std SR = 014015 --gt 5481 R = 03924Remarks 1 Lab rejected (46L)

000 050 100 150 200 250

k-values

10L

46L

4L

38L

12L

64L

26L

Mandels k statistics(Sludge 1 - Sum PBD)

-03 -02 -02 -01 -01 00 01 01 02 02

Deviation from Mean

10L

46L

4L

38L

12L

64L

26L

Labo

rato

ries

Sludge 1 - Sum PBD -- Mean PARM = 0256 [mgkg]

-200 -100 000 100 200

h-values

10L

46L

4L

38L

12L

64L

26L

Labo

rato

ries

Mandels h statistics(Sludge 1 - Sum PBD)

Sludge 1-Sum PBD

Unit mgkg

Mandels k statistics(Soil 3 - Sum PBD)Mandels h statistics(Soil 3 - Sum PBD)

Sample Soil 3 Soil 3 - Sum PBD -- Mean PARM = 0227 [mgkg]

Element Sum PBD

General calcparmT1= 610980E+00T2= 200876E+00T3= 26T4= 100T5= 13106E-02

n= variabelp= 7

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00028 0001 4 -037 000 Fail 00028 00005 4 3 -02226L 01179 0021 2 -036 003 Fail 01179 00208 2 1 -0114L 01305 0031 4 -036 004 Fail 01305 00308 4 3 -010

46L 02065 0035 4 -036 005 Fail 02065 00350 4 3 -00244L 02923 0037 4 -035 005 Fail 02923 00365 4 3 00712L 04051 0015 4 -034 002 Fail 04051 00149 4 3 01864L 04314 0022 4 -033 003 Fail 04314 00223 4 3 0203L 305500 2051 2 247 283 Fail - - 3L - - 3032

Totgem 4017 0276 mgkg 1-level 206 (181) 7 02266 (3L) 7 6Totstd= 10722 0717 5-level 175 (156) 1

RESULTS Mean = 022663 mgkg

Repeatability variance S2r = 000069Repeatability std Sr = 002626 --gt 1159 r = 00735Between lab variance S2L = 002568Reproducibility var S2R = 002637Reproducibility std SR = 016238 --gt 7165 R = 04547Remarks 1 Lab rejected (3L)

000 050 100 150 200 250 300

k-values

10L

26L

4L

46L

44L

12L

64L

3L

Mandels k statistics(Soil 3 - Sum PBD)

-50 00 50 100 150 200 250 300 350

Deviation from Mean

10L

26L

4L

46L

44L

12L

64L

3L

Labo

rato

ries

Soil 3 - Sum PBD -- Mean PARM = 0227 [mgkg]

-100 000 100 200 300

h-values

10L

26L

4L

46L

44L

12L

64L

3L

Labo

rato

ries

Mandels h statistics(Soil 3 - Sum PBD)

Soil 3-Sum PBD

19

Annex 4

Raw data submitted

Sample Compost1 Sample Compost 1 Sample Compost 1Element PBD 99 Element PBD 100 Element PBD 153

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]4L 00021 10L 00008 44L 000504L 00024 10L 00008 44L 000604L 00014 10L 00007 44L 000504L 00020 10L 00011 46L 00004

10L 00029 46L 00007 46L 0001210L 00027 46L 00012 46L 0000410L 00032 46L 00009 46L 0000946L 00025 46L 00007 12L 0000446L 00052 12L 00008 12L 0000846L 00029 12L 00012 12L 0000446L 00026 12L 00008 12L 0000712L 00026 12L 00014 26L 0000512L 00043 26L 00007 26L 0000512L 00026 26L 0000612L 0004726L 0002626L 00024

Sample Compost 1 Sample Compost 1 Sample Compost 1Element PBD 154 Element PBD 183 Element PBD 196

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]4L 00010 46L 00002 46L 00011

46L 00003 46L 00024 46L 0000846L 00007 46L 00021 12L 0000246L 00003 46L 00003 12L 0000346L 00004 12L 00003 12L 0000112L 00003 12L 00011 12L 0000212L 00005 12L 0000312L 00031 12L 0000312L 00006

Sample Compost 1 Sample Compost 1 Sample Compost 1Element PBD 197 Element PBD 203 Element PBD 209

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00002 46L 00010 4L 0004146L 00023 12L 00002 4L 0008946L 00022 12L 00003 44L 0041012L 00004 12L 00002 44L 0084012L 00006 12L 00002 44L 0064012L 00003 44L 0040012L 00004 12L 00079

12L 0007312L 0006512L 0009326L 0004926L 00049

Sample Compost 1Element PBD 47

LAB PARM [mgkg]26L 0003826L 00039

Element PBD 99 Element PBD 47 Element PBD 209LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]

4L 00170 10L 00210 4L 010004L 00200 10L 00220 4L 018004L 00170 10L 00210 4L 012004L 00190 46L 00300 4L 0220010L 00280 46L 00280 46L 0210010L 00300 46L 00250 46L 0200010L 00290 46L 00260 64L 0351846L 00340 64L 00059 64L 0363846L 00330 64L 00057 64L 0364546L 00300 64L 00062 64L 0350846L 00310 64L 00060 12L 0220964L 00194 12L 00191 12L 0177164L 00154 12L 00187 12L 0292264L 00185 12L 00190 12L 0164664L 00159 12L 00186 26L 0329712L 00242 26L 00666 26L 0300012L 00223 26L 0033212L 0022112L 0022226L 0024626L 00400

Element PBD 203 Element PBD 197 Element PBD 196LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00022 46L 00027 46L 0002446L 00014 46L 00024 46L 0002264L 00036 12L 00161 64L 0005864L 00058 12L 00060 64L 0006512L 00063 12L 00061 12L 0004812L 00034 12L 00036 12L 0002512L 00038 12L 0003212L 00027 12L 00022

Element PBD 183 Element PBD 154 Element PBD 153LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00049 4L 00020 4L 0002246L 00035 4L 00022 4L 0002446L 00036 4L 00020 4L 0002246L 00034 46L 00025 4L 0002664L 00027 46L 00025 46L 0004064L 00023 46L 00025 46L 0004264L 00024 46L 00023 46L 0003564L 00020 64L 00034 46L 0003812L 00230 64L 00023 64L 0007412L 00032 64L 00017 64L 0004712L 00031 64L 00011 64L 0004612L 00030 12L 00030 64L 0003026L 00007 12L 00021 12L 0006526L 00008 12L 00021 12L 00029

12L 00021 12L 0003226L 00015 12L 0002926L 00019 26L 00039

26L 00040

Element PBD 100LAB PARM [mgkg]

4L 000384L 000414L 000374L 00038

38L 0219038L 0220038L 0208038L 0220010L 0004410L 0005010L 0004310L 0004646L 0005746L 0005946L 0005346L 0005312L 0004312L 0004512L 0004312L 0004326L 0006226L 00057

Sample Soil 3 Sample Soil 3 Sample Soil 3Element PBD 99 Element PBD 47 Element PBD 100

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]10L 00016 10L 00011 10L 0000310L 00019 10L 00010 10L 0000410L 00013 10L 00012 10L 0000410L 00019 46L 00007 10L 0000246L 00025 46L 00022 46L 0000246L 00025 46L 00005 46L 0000646L 00008 46L 00007 46L 0000246L 00011 12L 00010 46L 0000264L 00005 12L 00017 3L 29100064L 00005 12L 00010 3L 32000064L 00006 12L 00009 26L 0000564L 00007 26L 00007 26L 0000512L 00012 26L 0000712L 0001312L 0001312L 0001226L 0000526L 00006

Sample Soil 3 Sample Soil 3 Sample Soil 3Element PBD 153 Element PBD 154 Element PBD 196

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]44L 00050 4L 00010 46L 0000744L 00050 46L 00001 46L 0001146L 00002 46L 00002 46L 0000846L 00003 46L 00001 46L 0001146L 00002 46L 00002 64L 0002646L 00002 64L 00001 64L 0002664L 00001 64L 00001 64L 0002964L 00001 64L 00001 64L 0003464L 00001 64L 00002 12L 0004564L 00002 12L 00003 12L 00032

12L 00002 12L 0002212L 00002 12L 0002112L 00002

Sample Soil 3 Sample Soil 3 Sample Soil 3Element PBD 197 Element PBD 203 Element PBD 209

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00006 46L 00011 4L 0091046L 00013 46L 00017 4L 0150046L 00011 46L 00015 4L 0120046L 00013 46L 00018 4L 0160012L 00090 64L 00013 44L 0337012L 00056 64L 00014 44L 0281012L 00033 64L 00016 44L 0287012L 00032 64L 00015 44L 02540

12L 00055 46L 0230012L 00041 46L 0220012L 00027 46L 0150012L 00026 46L 01900

64L 0438164L 0401664L 0414464L 0449812L 0367112L 0397812L 0409112L 03838

Sample Soil 3 26L 0102Element PBD 183 26L 0131

LAB PARM [mgkg]46L 0000746L 0000846L 0005846L 0000764L 0000264L 0000364L 0000364L 0000312L 0001512L 0001112L 0000712L 00007

European Commission EUR 23003 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on polybrominated diphenylethers Author(s) E Sobiecka H van der Sloot D Barcelo B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 68 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07403-5 Abstract Project HORIZONTAL is interdisciplinary aiming at a harmonisation and horizontal standardisation of test procedures in particular for sludge soils and biowastes In the context of this standardization project a series of draft technical specification were designed upon an extensive desk study fine-tuned after expert consultations and finally validated in international intercomparisons exercise This report summarises the work performed within the validation study of the draft standard for the determination of polybrominated diphenylethers (PBDE) in soils sludge and treated bio-waste using gas-chromatography method with mass selective detection (GC-MS) It further explains the underlying statistical concept for the calculation of reproducibility and repeatability from intercomparisons data In addition all single values results of the statistical evaluation as well as background information on the validation materials used are described and explained

The mission of the JRC is to provide customer-driven scientific and technical support for the conception development implementation and monitoring of EU policies As a service of the European Commission the JRC functions as a reference centre of science and technology for the Union Close to the policy-making process it serves the common interest of the Member States while being independent of special interests whether private or national

LB

-NA

-23003-EN

-C

Unit mgkg

Mandels k statistics(Compost 1 - PBD 209)Mandels h statistics(Compost 1 - PBD 209)

Sample Compost 1 NUM

Element PBD 209

General calcparmT1= NUMT2= NUMT3=T4=T5=

n= variabelp=

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 00065 0003 2 -049 032 - - 4L - - NUM

44L 00573 0021 4 150 197 Fail - - 44L - - NUM12L 00078 0001 4 -045 011 - - 12L - - NUM26L 00049 0000 2 -056 000 NUM - 26L - - NUM

Totgem 0019 0006 mgkg 1-level 149 (177) NUM (4L44L12L26L) -1Totstd= 0025 0010 5-level 142 (159) 4

RESULTS Mean = NUM mgkg

Repeatability variance S2r = DIV0Repeatability std Sr = DIV0 --gt DIV0 r = DIV0Between lab variance S2L = NUMReproducibility var S2R = NUMReproducibility std SR = NUM --gt NUM R = NUMRemarks 4 Labs rejected (4L44L12L26L)

000 050 100 150 200

k-values

4L

44L

12L

26L

Mandels k statistics(Compost 1 - PBD 209)

00 01 02 03 04 05 06 07 08 09 10

Deviation from Mean

4L

44L

12L

26L

Labo

rato

ries

NUM

-100 000 100 200

h-values

4L

44L

12L

26L

Labo

rato

ries

Mandels h statistics(Compost 1 - PBD 209)

Compost 1-PBD 209

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 209)Mandels h statistics(Sludge 1 - PBD 209)

Sample Sludge 1 Sludge 1 - PBD 209 -- Mean PARM = 0249 [mgkg]

Element PBD 209

General calcparmT1= 394542E+00T2= 107296E+00T3= 16T4= 56T5= 19723E-02

n= variabelp= 5

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 01550 0055 4 -112 148 Fail 01550 00551 4 3 -009

46L 02050 0007 2 -053 019 02050 00071 2 1 -00412L 02137 0058 4 -042 155 02137 00576 4 3 -00426L 03149 0021 2 078 057 Fail 03149 00210 2 1 00764L 03577 0007 4 129 020 Fail 03577 00074 4 3 011

Totgem 0249 0030 mgkg 1-level 172 (185) 5 02493 () 5 4Totstd= 0084 0025 5-level 157 (162)

RESULTS Mean = 024926 mgkg

Repeatability variance S2r = 000179Repeatability std Sr = 004234 --gt 1699 r = 01186Between lab variance S2L = 000743Reproducibility var S2R = 000922Reproducibility std SR = 009604 --gt 3853 R = 02689Remarks none

000 050 100 150 200

k-values

4L

46L

12L

26L

64L

Mandels k statistics(Sludge 1 - PBD 209)

-01 -01 00 01 01 02

Deviation from Mean

4L

46L

12L

26L

64L

Labo

rato

ries

Sludge 1 - PBD 209 -- Mean PARM = 0249 [mgkg]

-200 -100 000 100 200

h-values

4L

46L

12L

26L

64L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 209)

Sludge 1-PBD 209

Unit mgkg

Mandels k statistics(Soil 3 - PBD 209)Mandels h statistics(Soil 3 - PBD 209)

Sample Soil 3 Soil 3 - PBD 209 -- Mean PARM = 0258 [mgkg]

Element PBD 209

General calcparmT1= 596398E+00T2= 191917E+00T3= 22T4= 84T5= 13249E-02

n= variabelp= 6

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean26L 01162 0021 2 -108 074 Fail 01162 00207 2 1 -0144L 01303 0031 4 -097 111 Fail 01303 00312 4 3 -013

46L 01975 0036 4 -046 128 Fail 01975 00359 4 3 -00644L 02898 0035 4 024 124 Fail 02898 00346 4 3 00312L 03895 0018 4 100 065 Fail 03895 00181 4 3 01364L 04260 0022 4 127 078 Fail 04260 00219 4 3 017

Totgem 0258 0027 mgkg 1-level 187 (177) 6 02582 () 6 5Totstd= 0132 0008 5-level 166 (154)

RESULTS Mean = 025818 mgkg

Repeatability variance S2r = 000083Repeatability std Sr = 002878 --gt 1115 r = 00806Between lab variance S2L = 001640Reproducibility var S2R = 001723Reproducibility std SR = 013127 --gt 5084 R = 03676Remarks none

000 050 100 150

k-values

26L

4L

46L

44L

12L

64L

Mandels k statistics(Soil 3 - PBD 209)

-02 -01 -01 00 01 01 02 02

Deviation from Mean

26L

4L

46L

44L

12L

64L

Labo

rato

ries

Soil 3 - PBD 209 -- Mean PARM = 0258 [mgkg]

-200 -100 000 100 200

h-values

26L

4L

46L

44L

12L

64L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 209)

Soil 3-PBD 209

Unit mgkg

Mandels k statistics(Compost 1 - Sum PBD)Mandels h statistics(Compost 1 - Sum PBD)

Sample Compost 1 Compost 1 - Sum PBD -- Mean PARM = 0009 [mgkg]

Element Sum PBD

General calcparmT1= 154064E-01T2= 169065E-03T3= 18T4= 68T5= 11354E-04

n= variabelp= 5

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00031 0002 4 -067 016 00031 00016 4 3 -0014L 00055 0005 4 -056 048 00055 00047 4 3 000

46L 00085 0003 4 -042 031 00085 00030 4 3 00026L 00123 0000 2 -024 003 00123 00002 2 1 00012L 00154 0002 4 -011 021 00154 00021 4 3 00144L 00613 0023 4 200 237 Fail - - 44L - - 005

Totgem 0018 0006 mgkg 1-level 187 (177) 5 00089 (44L) 5 4Totstd= 0022 0009 5-level 166 (154) 1

RESULTS Mean = 000893 mgkg

Repeatability variance S2r = 000001Repeatability std Sr = 000296 --gt 3308 r = 00083Between lab variance S2L = 000002Reproducibility var S2R = 000003Reproducibility std SR = 000570 --gt 6374 R = 00159Remarks 1 Lab rejected (44L)

000 050 100 150 200 250

k-values

10L

4L

46L

26L

12L

44L

Mandels k statistics(Compost 1 - Sum PBD)

00 00 00 00 00 00 01 01

Deviation from Mean

10L

4L

46L

26L

12L

44L

Labo

rato

ries

Compost 1 - Sum PBD -- Mean PARM = 0009 [mgkg]

-100 000 100 200

h-values

10L

4L

46L

26L

12L

44L

Labo

rato

ries

Mandels h statistics(Compost 1 - Sum PBD)

Compost 1-Sum PBD

Unit mgkg

Mandels k statistics(Sludge 1 - Sum PBD)Mandels h statistics(Sludge 1 - Sum PBD)

Sample Sludge 1 Sludge 1 - Sum PBD -- Mean PARM = 0256 [mgkg]

Element Sum PBD

General calcparmT1= 531806E+00T2= 162188E+00T3= 22T4= 84T5= 25223E-02

n= variabelp= 6

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00423 0025 4 -156 044 Fail 00423 00252 4 3 -02146L 01808 0118 4 -049 205 - - 46L - - -0074L 01810 0056 4 -049 097 01810 00558 4 3 -007

38L 02168 0006 4 -022 010 02168 00059 4 3 -00412L 02890 0065 4 034 113 02890 00647 4 3 00364L 03958 0008 4 116 014 Fail 03958 00079 4 3 01426L 04094 0034 2 126 059 Fail 04094 00337 2 1 015

Totgem 0245 0044 mgkg 1-level 198 (179) 6 02557 (46L) 6 5Totstd= 0130 0039 5-level 171 (155) 1

RESULTS Mean = 025570 mgkg

Repeatability variance S2r = 000158Repeatability std Sr = 003970 --gt 1553 r = 01112Between lab variance S2L = 001807Reproducibility var S2R = 001964Reproducibility std SR = 014015 --gt 5481 R = 03924Remarks 1 Lab rejected (46L)

000 050 100 150 200 250

k-values

10L

46L

4L

38L

12L

64L

26L

Mandels k statistics(Sludge 1 - Sum PBD)

-03 -02 -02 -01 -01 00 01 01 02 02

Deviation from Mean

10L

46L

4L

38L

12L

64L

26L

Labo

rato

ries

Sludge 1 - Sum PBD -- Mean PARM = 0256 [mgkg]

-200 -100 000 100 200

h-values

10L

46L

4L

38L

12L

64L

26L

Labo

rato

ries

Mandels h statistics(Sludge 1 - Sum PBD)

Sludge 1-Sum PBD

Unit mgkg

Mandels k statistics(Soil 3 - Sum PBD)Mandels h statistics(Soil 3 - Sum PBD)

Sample Soil 3 Soil 3 - Sum PBD -- Mean PARM = 0227 [mgkg]

Element Sum PBD

General calcparmT1= 610980E+00T2= 200876E+00T3= 26T4= 100T5= 13106E-02

n= variabelp= 7

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00028 0001 4 -037 000 Fail 00028 00005 4 3 -02226L 01179 0021 2 -036 003 Fail 01179 00208 2 1 -0114L 01305 0031 4 -036 004 Fail 01305 00308 4 3 -010

46L 02065 0035 4 -036 005 Fail 02065 00350 4 3 -00244L 02923 0037 4 -035 005 Fail 02923 00365 4 3 00712L 04051 0015 4 -034 002 Fail 04051 00149 4 3 01864L 04314 0022 4 -033 003 Fail 04314 00223 4 3 0203L 305500 2051 2 247 283 Fail - - 3L - - 3032

Totgem 4017 0276 mgkg 1-level 206 (181) 7 02266 (3L) 7 6Totstd= 10722 0717 5-level 175 (156) 1

RESULTS Mean = 022663 mgkg

Repeatability variance S2r = 000069Repeatability std Sr = 002626 --gt 1159 r = 00735Between lab variance S2L = 002568Reproducibility var S2R = 002637Reproducibility std SR = 016238 --gt 7165 R = 04547Remarks 1 Lab rejected (3L)

000 050 100 150 200 250 300

k-values

10L

26L

4L

46L

44L

12L

64L

3L

Mandels k statistics(Soil 3 - Sum PBD)

-50 00 50 100 150 200 250 300 350

Deviation from Mean

10L

26L

4L

46L

44L

12L

64L

3L

Labo

rato

ries

Soil 3 - Sum PBD -- Mean PARM = 0227 [mgkg]

-100 000 100 200 300

h-values

10L

26L

4L

46L

44L

12L

64L

3L

Labo

rato

ries

Mandels h statistics(Soil 3 - Sum PBD)

Soil 3-Sum PBD

19

Annex 4

Raw data submitted

Sample Compost1 Sample Compost 1 Sample Compost 1Element PBD 99 Element PBD 100 Element PBD 153

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]4L 00021 10L 00008 44L 000504L 00024 10L 00008 44L 000604L 00014 10L 00007 44L 000504L 00020 10L 00011 46L 00004

10L 00029 46L 00007 46L 0001210L 00027 46L 00012 46L 0000410L 00032 46L 00009 46L 0000946L 00025 46L 00007 12L 0000446L 00052 12L 00008 12L 0000846L 00029 12L 00012 12L 0000446L 00026 12L 00008 12L 0000712L 00026 12L 00014 26L 0000512L 00043 26L 00007 26L 0000512L 00026 26L 0000612L 0004726L 0002626L 00024

Sample Compost 1 Sample Compost 1 Sample Compost 1Element PBD 154 Element PBD 183 Element PBD 196

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]4L 00010 46L 00002 46L 00011

46L 00003 46L 00024 46L 0000846L 00007 46L 00021 12L 0000246L 00003 46L 00003 12L 0000346L 00004 12L 00003 12L 0000112L 00003 12L 00011 12L 0000212L 00005 12L 0000312L 00031 12L 0000312L 00006

Sample Compost 1 Sample Compost 1 Sample Compost 1Element PBD 197 Element PBD 203 Element PBD 209

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00002 46L 00010 4L 0004146L 00023 12L 00002 4L 0008946L 00022 12L 00003 44L 0041012L 00004 12L 00002 44L 0084012L 00006 12L 00002 44L 0064012L 00003 44L 0040012L 00004 12L 00079

12L 0007312L 0006512L 0009326L 0004926L 00049

Sample Compost 1Element PBD 47

LAB PARM [mgkg]26L 0003826L 00039

Element PBD 99 Element PBD 47 Element PBD 209LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]

4L 00170 10L 00210 4L 010004L 00200 10L 00220 4L 018004L 00170 10L 00210 4L 012004L 00190 46L 00300 4L 0220010L 00280 46L 00280 46L 0210010L 00300 46L 00250 46L 0200010L 00290 46L 00260 64L 0351846L 00340 64L 00059 64L 0363846L 00330 64L 00057 64L 0364546L 00300 64L 00062 64L 0350846L 00310 64L 00060 12L 0220964L 00194 12L 00191 12L 0177164L 00154 12L 00187 12L 0292264L 00185 12L 00190 12L 0164664L 00159 12L 00186 26L 0329712L 00242 26L 00666 26L 0300012L 00223 26L 0033212L 0022112L 0022226L 0024626L 00400

Element PBD 203 Element PBD 197 Element PBD 196LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00022 46L 00027 46L 0002446L 00014 46L 00024 46L 0002264L 00036 12L 00161 64L 0005864L 00058 12L 00060 64L 0006512L 00063 12L 00061 12L 0004812L 00034 12L 00036 12L 0002512L 00038 12L 0003212L 00027 12L 00022

Element PBD 183 Element PBD 154 Element PBD 153LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00049 4L 00020 4L 0002246L 00035 4L 00022 4L 0002446L 00036 4L 00020 4L 0002246L 00034 46L 00025 4L 0002664L 00027 46L 00025 46L 0004064L 00023 46L 00025 46L 0004264L 00024 46L 00023 46L 0003564L 00020 64L 00034 46L 0003812L 00230 64L 00023 64L 0007412L 00032 64L 00017 64L 0004712L 00031 64L 00011 64L 0004612L 00030 12L 00030 64L 0003026L 00007 12L 00021 12L 0006526L 00008 12L 00021 12L 00029

12L 00021 12L 0003226L 00015 12L 0002926L 00019 26L 00039

26L 00040

Element PBD 100LAB PARM [mgkg]

4L 000384L 000414L 000374L 00038

38L 0219038L 0220038L 0208038L 0220010L 0004410L 0005010L 0004310L 0004646L 0005746L 0005946L 0005346L 0005312L 0004312L 0004512L 0004312L 0004326L 0006226L 00057

Sample Soil 3 Sample Soil 3 Sample Soil 3Element PBD 99 Element PBD 47 Element PBD 100

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]10L 00016 10L 00011 10L 0000310L 00019 10L 00010 10L 0000410L 00013 10L 00012 10L 0000410L 00019 46L 00007 10L 0000246L 00025 46L 00022 46L 0000246L 00025 46L 00005 46L 0000646L 00008 46L 00007 46L 0000246L 00011 12L 00010 46L 0000264L 00005 12L 00017 3L 29100064L 00005 12L 00010 3L 32000064L 00006 12L 00009 26L 0000564L 00007 26L 00007 26L 0000512L 00012 26L 0000712L 0001312L 0001312L 0001226L 0000526L 00006

Sample Soil 3 Sample Soil 3 Sample Soil 3Element PBD 153 Element PBD 154 Element PBD 196

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]44L 00050 4L 00010 46L 0000744L 00050 46L 00001 46L 0001146L 00002 46L 00002 46L 0000846L 00003 46L 00001 46L 0001146L 00002 46L 00002 64L 0002646L 00002 64L 00001 64L 0002664L 00001 64L 00001 64L 0002964L 00001 64L 00001 64L 0003464L 00001 64L 00002 12L 0004564L 00002 12L 00003 12L 00032

12L 00002 12L 0002212L 00002 12L 0002112L 00002

Sample Soil 3 Sample Soil 3 Sample Soil 3Element PBD 197 Element PBD 203 Element PBD 209

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00006 46L 00011 4L 0091046L 00013 46L 00017 4L 0150046L 00011 46L 00015 4L 0120046L 00013 46L 00018 4L 0160012L 00090 64L 00013 44L 0337012L 00056 64L 00014 44L 0281012L 00033 64L 00016 44L 0287012L 00032 64L 00015 44L 02540

12L 00055 46L 0230012L 00041 46L 0220012L 00027 46L 0150012L 00026 46L 01900

64L 0438164L 0401664L 0414464L 0449812L 0367112L 0397812L 0409112L 03838

Sample Soil 3 26L 0102Element PBD 183 26L 0131

LAB PARM [mgkg]46L 0000746L 0000846L 0005846L 0000764L 0000264L 0000364L 0000364L 0000312L 0001512L 0001112L 0000712L 00007

European Commission EUR 23003 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on polybrominated diphenylethers Author(s) E Sobiecka H van der Sloot D Barcelo B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 68 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07403-5 Abstract Project HORIZONTAL is interdisciplinary aiming at a harmonisation and horizontal standardisation of test procedures in particular for sludge soils and biowastes In the context of this standardization project a series of draft technical specification were designed upon an extensive desk study fine-tuned after expert consultations and finally validated in international intercomparisons exercise This report summarises the work performed within the validation study of the draft standard for the determination of polybrominated diphenylethers (PBDE) in soils sludge and treated bio-waste using gas-chromatography method with mass selective detection (GC-MS) It further explains the underlying statistical concept for the calculation of reproducibility and repeatability from intercomparisons data In addition all single values results of the statistical evaluation as well as background information on the validation materials used are described and explained

The mission of the JRC is to provide customer-driven scientific and technical support for the conception development implementation and monitoring of EU policies As a service of the European Commission the JRC functions as a reference centre of science and technology for the Union Close to the policy-making process it serves the common interest of the Member States while being independent of special interests whether private or national

LB

-NA

-23003-EN

-C

Unit mgkg

Mandels k statistics(Sludge 1 - PBD 209)Mandels h statistics(Sludge 1 - PBD 209)

Sample Sludge 1 Sludge 1 - PBD 209 -- Mean PARM = 0249 [mgkg]

Element PBD 209

General calcparmT1= 394542E+00T2= 107296E+00T3= 16T4= 56T5= 19723E-02

n= variabelp= 5

N-table= 3

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean4L 01550 0055 4 -112 148 Fail 01550 00551 4 3 -009

46L 02050 0007 2 -053 019 02050 00071 2 1 -00412L 02137 0058 4 -042 155 02137 00576 4 3 -00426L 03149 0021 2 078 057 Fail 03149 00210 2 1 00764L 03577 0007 4 129 020 Fail 03577 00074 4 3 011

Totgem 0249 0030 mgkg 1-level 172 (185) 5 02493 () 5 4Totstd= 0084 0025 5-level 157 (162)

RESULTS Mean = 024926 mgkg

Repeatability variance S2r = 000179Repeatability std Sr = 004234 --gt 1699 r = 01186Between lab variance S2L = 000743Reproducibility var S2R = 000922Reproducibility std SR = 009604 --gt 3853 R = 02689Remarks none

000 050 100 150 200

k-values

4L

46L

12L

26L

64L

Mandels k statistics(Sludge 1 - PBD 209)

-01 -01 00 01 01 02

Deviation from Mean

4L

46L

12L

26L

64L

Labo

rato

ries

Sludge 1 - PBD 209 -- Mean PARM = 0249 [mgkg]

-200 -100 000 100 200

h-values

4L

46L

12L

26L

64L

Labo

rato

ries

Mandels h statistics(Sludge 1 - PBD 209)

Sludge 1-PBD 209

Unit mgkg

Mandels k statistics(Soil 3 - PBD 209)Mandels h statistics(Soil 3 - PBD 209)

Sample Soil 3 Soil 3 - PBD 209 -- Mean PARM = 0258 [mgkg]

Element PBD 209

General calcparmT1= 596398E+00T2= 191917E+00T3= 22T4= 84T5= 13249E-02

n= variabelp= 6

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean26L 01162 0021 2 -108 074 Fail 01162 00207 2 1 -0144L 01303 0031 4 -097 111 Fail 01303 00312 4 3 -013

46L 01975 0036 4 -046 128 Fail 01975 00359 4 3 -00644L 02898 0035 4 024 124 Fail 02898 00346 4 3 00312L 03895 0018 4 100 065 Fail 03895 00181 4 3 01364L 04260 0022 4 127 078 Fail 04260 00219 4 3 017

Totgem 0258 0027 mgkg 1-level 187 (177) 6 02582 () 6 5Totstd= 0132 0008 5-level 166 (154)

RESULTS Mean = 025818 mgkg

Repeatability variance S2r = 000083Repeatability std Sr = 002878 --gt 1115 r = 00806Between lab variance S2L = 001640Reproducibility var S2R = 001723Reproducibility std SR = 013127 --gt 5084 R = 03676Remarks none

000 050 100 150

k-values

26L

4L

46L

44L

12L

64L

Mandels k statistics(Soil 3 - PBD 209)

-02 -01 -01 00 01 01 02 02

Deviation from Mean

26L

4L

46L

44L

12L

64L

Labo

rato

ries

Soil 3 - PBD 209 -- Mean PARM = 0258 [mgkg]

-200 -100 000 100 200

h-values

26L

4L

46L

44L

12L

64L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 209)

Soil 3-PBD 209

Unit mgkg

Mandels k statistics(Compost 1 - Sum PBD)Mandels h statistics(Compost 1 - Sum PBD)

Sample Compost 1 Compost 1 - Sum PBD -- Mean PARM = 0009 [mgkg]

Element Sum PBD

General calcparmT1= 154064E-01T2= 169065E-03T3= 18T4= 68T5= 11354E-04

n= variabelp= 5

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00031 0002 4 -067 016 00031 00016 4 3 -0014L 00055 0005 4 -056 048 00055 00047 4 3 000

46L 00085 0003 4 -042 031 00085 00030 4 3 00026L 00123 0000 2 -024 003 00123 00002 2 1 00012L 00154 0002 4 -011 021 00154 00021 4 3 00144L 00613 0023 4 200 237 Fail - - 44L - - 005

Totgem 0018 0006 mgkg 1-level 187 (177) 5 00089 (44L) 5 4Totstd= 0022 0009 5-level 166 (154) 1

RESULTS Mean = 000893 mgkg

Repeatability variance S2r = 000001Repeatability std Sr = 000296 --gt 3308 r = 00083Between lab variance S2L = 000002Reproducibility var S2R = 000003Reproducibility std SR = 000570 --gt 6374 R = 00159Remarks 1 Lab rejected (44L)

000 050 100 150 200 250

k-values

10L

4L

46L

26L

12L

44L

Mandels k statistics(Compost 1 - Sum PBD)

00 00 00 00 00 00 01 01

Deviation from Mean

10L

4L

46L

26L

12L

44L

Labo

rato

ries

Compost 1 - Sum PBD -- Mean PARM = 0009 [mgkg]

-100 000 100 200

h-values

10L

4L

46L

26L

12L

44L

Labo

rato

ries

Mandels h statistics(Compost 1 - Sum PBD)

Compost 1-Sum PBD

Unit mgkg

Mandels k statistics(Sludge 1 - Sum PBD)Mandels h statistics(Sludge 1 - Sum PBD)

Sample Sludge 1 Sludge 1 - Sum PBD -- Mean PARM = 0256 [mgkg]

Element Sum PBD

General calcparmT1= 531806E+00T2= 162188E+00T3= 22T4= 84T5= 25223E-02

n= variabelp= 6

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00423 0025 4 -156 044 Fail 00423 00252 4 3 -02146L 01808 0118 4 -049 205 - - 46L - - -0074L 01810 0056 4 -049 097 01810 00558 4 3 -007

38L 02168 0006 4 -022 010 02168 00059 4 3 -00412L 02890 0065 4 034 113 02890 00647 4 3 00364L 03958 0008 4 116 014 Fail 03958 00079 4 3 01426L 04094 0034 2 126 059 Fail 04094 00337 2 1 015

Totgem 0245 0044 mgkg 1-level 198 (179) 6 02557 (46L) 6 5Totstd= 0130 0039 5-level 171 (155) 1

RESULTS Mean = 025570 mgkg

Repeatability variance S2r = 000158Repeatability std Sr = 003970 --gt 1553 r = 01112Between lab variance S2L = 001807Reproducibility var S2R = 001964Reproducibility std SR = 014015 --gt 5481 R = 03924Remarks 1 Lab rejected (46L)

000 050 100 150 200 250

k-values

10L

46L

4L

38L

12L

64L

26L

Mandels k statistics(Sludge 1 - Sum PBD)

-03 -02 -02 -01 -01 00 01 01 02 02

Deviation from Mean

10L

46L

4L

38L

12L

64L

26L

Labo

rato

ries

Sludge 1 - Sum PBD -- Mean PARM = 0256 [mgkg]

-200 -100 000 100 200

h-values

10L

46L

4L

38L

12L

64L

26L

Labo

rato

ries

Mandels h statistics(Sludge 1 - Sum PBD)

Sludge 1-Sum PBD

Unit mgkg

Mandels k statistics(Soil 3 - Sum PBD)Mandels h statistics(Soil 3 - Sum PBD)

Sample Soil 3 Soil 3 - Sum PBD -- Mean PARM = 0227 [mgkg]

Element Sum PBD

General calcparmT1= 610980E+00T2= 200876E+00T3= 26T4= 100T5= 13106E-02

n= variabelp= 7

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00028 0001 4 -037 000 Fail 00028 00005 4 3 -02226L 01179 0021 2 -036 003 Fail 01179 00208 2 1 -0114L 01305 0031 4 -036 004 Fail 01305 00308 4 3 -010

46L 02065 0035 4 -036 005 Fail 02065 00350 4 3 -00244L 02923 0037 4 -035 005 Fail 02923 00365 4 3 00712L 04051 0015 4 -034 002 Fail 04051 00149 4 3 01864L 04314 0022 4 -033 003 Fail 04314 00223 4 3 0203L 305500 2051 2 247 283 Fail - - 3L - - 3032

Totgem 4017 0276 mgkg 1-level 206 (181) 7 02266 (3L) 7 6Totstd= 10722 0717 5-level 175 (156) 1

RESULTS Mean = 022663 mgkg

Repeatability variance S2r = 000069Repeatability std Sr = 002626 --gt 1159 r = 00735Between lab variance S2L = 002568Reproducibility var S2R = 002637Reproducibility std SR = 016238 --gt 7165 R = 04547Remarks 1 Lab rejected (3L)

000 050 100 150 200 250 300

k-values

10L

26L

4L

46L

44L

12L

64L

3L

Mandels k statistics(Soil 3 - Sum PBD)

-50 00 50 100 150 200 250 300 350

Deviation from Mean

10L

26L

4L

46L

44L

12L

64L

3L

Labo

rato

ries

Soil 3 - Sum PBD -- Mean PARM = 0227 [mgkg]

-100 000 100 200 300

h-values

10L

26L

4L

46L

44L

12L

64L

3L

Labo

rato

ries

Mandels h statistics(Soil 3 - Sum PBD)

Soil 3-Sum PBD

19

Annex 4

Raw data submitted

Sample Compost1 Sample Compost 1 Sample Compost 1Element PBD 99 Element PBD 100 Element PBD 153

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]4L 00021 10L 00008 44L 000504L 00024 10L 00008 44L 000604L 00014 10L 00007 44L 000504L 00020 10L 00011 46L 00004

10L 00029 46L 00007 46L 0001210L 00027 46L 00012 46L 0000410L 00032 46L 00009 46L 0000946L 00025 46L 00007 12L 0000446L 00052 12L 00008 12L 0000846L 00029 12L 00012 12L 0000446L 00026 12L 00008 12L 0000712L 00026 12L 00014 26L 0000512L 00043 26L 00007 26L 0000512L 00026 26L 0000612L 0004726L 0002626L 00024

Sample Compost 1 Sample Compost 1 Sample Compost 1Element PBD 154 Element PBD 183 Element PBD 196

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]4L 00010 46L 00002 46L 00011

46L 00003 46L 00024 46L 0000846L 00007 46L 00021 12L 0000246L 00003 46L 00003 12L 0000346L 00004 12L 00003 12L 0000112L 00003 12L 00011 12L 0000212L 00005 12L 0000312L 00031 12L 0000312L 00006

Sample Compost 1 Sample Compost 1 Sample Compost 1Element PBD 197 Element PBD 203 Element PBD 209

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00002 46L 00010 4L 0004146L 00023 12L 00002 4L 0008946L 00022 12L 00003 44L 0041012L 00004 12L 00002 44L 0084012L 00006 12L 00002 44L 0064012L 00003 44L 0040012L 00004 12L 00079

12L 0007312L 0006512L 0009326L 0004926L 00049

Sample Compost 1Element PBD 47

LAB PARM [mgkg]26L 0003826L 00039

Element PBD 99 Element PBD 47 Element PBD 209LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]

4L 00170 10L 00210 4L 010004L 00200 10L 00220 4L 018004L 00170 10L 00210 4L 012004L 00190 46L 00300 4L 0220010L 00280 46L 00280 46L 0210010L 00300 46L 00250 46L 0200010L 00290 46L 00260 64L 0351846L 00340 64L 00059 64L 0363846L 00330 64L 00057 64L 0364546L 00300 64L 00062 64L 0350846L 00310 64L 00060 12L 0220964L 00194 12L 00191 12L 0177164L 00154 12L 00187 12L 0292264L 00185 12L 00190 12L 0164664L 00159 12L 00186 26L 0329712L 00242 26L 00666 26L 0300012L 00223 26L 0033212L 0022112L 0022226L 0024626L 00400

Element PBD 203 Element PBD 197 Element PBD 196LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00022 46L 00027 46L 0002446L 00014 46L 00024 46L 0002264L 00036 12L 00161 64L 0005864L 00058 12L 00060 64L 0006512L 00063 12L 00061 12L 0004812L 00034 12L 00036 12L 0002512L 00038 12L 0003212L 00027 12L 00022

Element PBD 183 Element PBD 154 Element PBD 153LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00049 4L 00020 4L 0002246L 00035 4L 00022 4L 0002446L 00036 4L 00020 4L 0002246L 00034 46L 00025 4L 0002664L 00027 46L 00025 46L 0004064L 00023 46L 00025 46L 0004264L 00024 46L 00023 46L 0003564L 00020 64L 00034 46L 0003812L 00230 64L 00023 64L 0007412L 00032 64L 00017 64L 0004712L 00031 64L 00011 64L 0004612L 00030 12L 00030 64L 0003026L 00007 12L 00021 12L 0006526L 00008 12L 00021 12L 00029

12L 00021 12L 0003226L 00015 12L 0002926L 00019 26L 00039

26L 00040

Element PBD 100LAB PARM [mgkg]

4L 000384L 000414L 000374L 00038

38L 0219038L 0220038L 0208038L 0220010L 0004410L 0005010L 0004310L 0004646L 0005746L 0005946L 0005346L 0005312L 0004312L 0004512L 0004312L 0004326L 0006226L 00057

Sample Soil 3 Sample Soil 3 Sample Soil 3Element PBD 99 Element PBD 47 Element PBD 100

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]10L 00016 10L 00011 10L 0000310L 00019 10L 00010 10L 0000410L 00013 10L 00012 10L 0000410L 00019 46L 00007 10L 0000246L 00025 46L 00022 46L 0000246L 00025 46L 00005 46L 0000646L 00008 46L 00007 46L 0000246L 00011 12L 00010 46L 0000264L 00005 12L 00017 3L 29100064L 00005 12L 00010 3L 32000064L 00006 12L 00009 26L 0000564L 00007 26L 00007 26L 0000512L 00012 26L 0000712L 0001312L 0001312L 0001226L 0000526L 00006

Sample Soil 3 Sample Soil 3 Sample Soil 3Element PBD 153 Element PBD 154 Element PBD 196

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]44L 00050 4L 00010 46L 0000744L 00050 46L 00001 46L 0001146L 00002 46L 00002 46L 0000846L 00003 46L 00001 46L 0001146L 00002 46L 00002 64L 0002646L 00002 64L 00001 64L 0002664L 00001 64L 00001 64L 0002964L 00001 64L 00001 64L 0003464L 00001 64L 00002 12L 0004564L 00002 12L 00003 12L 00032

12L 00002 12L 0002212L 00002 12L 0002112L 00002

Sample Soil 3 Sample Soil 3 Sample Soil 3Element PBD 197 Element PBD 203 Element PBD 209

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00006 46L 00011 4L 0091046L 00013 46L 00017 4L 0150046L 00011 46L 00015 4L 0120046L 00013 46L 00018 4L 0160012L 00090 64L 00013 44L 0337012L 00056 64L 00014 44L 0281012L 00033 64L 00016 44L 0287012L 00032 64L 00015 44L 02540

12L 00055 46L 0230012L 00041 46L 0220012L 00027 46L 0150012L 00026 46L 01900

64L 0438164L 0401664L 0414464L 0449812L 0367112L 0397812L 0409112L 03838

Sample Soil 3 26L 0102Element PBD 183 26L 0131

LAB PARM [mgkg]46L 0000746L 0000846L 0005846L 0000764L 0000264L 0000364L 0000364L 0000312L 0001512L 0001112L 0000712L 00007

European Commission EUR 23003 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on polybrominated diphenylethers Author(s) E Sobiecka H van der Sloot D Barcelo B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 68 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07403-5 Abstract Project HORIZONTAL is interdisciplinary aiming at a harmonisation and horizontal standardisation of test procedures in particular for sludge soils and biowastes In the context of this standardization project a series of draft technical specification were designed upon an extensive desk study fine-tuned after expert consultations and finally validated in international intercomparisons exercise This report summarises the work performed within the validation study of the draft standard for the determination of polybrominated diphenylethers (PBDE) in soils sludge and treated bio-waste using gas-chromatography method with mass selective detection (GC-MS) It further explains the underlying statistical concept for the calculation of reproducibility and repeatability from intercomparisons data In addition all single values results of the statistical evaluation as well as background information on the validation materials used are described and explained

The mission of the JRC is to provide customer-driven scientific and technical support for the conception development implementation and monitoring of EU policies As a service of the European Commission the JRC functions as a reference centre of science and technology for the Union Close to the policy-making process it serves the common interest of the Member States while being independent of special interests whether private or national

LB

-NA

-23003-EN

-C

Unit mgkg

Mandels k statistics(Soil 3 - PBD 209)Mandels h statistics(Soil 3 - PBD 209)

Sample Soil 3 Soil 3 - PBD 209 -- Mean PARM = 0258 [mgkg]

Element PBD 209

General calcparmT1= 596398E+00T2= 191917E+00T3= 22T4= 84T5= 13249E-02

n= variabelp= 6

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean26L 01162 0021 2 -108 074 Fail 01162 00207 2 1 -0144L 01303 0031 4 -097 111 Fail 01303 00312 4 3 -013

46L 01975 0036 4 -046 128 Fail 01975 00359 4 3 -00644L 02898 0035 4 024 124 Fail 02898 00346 4 3 00312L 03895 0018 4 100 065 Fail 03895 00181 4 3 01364L 04260 0022 4 127 078 Fail 04260 00219 4 3 017

Totgem 0258 0027 mgkg 1-level 187 (177) 6 02582 () 6 5Totstd= 0132 0008 5-level 166 (154)

RESULTS Mean = 025818 mgkg

Repeatability variance S2r = 000083Repeatability std Sr = 002878 --gt 1115 r = 00806Between lab variance S2L = 001640Reproducibility var S2R = 001723Reproducibility std SR = 013127 --gt 5084 R = 03676Remarks none

000 050 100 150

k-values

26L

4L

46L

44L

12L

64L

Mandels k statistics(Soil 3 - PBD 209)

-02 -01 -01 00 01 01 02 02

Deviation from Mean

26L

4L

46L

44L

12L

64L

Labo

rato

ries

Soil 3 - PBD 209 -- Mean PARM = 0258 [mgkg]

-200 -100 000 100 200

h-values

26L

4L

46L

44L

12L

64L

Labo

rato

ries

Mandels h statistics(Soil 3 - PBD 209)

Soil 3-PBD 209

Unit mgkg

Mandels k statistics(Compost 1 - Sum PBD)Mandels h statistics(Compost 1 - Sum PBD)

Sample Compost 1 Compost 1 - Sum PBD -- Mean PARM = 0009 [mgkg]

Element Sum PBD

General calcparmT1= 154064E-01T2= 169065E-03T3= 18T4= 68T5= 11354E-04

n= variabelp= 5

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00031 0002 4 -067 016 00031 00016 4 3 -0014L 00055 0005 4 -056 048 00055 00047 4 3 000

46L 00085 0003 4 -042 031 00085 00030 4 3 00026L 00123 0000 2 -024 003 00123 00002 2 1 00012L 00154 0002 4 -011 021 00154 00021 4 3 00144L 00613 0023 4 200 237 Fail - - 44L - - 005

Totgem 0018 0006 mgkg 1-level 187 (177) 5 00089 (44L) 5 4Totstd= 0022 0009 5-level 166 (154) 1

RESULTS Mean = 000893 mgkg

Repeatability variance S2r = 000001Repeatability std Sr = 000296 --gt 3308 r = 00083Between lab variance S2L = 000002Reproducibility var S2R = 000003Reproducibility std SR = 000570 --gt 6374 R = 00159Remarks 1 Lab rejected (44L)

000 050 100 150 200 250

k-values

10L

4L

46L

26L

12L

44L

Mandels k statistics(Compost 1 - Sum PBD)

00 00 00 00 00 00 01 01

Deviation from Mean

10L

4L

46L

26L

12L

44L

Labo

rato

ries

Compost 1 - Sum PBD -- Mean PARM = 0009 [mgkg]

-100 000 100 200

h-values

10L

4L

46L

26L

12L

44L

Labo

rato

ries

Mandels h statistics(Compost 1 - Sum PBD)

Compost 1-Sum PBD

Unit mgkg

Mandels k statistics(Sludge 1 - Sum PBD)Mandels h statistics(Sludge 1 - Sum PBD)

Sample Sludge 1 Sludge 1 - Sum PBD -- Mean PARM = 0256 [mgkg]

Element Sum PBD

General calcparmT1= 531806E+00T2= 162188E+00T3= 22T4= 84T5= 25223E-02

n= variabelp= 6

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00423 0025 4 -156 044 Fail 00423 00252 4 3 -02146L 01808 0118 4 -049 205 - - 46L - - -0074L 01810 0056 4 -049 097 01810 00558 4 3 -007

38L 02168 0006 4 -022 010 02168 00059 4 3 -00412L 02890 0065 4 034 113 02890 00647 4 3 00364L 03958 0008 4 116 014 Fail 03958 00079 4 3 01426L 04094 0034 2 126 059 Fail 04094 00337 2 1 015

Totgem 0245 0044 mgkg 1-level 198 (179) 6 02557 (46L) 6 5Totstd= 0130 0039 5-level 171 (155) 1

RESULTS Mean = 025570 mgkg

Repeatability variance S2r = 000158Repeatability std Sr = 003970 --gt 1553 r = 01112Between lab variance S2L = 001807Reproducibility var S2R = 001964Reproducibility std SR = 014015 --gt 5481 R = 03924Remarks 1 Lab rejected (46L)

000 050 100 150 200 250

k-values

10L

46L

4L

38L

12L

64L

26L

Mandels k statistics(Sludge 1 - Sum PBD)

-03 -02 -02 -01 -01 00 01 01 02 02

Deviation from Mean

10L

46L

4L

38L

12L

64L

26L

Labo

rato

ries

Sludge 1 - Sum PBD -- Mean PARM = 0256 [mgkg]

-200 -100 000 100 200

h-values

10L

46L

4L

38L

12L

64L

26L

Labo

rato

ries

Mandels h statistics(Sludge 1 - Sum PBD)

Sludge 1-Sum PBD

Unit mgkg

Mandels k statistics(Soil 3 - Sum PBD)Mandels h statistics(Soil 3 - Sum PBD)

Sample Soil 3 Soil 3 - Sum PBD -- Mean PARM = 0227 [mgkg]

Element Sum PBD

General calcparmT1= 610980E+00T2= 200876E+00T3= 26T4= 100T5= 13106E-02

n= variabelp= 7

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00028 0001 4 -037 000 Fail 00028 00005 4 3 -02226L 01179 0021 2 -036 003 Fail 01179 00208 2 1 -0114L 01305 0031 4 -036 004 Fail 01305 00308 4 3 -010

46L 02065 0035 4 -036 005 Fail 02065 00350 4 3 -00244L 02923 0037 4 -035 005 Fail 02923 00365 4 3 00712L 04051 0015 4 -034 002 Fail 04051 00149 4 3 01864L 04314 0022 4 -033 003 Fail 04314 00223 4 3 0203L 305500 2051 2 247 283 Fail - - 3L - - 3032

Totgem 4017 0276 mgkg 1-level 206 (181) 7 02266 (3L) 7 6Totstd= 10722 0717 5-level 175 (156) 1

RESULTS Mean = 022663 mgkg

Repeatability variance S2r = 000069Repeatability std Sr = 002626 --gt 1159 r = 00735Between lab variance S2L = 002568Reproducibility var S2R = 002637Reproducibility std SR = 016238 --gt 7165 R = 04547Remarks 1 Lab rejected (3L)

000 050 100 150 200 250 300

k-values

10L

26L

4L

46L

44L

12L

64L

3L

Mandels k statistics(Soil 3 - Sum PBD)

-50 00 50 100 150 200 250 300 350

Deviation from Mean

10L

26L

4L

46L

44L

12L

64L

3L

Labo

rato

ries

Soil 3 - Sum PBD -- Mean PARM = 0227 [mgkg]

-100 000 100 200 300

h-values

10L

26L

4L

46L

44L

12L

64L

3L

Labo

rato

ries

Mandels h statistics(Soil 3 - Sum PBD)

Soil 3-Sum PBD

19

Annex 4

Raw data submitted

Sample Compost1 Sample Compost 1 Sample Compost 1Element PBD 99 Element PBD 100 Element PBD 153

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]4L 00021 10L 00008 44L 000504L 00024 10L 00008 44L 000604L 00014 10L 00007 44L 000504L 00020 10L 00011 46L 00004

10L 00029 46L 00007 46L 0001210L 00027 46L 00012 46L 0000410L 00032 46L 00009 46L 0000946L 00025 46L 00007 12L 0000446L 00052 12L 00008 12L 0000846L 00029 12L 00012 12L 0000446L 00026 12L 00008 12L 0000712L 00026 12L 00014 26L 0000512L 00043 26L 00007 26L 0000512L 00026 26L 0000612L 0004726L 0002626L 00024

Sample Compost 1 Sample Compost 1 Sample Compost 1Element PBD 154 Element PBD 183 Element PBD 196

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]4L 00010 46L 00002 46L 00011

46L 00003 46L 00024 46L 0000846L 00007 46L 00021 12L 0000246L 00003 46L 00003 12L 0000346L 00004 12L 00003 12L 0000112L 00003 12L 00011 12L 0000212L 00005 12L 0000312L 00031 12L 0000312L 00006

Sample Compost 1 Sample Compost 1 Sample Compost 1Element PBD 197 Element PBD 203 Element PBD 209

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00002 46L 00010 4L 0004146L 00023 12L 00002 4L 0008946L 00022 12L 00003 44L 0041012L 00004 12L 00002 44L 0084012L 00006 12L 00002 44L 0064012L 00003 44L 0040012L 00004 12L 00079

12L 0007312L 0006512L 0009326L 0004926L 00049

Sample Compost 1Element PBD 47

LAB PARM [mgkg]26L 0003826L 00039

Element PBD 99 Element PBD 47 Element PBD 209LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]

4L 00170 10L 00210 4L 010004L 00200 10L 00220 4L 018004L 00170 10L 00210 4L 012004L 00190 46L 00300 4L 0220010L 00280 46L 00280 46L 0210010L 00300 46L 00250 46L 0200010L 00290 46L 00260 64L 0351846L 00340 64L 00059 64L 0363846L 00330 64L 00057 64L 0364546L 00300 64L 00062 64L 0350846L 00310 64L 00060 12L 0220964L 00194 12L 00191 12L 0177164L 00154 12L 00187 12L 0292264L 00185 12L 00190 12L 0164664L 00159 12L 00186 26L 0329712L 00242 26L 00666 26L 0300012L 00223 26L 0033212L 0022112L 0022226L 0024626L 00400

Element PBD 203 Element PBD 197 Element PBD 196LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00022 46L 00027 46L 0002446L 00014 46L 00024 46L 0002264L 00036 12L 00161 64L 0005864L 00058 12L 00060 64L 0006512L 00063 12L 00061 12L 0004812L 00034 12L 00036 12L 0002512L 00038 12L 0003212L 00027 12L 00022

Element PBD 183 Element PBD 154 Element PBD 153LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00049 4L 00020 4L 0002246L 00035 4L 00022 4L 0002446L 00036 4L 00020 4L 0002246L 00034 46L 00025 4L 0002664L 00027 46L 00025 46L 0004064L 00023 46L 00025 46L 0004264L 00024 46L 00023 46L 0003564L 00020 64L 00034 46L 0003812L 00230 64L 00023 64L 0007412L 00032 64L 00017 64L 0004712L 00031 64L 00011 64L 0004612L 00030 12L 00030 64L 0003026L 00007 12L 00021 12L 0006526L 00008 12L 00021 12L 00029

12L 00021 12L 0003226L 00015 12L 0002926L 00019 26L 00039

26L 00040

Element PBD 100LAB PARM [mgkg]

4L 000384L 000414L 000374L 00038

38L 0219038L 0220038L 0208038L 0220010L 0004410L 0005010L 0004310L 0004646L 0005746L 0005946L 0005346L 0005312L 0004312L 0004512L 0004312L 0004326L 0006226L 00057

Sample Soil 3 Sample Soil 3 Sample Soil 3Element PBD 99 Element PBD 47 Element PBD 100

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]10L 00016 10L 00011 10L 0000310L 00019 10L 00010 10L 0000410L 00013 10L 00012 10L 0000410L 00019 46L 00007 10L 0000246L 00025 46L 00022 46L 0000246L 00025 46L 00005 46L 0000646L 00008 46L 00007 46L 0000246L 00011 12L 00010 46L 0000264L 00005 12L 00017 3L 29100064L 00005 12L 00010 3L 32000064L 00006 12L 00009 26L 0000564L 00007 26L 00007 26L 0000512L 00012 26L 0000712L 0001312L 0001312L 0001226L 0000526L 00006

Sample Soil 3 Sample Soil 3 Sample Soil 3Element PBD 153 Element PBD 154 Element PBD 196

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]44L 00050 4L 00010 46L 0000744L 00050 46L 00001 46L 0001146L 00002 46L 00002 46L 0000846L 00003 46L 00001 46L 0001146L 00002 46L 00002 64L 0002646L 00002 64L 00001 64L 0002664L 00001 64L 00001 64L 0002964L 00001 64L 00001 64L 0003464L 00001 64L 00002 12L 0004564L 00002 12L 00003 12L 00032

12L 00002 12L 0002212L 00002 12L 0002112L 00002

Sample Soil 3 Sample Soil 3 Sample Soil 3Element PBD 197 Element PBD 203 Element PBD 209

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00006 46L 00011 4L 0091046L 00013 46L 00017 4L 0150046L 00011 46L 00015 4L 0120046L 00013 46L 00018 4L 0160012L 00090 64L 00013 44L 0337012L 00056 64L 00014 44L 0281012L 00033 64L 00016 44L 0287012L 00032 64L 00015 44L 02540

12L 00055 46L 0230012L 00041 46L 0220012L 00027 46L 0150012L 00026 46L 01900

64L 0438164L 0401664L 0414464L 0449812L 0367112L 0397812L 0409112L 03838

Sample Soil 3 26L 0102Element PBD 183 26L 0131

LAB PARM [mgkg]46L 0000746L 0000846L 0005846L 0000764L 0000264L 0000364L 0000364L 0000312L 0001512L 0001112L 0000712L 00007

European Commission EUR 23003 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on polybrominated diphenylethers Author(s) E Sobiecka H van der Sloot D Barcelo B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 68 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07403-5 Abstract Project HORIZONTAL is interdisciplinary aiming at a harmonisation and horizontal standardisation of test procedures in particular for sludge soils and biowastes In the context of this standardization project a series of draft technical specification were designed upon an extensive desk study fine-tuned after expert consultations and finally validated in international intercomparisons exercise This report summarises the work performed within the validation study of the draft standard for the determination of polybrominated diphenylethers (PBDE) in soils sludge and treated bio-waste using gas-chromatography method with mass selective detection (GC-MS) It further explains the underlying statistical concept for the calculation of reproducibility and repeatability from intercomparisons data In addition all single values results of the statistical evaluation as well as background information on the validation materials used are described and explained

The mission of the JRC is to provide customer-driven scientific and technical support for the conception development implementation and monitoring of EU policies As a service of the European Commission the JRC functions as a reference centre of science and technology for the Union Close to the policy-making process it serves the common interest of the Member States while being independent of special interests whether private or national

LB

-NA

-23003-EN

-C

Unit mgkg

Mandels k statistics(Compost 1 - Sum PBD)Mandels h statistics(Compost 1 - Sum PBD)

Sample Compost 1 Compost 1 - Sum PBD -- Mean PARM = 0009 [mgkg]

Element Sum PBD

General calcparmT1= 154064E-01T2= 169065E-03T3= 18T4= 68T5= 11354E-04

n= variabelp= 5

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00031 0002 4 -067 016 00031 00016 4 3 -0014L 00055 0005 4 -056 048 00055 00047 4 3 000

46L 00085 0003 4 -042 031 00085 00030 4 3 00026L 00123 0000 2 -024 003 00123 00002 2 1 00012L 00154 0002 4 -011 021 00154 00021 4 3 00144L 00613 0023 4 200 237 Fail - - 44L - - 005

Totgem 0018 0006 mgkg 1-level 187 (177) 5 00089 (44L) 5 4Totstd= 0022 0009 5-level 166 (154) 1

RESULTS Mean = 000893 mgkg

Repeatability variance S2r = 000001Repeatability std Sr = 000296 --gt 3308 r = 00083Between lab variance S2L = 000002Reproducibility var S2R = 000003Reproducibility std SR = 000570 --gt 6374 R = 00159Remarks 1 Lab rejected (44L)

000 050 100 150 200 250

k-values

10L

4L

46L

26L

12L

44L

Mandels k statistics(Compost 1 - Sum PBD)

00 00 00 00 00 00 01 01

Deviation from Mean

10L

4L

46L

26L

12L

44L

Labo

rato

ries

Compost 1 - Sum PBD -- Mean PARM = 0009 [mgkg]

-100 000 100 200

h-values

10L

4L

46L

26L

12L

44L

Labo

rato

ries

Mandels h statistics(Compost 1 - Sum PBD)

Compost 1-Sum PBD

Unit mgkg

Mandels k statistics(Sludge 1 - Sum PBD)Mandels h statistics(Sludge 1 - Sum PBD)

Sample Sludge 1 Sludge 1 - Sum PBD -- Mean PARM = 0256 [mgkg]

Element Sum PBD

General calcparmT1= 531806E+00T2= 162188E+00T3= 22T4= 84T5= 25223E-02

n= variabelp= 6

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00423 0025 4 -156 044 Fail 00423 00252 4 3 -02146L 01808 0118 4 -049 205 - - 46L - - -0074L 01810 0056 4 -049 097 01810 00558 4 3 -007

38L 02168 0006 4 -022 010 02168 00059 4 3 -00412L 02890 0065 4 034 113 02890 00647 4 3 00364L 03958 0008 4 116 014 Fail 03958 00079 4 3 01426L 04094 0034 2 126 059 Fail 04094 00337 2 1 015

Totgem 0245 0044 mgkg 1-level 198 (179) 6 02557 (46L) 6 5Totstd= 0130 0039 5-level 171 (155) 1

RESULTS Mean = 025570 mgkg

Repeatability variance S2r = 000158Repeatability std Sr = 003970 --gt 1553 r = 01112Between lab variance S2L = 001807Reproducibility var S2R = 001964Reproducibility std SR = 014015 --gt 5481 R = 03924Remarks 1 Lab rejected (46L)

000 050 100 150 200 250

k-values

10L

46L

4L

38L

12L

64L

26L

Mandels k statistics(Sludge 1 - Sum PBD)

-03 -02 -02 -01 -01 00 01 01 02 02

Deviation from Mean

10L

46L

4L

38L

12L

64L

26L

Labo

rato

ries

Sludge 1 - Sum PBD -- Mean PARM = 0256 [mgkg]

-200 -100 000 100 200

h-values

10L

46L

4L

38L

12L

64L

26L

Labo

rato

ries

Mandels h statistics(Sludge 1 - Sum PBD)

Sludge 1-Sum PBD

Unit mgkg

Mandels k statistics(Soil 3 - Sum PBD)Mandels h statistics(Soil 3 - Sum PBD)

Sample Soil 3 Soil 3 - Sum PBD -- Mean PARM = 0227 [mgkg]

Element Sum PBD

General calcparmT1= 610980E+00T2= 200876E+00T3= 26T4= 100T5= 13106E-02

n= variabelp= 7

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00028 0001 4 -037 000 Fail 00028 00005 4 3 -02226L 01179 0021 2 -036 003 Fail 01179 00208 2 1 -0114L 01305 0031 4 -036 004 Fail 01305 00308 4 3 -010

46L 02065 0035 4 -036 005 Fail 02065 00350 4 3 -00244L 02923 0037 4 -035 005 Fail 02923 00365 4 3 00712L 04051 0015 4 -034 002 Fail 04051 00149 4 3 01864L 04314 0022 4 -033 003 Fail 04314 00223 4 3 0203L 305500 2051 2 247 283 Fail - - 3L - - 3032

Totgem 4017 0276 mgkg 1-level 206 (181) 7 02266 (3L) 7 6Totstd= 10722 0717 5-level 175 (156) 1

RESULTS Mean = 022663 mgkg

Repeatability variance S2r = 000069Repeatability std Sr = 002626 --gt 1159 r = 00735Between lab variance S2L = 002568Reproducibility var S2R = 002637Reproducibility std SR = 016238 --gt 7165 R = 04547Remarks 1 Lab rejected (3L)

000 050 100 150 200 250 300

k-values

10L

26L

4L

46L

44L

12L

64L

3L

Mandels k statistics(Soil 3 - Sum PBD)

-50 00 50 100 150 200 250 300 350

Deviation from Mean

10L

26L

4L

46L

44L

12L

64L

3L

Labo

rato

ries

Soil 3 - Sum PBD -- Mean PARM = 0227 [mgkg]

-100 000 100 200 300

h-values

10L

26L

4L

46L

44L

12L

64L

3L

Labo

rato

ries

Mandels h statistics(Soil 3 - Sum PBD)

Soil 3-Sum PBD

19

Annex 4

Raw data submitted

Sample Compost1 Sample Compost 1 Sample Compost 1Element PBD 99 Element PBD 100 Element PBD 153

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]4L 00021 10L 00008 44L 000504L 00024 10L 00008 44L 000604L 00014 10L 00007 44L 000504L 00020 10L 00011 46L 00004

10L 00029 46L 00007 46L 0001210L 00027 46L 00012 46L 0000410L 00032 46L 00009 46L 0000946L 00025 46L 00007 12L 0000446L 00052 12L 00008 12L 0000846L 00029 12L 00012 12L 0000446L 00026 12L 00008 12L 0000712L 00026 12L 00014 26L 0000512L 00043 26L 00007 26L 0000512L 00026 26L 0000612L 0004726L 0002626L 00024

Sample Compost 1 Sample Compost 1 Sample Compost 1Element PBD 154 Element PBD 183 Element PBD 196

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]4L 00010 46L 00002 46L 00011

46L 00003 46L 00024 46L 0000846L 00007 46L 00021 12L 0000246L 00003 46L 00003 12L 0000346L 00004 12L 00003 12L 0000112L 00003 12L 00011 12L 0000212L 00005 12L 0000312L 00031 12L 0000312L 00006

Sample Compost 1 Sample Compost 1 Sample Compost 1Element PBD 197 Element PBD 203 Element PBD 209

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00002 46L 00010 4L 0004146L 00023 12L 00002 4L 0008946L 00022 12L 00003 44L 0041012L 00004 12L 00002 44L 0084012L 00006 12L 00002 44L 0064012L 00003 44L 0040012L 00004 12L 00079

12L 0007312L 0006512L 0009326L 0004926L 00049

Sample Compost 1Element PBD 47

LAB PARM [mgkg]26L 0003826L 00039

Element PBD 99 Element PBD 47 Element PBD 209LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]

4L 00170 10L 00210 4L 010004L 00200 10L 00220 4L 018004L 00170 10L 00210 4L 012004L 00190 46L 00300 4L 0220010L 00280 46L 00280 46L 0210010L 00300 46L 00250 46L 0200010L 00290 46L 00260 64L 0351846L 00340 64L 00059 64L 0363846L 00330 64L 00057 64L 0364546L 00300 64L 00062 64L 0350846L 00310 64L 00060 12L 0220964L 00194 12L 00191 12L 0177164L 00154 12L 00187 12L 0292264L 00185 12L 00190 12L 0164664L 00159 12L 00186 26L 0329712L 00242 26L 00666 26L 0300012L 00223 26L 0033212L 0022112L 0022226L 0024626L 00400

Element PBD 203 Element PBD 197 Element PBD 196LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00022 46L 00027 46L 0002446L 00014 46L 00024 46L 0002264L 00036 12L 00161 64L 0005864L 00058 12L 00060 64L 0006512L 00063 12L 00061 12L 0004812L 00034 12L 00036 12L 0002512L 00038 12L 0003212L 00027 12L 00022

Element PBD 183 Element PBD 154 Element PBD 153LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00049 4L 00020 4L 0002246L 00035 4L 00022 4L 0002446L 00036 4L 00020 4L 0002246L 00034 46L 00025 4L 0002664L 00027 46L 00025 46L 0004064L 00023 46L 00025 46L 0004264L 00024 46L 00023 46L 0003564L 00020 64L 00034 46L 0003812L 00230 64L 00023 64L 0007412L 00032 64L 00017 64L 0004712L 00031 64L 00011 64L 0004612L 00030 12L 00030 64L 0003026L 00007 12L 00021 12L 0006526L 00008 12L 00021 12L 00029

12L 00021 12L 0003226L 00015 12L 0002926L 00019 26L 00039

26L 00040

Element PBD 100LAB PARM [mgkg]

4L 000384L 000414L 000374L 00038

38L 0219038L 0220038L 0208038L 0220010L 0004410L 0005010L 0004310L 0004646L 0005746L 0005946L 0005346L 0005312L 0004312L 0004512L 0004312L 0004326L 0006226L 00057

Sample Soil 3 Sample Soil 3 Sample Soil 3Element PBD 99 Element PBD 47 Element PBD 100

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]10L 00016 10L 00011 10L 0000310L 00019 10L 00010 10L 0000410L 00013 10L 00012 10L 0000410L 00019 46L 00007 10L 0000246L 00025 46L 00022 46L 0000246L 00025 46L 00005 46L 0000646L 00008 46L 00007 46L 0000246L 00011 12L 00010 46L 0000264L 00005 12L 00017 3L 29100064L 00005 12L 00010 3L 32000064L 00006 12L 00009 26L 0000564L 00007 26L 00007 26L 0000512L 00012 26L 0000712L 0001312L 0001312L 0001226L 0000526L 00006

Sample Soil 3 Sample Soil 3 Sample Soil 3Element PBD 153 Element PBD 154 Element PBD 196

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]44L 00050 4L 00010 46L 0000744L 00050 46L 00001 46L 0001146L 00002 46L 00002 46L 0000846L 00003 46L 00001 46L 0001146L 00002 46L 00002 64L 0002646L 00002 64L 00001 64L 0002664L 00001 64L 00001 64L 0002964L 00001 64L 00001 64L 0003464L 00001 64L 00002 12L 0004564L 00002 12L 00003 12L 00032

12L 00002 12L 0002212L 00002 12L 0002112L 00002

Sample Soil 3 Sample Soil 3 Sample Soil 3Element PBD 197 Element PBD 203 Element PBD 209

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00006 46L 00011 4L 0091046L 00013 46L 00017 4L 0150046L 00011 46L 00015 4L 0120046L 00013 46L 00018 4L 0160012L 00090 64L 00013 44L 0337012L 00056 64L 00014 44L 0281012L 00033 64L 00016 44L 0287012L 00032 64L 00015 44L 02540

12L 00055 46L 0230012L 00041 46L 0220012L 00027 46L 0150012L 00026 46L 01900

64L 0438164L 0401664L 0414464L 0449812L 0367112L 0397812L 0409112L 03838

Sample Soil 3 26L 0102Element PBD 183 26L 0131

LAB PARM [mgkg]46L 0000746L 0000846L 0005846L 0000764L 0000264L 0000364L 0000364L 0000312L 0001512L 0001112L 0000712L 00007

European Commission EUR 23003 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on polybrominated diphenylethers Author(s) E Sobiecka H van der Sloot D Barcelo B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 68 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07403-5 Abstract Project HORIZONTAL is interdisciplinary aiming at a harmonisation and horizontal standardisation of test procedures in particular for sludge soils and biowastes In the context of this standardization project a series of draft technical specification were designed upon an extensive desk study fine-tuned after expert consultations and finally validated in international intercomparisons exercise This report summarises the work performed within the validation study of the draft standard for the determination of polybrominated diphenylethers (PBDE) in soils sludge and treated bio-waste using gas-chromatography method with mass selective detection (GC-MS) It further explains the underlying statistical concept for the calculation of reproducibility and repeatability from intercomparisons data In addition all single values results of the statistical evaluation as well as background information on the validation materials used are described and explained

The mission of the JRC is to provide customer-driven scientific and technical support for the conception development implementation and monitoring of EU policies As a service of the European Commission the JRC functions as a reference centre of science and technology for the Union Close to the policy-making process it serves the common interest of the Member States while being independent of special interests whether private or national

LB

-NA

-23003-EN

-C

Unit mgkg

Mandels k statistics(Sludge 1 - Sum PBD)Mandels h statistics(Sludge 1 - Sum PBD)

Sample Sludge 1 Sludge 1 - Sum PBD -- Mean PARM = 0256 [mgkg]

Element Sum PBD

General calcparmT1= 531806E+00T2= 162188E+00T3= 22T4= 84T5= 25223E-02

n= variabelp= 6

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00423 0025 4 -156 044 Fail 00423 00252 4 3 -02146L 01808 0118 4 -049 205 - - 46L - - -0074L 01810 0056 4 -049 097 01810 00558 4 3 -007

38L 02168 0006 4 -022 010 02168 00059 4 3 -00412L 02890 0065 4 034 113 02890 00647 4 3 00364L 03958 0008 4 116 014 Fail 03958 00079 4 3 01426L 04094 0034 2 126 059 Fail 04094 00337 2 1 015

Totgem 0245 0044 mgkg 1-level 198 (179) 6 02557 (46L) 6 5Totstd= 0130 0039 5-level 171 (155) 1

RESULTS Mean = 025570 mgkg

Repeatability variance S2r = 000158Repeatability std Sr = 003970 --gt 1553 r = 01112Between lab variance S2L = 001807Reproducibility var S2R = 001964Reproducibility std SR = 014015 --gt 5481 R = 03924Remarks 1 Lab rejected (46L)

000 050 100 150 200 250

k-values

10L

46L

4L

38L

12L

64L

26L

Mandels k statistics(Sludge 1 - Sum PBD)

-03 -02 -02 -01 -01 00 01 01 02 02

Deviation from Mean

10L

46L

4L

38L

12L

64L

26L

Labo

rato

ries

Sludge 1 - Sum PBD -- Mean PARM = 0256 [mgkg]

-200 -100 000 100 200

h-values

10L

46L

4L

38L

12L

64L

26L

Labo

rato

ries

Mandels h statistics(Sludge 1 - Sum PBD)

Sludge 1-Sum PBD

Unit mgkg

Mandels k statistics(Soil 3 - Sum PBD)Mandels h statistics(Soil 3 - Sum PBD)

Sample Soil 3 Soil 3 - Sum PBD -- Mean PARM = 0227 [mgkg]

Element Sum PBD

General calcparmT1= 610980E+00T2= 200876E+00T3= 26T4= 100T5= 13106E-02

n= variabelp= 7

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00028 0001 4 -037 000 Fail 00028 00005 4 3 -02226L 01179 0021 2 -036 003 Fail 01179 00208 2 1 -0114L 01305 0031 4 -036 004 Fail 01305 00308 4 3 -010

46L 02065 0035 4 -036 005 Fail 02065 00350 4 3 -00244L 02923 0037 4 -035 005 Fail 02923 00365 4 3 00712L 04051 0015 4 -034 002 Fail 04051 00149 4 3 01864L 04314 0022 4 -033 003 Fail 04314 00223 4 3 0203L 305500 2051 2 247 283 Fail - - 3L - - 3032

Totgem 4017 0276 mgkg 1-level 206 (181) 7 02266 (3L) 7 6Totstd= 10722 0717 5-level 175 (156) 1

RESULTS Mean = 022663 mgkg

Repeatability variance S2r = 000069Repeatability std Sr = 002626 --gt 1159 r = 00735Between lab variance S2L = 002568Reproducibility var S2R = 002637Reproducibility std SR = 016238 --gt 7165 R = 04547Remarks 1 Lab rejected (3L)

000 050 100 150 200 250 300

k-values

10L

26L

4L

46L

44L

12L

64L

3L

Mandels k statistics(Soil 3 - Sum PBD)

-50 00 50 100 150 200 250 300 350

Deviation from Mean

10L

26L

4L

46L

44L

12L

64L

3L

Labo

rato

ries

Soil 3 - Sum PBD -- Mean PARM = 0227 [mgkg]

-100 000 100 200 300

h-values

10L

26L

4L

46L

44L

12L

64L

3L

Labo

rato

ries

Mandels h statistics(Soil 3 - Sum PBD)

Soil 3-Sum PBD

19

Annex 4

Raw data submitted

Sample Compost1 Sample Compost 1 Sample Compost 1Element PBD 99 Element PBD 100 Element PBD 153

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]4L 00021 10L 00008 44L 000504L 00024 10L 00008 44L 000604L 00014 10L 00007 44L 000504L 00020 10L 00011 46L 00004

10L 00029 46L 00007 46L 0001210L 00027 46L 00012 46L 0000410L 00032 46L 00009 46L 0000946L 00025 46L 00007 12L 0000446L 00052 12L 00008 12L 0000846L 00029 12L 00012 12L 0000446L 00026 12L 00008 12L 0000712L 00026 12L 00014 26L 0000512L 00043 26L 00007 26L 0000512L 00026 26L 0000612L 0004726L 0002626L 00024

Sample Compost 1 Sample Compost 1 Sample Compost 1Element PBD 154 Element PBD 183 Element PBD 196

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]4L 00010 46L 00002 46L 00011

46L 00003 46L 00024 46L 0000846L 00007 46L 00021 12L 0000246L 00003 46L 00003 12L 0000346L 00004 12L 00003 12L 0000112L 00003 12L 00011 12L 0000212L 00005 12L 0000312L 00031 12L 0000312L 00006

Sample Compost 1 Sample Compost 1 Sample Compost 1Element PBD 197 Element PBD 203 Element PBD 209

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00002 46L 00010 4L 0004146L 00023 12L 00002 4L 0008946L 00022 12L 00003 44L 0041012L 00004 12L 00002 44L 0084012L 00006 12L 00002 44L 0064012L 00003 44L 0040012L 00004 12L 00079

12L 0007312L 0006512L 0009326L 0004926L 00049

Sample Compost 1Element PBD 47

LAB PARM [mgkg]26L 0003826L 00039

Element PBD 99 Element PBD 47 Element PBD 209LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]

4L 00170 10L 00210 4L 010004L 00200 10L 00220 4L 018004L 00170 10L 00210 4L 012004L 00190 46L 00300 4L 0220010L 00280 46L 00280 46L 0210010L 00300 46L 00250 46L 0200010L 00290 46L 00260 64L 0351846L 00340 64L 00059 64L 0363846L 00330 64L 00057 64L 0364546L 00300 64L 00062 64L 0350846L 00310 64L 00060 12L 0220964L 00194 12L 00191 12L 0177164L 00154 12L 00187 12L 0292264L 00185 12L 00190 12L 0164664L 00159 12L 00186 26L 0329712L 00242 26L 00666 26L 0300012L 00223 26L 0033212L 0022112L 0022226L 0024626L 00400

Element PBD 203 Element PBD 197 Element PBD 196LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00022 46L 00027 46L 0002446L 00014 46L 00024 46L 0002264L 00036 12L 00161 64L 0005864L 00058 12L 00060 64L 0006512L 00063 12L 00061 12L 0004812L 00034 12L 00036 12L 0002512L 00038 12L 0003212L 00027 12L 00022

Element PBD 183 Element PBD 154 Element PBD 153LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00049 4L 00020 4L 0002246L 00035 4L 00022 4L 0002446L 00036 4L 00020 4L 0002246L 00034 46L 00025 4L 0002664L 00027 46L 00025 46L 0004064L 00023 46L 00025 46L 0004264L 00024 46L 00023 46L 0003564L 00020 64L 00034 46L 0003812L 00230 64L 00023 64L 0007412L 00032 64L 00017 64L 0004712L 00031 64L 00011 64L 0004612L 00030 12L 00030 64L 0003026L 00007 12L 00021 12L 0006526L 00008 12L 00021 12L 00029

12L 00021 12L 0003226L 00015 12L 0002926L 00019 26L 00039

26L 00040

Element PBD 100LAB PARM [mgkg]

4L 000384L 000414L 000374L 00038

38L 0219038L 0220038L 0208038L 0220010L 0004410L 0005010L 0004310L 0004646L 0005746L 0005946L 0005346L 0005312L 0004312L 0004512L 0004312L 0004326L 0006226L 00057

Sample Soil 3 Sample Soil 3 Sample Soil 3Element PBD 99 Element PBD 47 Element PBD 100

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]10L 00016 10L 00011 10L 0000310L 00019 10L 00010 10L 0000410L 00013 10L 00012 10L 0000410L 00019 46L 00007 10L 0000246L 00025 46L 00022 46L 0000246L 00025 46L 00005 46L 0000646L 00008 46L 00007 46L 0000246L 00011 12L 00010 46L 0000264L 00005 12L 00017 3L 29100064L 00005 12L 00010 3L 32000064L 00006 12L 00009 26L 0000564L 00007 26L 00007 26L 0000512L 00012 26L 0000712L 0001312L 0001312L 0001226L 0000526L 00006

Sample Soil 3 Sample Soil 3 Sample Soil 3Element PBD 153 Element PBD 154 Element PBD 196

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]44L 00050 4L 00010 46L 0000744L 00050 46L 00001 46L 0001146L 00002 46L 00002 46L 0000846L 00003 46L 00001 46L 0001146L 00002 46L 00002 64L 0002646L 00002 64L 00001 64L 0002664L 00001 64L 00001 64L 0002964L 00001 64L 00001 64L 0003464L 00001 64L 00002 12L 0004564L 00002 12L 00003 12L 00032

12L 00002 12L 0002212L 00002 12L 0002112L 00002

Sample Soil 3 Sample Soil 3 Sample Soil 3Element PBD 197 Element PBD 203 Element PBD 209

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00006 46L 00011 4L 0091046L 00013 46L 00017 4L 0150046L 00011 46L 00015 4L 0120046L 00013 46L 00018 4L 0160012L 00090 64L 00013 44L 0337012L 00056 64L 00014 44L 0281012L 00033 64L 00016 44L 0287012L 00032 64L 00015 44L 02540

12L 00055 46L 0230012L 00041 46L 0220012L 00027 46L 0150012L 00026 46L 01900

64L 0438164L 0401664L 0414464L 0449812L 0367112L 0397812L 0409112L 03838

Sample Soil 3 26L 0102Element PBD 183 26L 0131

LAB PARM [mgkg]46L 0000746L 0000846L 0005846L 0000764L 0000264L 0000364L 0000364L 0000312L 0001512L 0001112L 0000712L 00007

European Commission EUR 23003 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on polybrominated diphenylethers Author(s) E Sobiecka H van der Sloot D Barcelo B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 68 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07403-5 Abstract Project HORIZONTAL is interdisciplinary aiming at a harmonisation and horizontal standardisation of test procedures in particular for sludge soils and biowastes In the context of this standardization project a series of draft technical specification were designed upon an extensive desk study fine-tuned after expert consultations and finally validated in international intercomparisons exercise This report summarises the work performed within the validation study of the draft standard for the determination of polybrominated diphenylethers (PBDE) in soils sludge and treated bio-waste using gas-chromatography method with mass selective detection (GC-MS) It further explains the underlying statistical concept for the calculation of reproducibility and repeatability from intercomparisons data In addition all single values results of the statistical evaluation as well as background information on the validation materials used are described and explained

The mission of the JRC is to provide customer-driven scientific and technical support for the conception development implementation and monitoring of EU policies As a service of the European Commission the JRC functions as a reference centre of science and technology for the Union Close to the policy-making process it serves the common interest of the Member States while being independent of special interests whether private or national

LB

-NA

-23003-EN

-C

Unit mgkg

Mandels k statistics(Soil 3 - Sum PBD)Mandels h statistics(Soil 3 - Sum PBD)

Sample Soil 3 Soil 3 - Sum PBD -- Mean PARM = 0227 [mgkg]

Element Sum PBD

General calcparmT1= 610980E+00T2= 200876E+00T3= 26T4= 100T5= 13106E-02

n= variabelp= 7

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean10L 00028 0001 4 -037 000 Fail 00028 00005 4 3 -02226L 01179 0021 2 -036 003 Fail 01179 00208 2 1 -0114L 01305 0031 4 -036 004 Fail 01305 00308 4 3 -010

46L 02065 0035 4 -036 005 Fail 02065 00350 4 3 -00244L 02923 0037 4 -035 005 Fail 02923 00365 4 3 00712L 04051 0015 4 -034 002 Fail 04051 00149 4 3 01864L 04314 0022 4 -033 003 Fail 04314 00223 4 3 0203L 305500 2051 2 247 283 Fail - - 3L - - 3032

Totgem 4017 0276 mgkg 1-level 206 (181) 7 02266 (3L) 7 6Totstd= 10722 0717 5-level 175 (156) 1

RESULTS Mean = 022663 mgkg

Repeatability variance S2r = 000069Repeatability std Sr = 002626 --gt 1159 r = 00735Between lab variance S2L = 002568Reproducibility var S2R = 002637Reproducibility std SR = 016238 --gt 7165 R = 04547Remarks 1 Lab rejected (3L)

000 050 100 150 200 250 300

k-values

10L

26L

4L

46L

44L

12L

64L

3L

Mandels k statistics(Soil 3 - Sum PBD)

-50 00 50 100 150 200 250 300 350

Deviation from Mean

10L

26L

4L

46L

44L

12L

64L

3L

Labo

rato

ries

Soil 3 - Sum PBD -- Mean PARM = 0227 [mgkg]

-100 000 100 200 300

h-values

10L

26L

4L

46L

44L

12L

64L

3L

Labo

rato

ries

Mandels h statistics(Soil 3 - Sum PBD)

Soil 3-Sum PBD

19

Annex 4

Raw data submitted

Sample Compost1 Sample Compost 1 Sample Compost 1Element PBD 99 Element PBD 100 Element PBD 153

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]4L 00021 10L 00008 44L 000504L 00024 10L 00008 44L 000604L 00014 10L 00007 44L 000504L 00020 10L 00011 46L 00004

10L 00029 46L 00007 46L 0001210L 00027 46L 00012 46L 0000410L 00032 46L 00009 46L 0000946L 00025 46L 00007 12L 0000446L 00052 12L 00008 12L 0000846L 00029 12L 00012 12L 0000446L 00026 12L 00008 12L 0000712L 00026 12L 00014 26L 0000512L 00043 26L 00007 26L 0000512L 00026 26L 0000612L 0004726L 0002626L 00024

Sample Compost 1 Sample Compost 1 Sample Compost 1Element PBD 154 Element PBD 183 Element PBD 196

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]4L 00010 46L 00002 46L 00011

46L 00003 46L 00024 46L 0000846L 00007 46L 00021 12L 0000246L 00003 46L 00003 12L 0000346L 00004 12L 00003 12L 0000112L 00003 12L 00011 12L 0000212L 00005 12L 0000312L 00031 12L 0000312L 00006

Sample Compost 1 Sample Compost 1 Sample Compost 1Element PBD 197 Element PBD 203 Element PBD 209

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00002 46L 00010 4L 0004146L 00023 12L 00002 4L 0008946L 00022 12L 00003 44L 0041012L 00004 12L 00002 44L 0084012L 00006 12L 00002 44L 0064012L 00003 44L 0040012L 00004 12L 00079

12L 0007312L 0006512L 0009326L 0004926L 00049

Sample Compost 1Element PBD 47

LAB PARM [mgkg]26L 0003826L 00039

Element PBD 99 Element PBD 47 Element PBD 209LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]

4L 00170 10L 00210 4L 010004L 00200 10L 00220 4L 018004L 00170 10L 00210 4L 012004L 00190 46L 00300 4L 0220010L 00280 46L 00280 46L 0210010L 00300 46L 00250 46L 0200010L 00290 46L 00260 64L 0351846L 00340 64L 00059 64L 0363846L 00330 64L 00057 64L 0364546L 00300 64L 00062 64L 0350846L 00310 64L 00060 12L 0220964L 00194 12L 00191 12L 0177164L 00154 12L 00187 12L 0292264L 00185 12L 00190 12L 0164664L 00159 12L 00186 26L 0329712L 00242 26L 00666 26L 0300012L 00223 26L 0033212L 0022112L 0022226L 0024626L 00400

Element PBD 203 Element PBD 197 Element PBD 196LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00022 46L 00027 46L 0002446L 00014 46L 00024 46L 0002264L 00036 12L 00161 64L 0005864L 00058 12L 00060 64L 0006512L 00063 12L 00061 12L 0004812L 00034 12L 00036 12L 0002512L 00038 12L 0003212L 00027 12L 00022

Element PBD 183 Element PBD 154 Element PBD 153LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00049 4L 00020 4L 0002246L 00035 4L 00022 4L 0002446L 00036 4L 00020 4L 0002246L 00034 46L 00025 4L 0002664L 00027 46L 00025 46L 0004064L 00023 46L 00025 46L 0004264L 00024 46L 00023 46L 0003564L 00020 64L 00034 46L 0003812L 00230 64L 00023 64L 0007412L 00032 64L 00017 64L 0004712L 00031 64L 00011 64L 0004612L 00030 12L 00030 64L 0003026L 00007 12L 00021 12L 0006526L 00008 12L 00021 12L 00029

12L 00021 12L 0003226L 00015 12L 0002926L 00019 26L 00039

26L 00040

Element PBD 100LAB PARM [mgkg]

4L 000384L 000414L 000374L 00038

38L 0219038L 0220038L 0208038L 0220010L 0004410L 0005010L 0004310L 0004646L 0005746L 0005946L 0005346L 0005312L 0004312L 0004512L 0004312L 0004326L 0006226L 00057

Sample Soil 3 Sample Soil 3 Sample Soil 3Element PBD 99 Element PBD 47 Element PBD 100

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]10L 00016 10L 00011 10L 0000310L 00019 10L 00010 10L 0000410L 00013 10L 00012 10L 0000410L 00019 46L 00007 10L 0000246L 00025 46L 00022 46L 0000246L 00025 46L 00005 46L 0000646L 00008 46L 00007 46L 0000246L 00011 12L 00010 46L 0000264L 00005 12L 00017 3L 29100064L 00005 12L 00010 3L 32000064L 00006 12L 00009 26L 0000564L 00007 26L 00007 26L 0000512L 00012 26L 0000712L 0001312L 0001312L 0001226L 0000526L 00006

Sample Soil 3 Sample Soil 3 Sample Soil 3Element PBD 153 Element PBD 154 Element PBD 196

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]44L 00050 4L 00010 46L 0000744L 00050 46L 00001 46L 0001146L 00002 46L 00002 46L 0000846L 00003 46L 00001 46L 0001146L 00002 46L 00002 64L 0002646L 00002 64L 00001 64L 0002664L 00001 64L 00001 64L 0002964L 00001 64L 00001 64L 0003464L 00001 64L 00002 12L 0004564L 00002 12L 00003 12L 00032

12L 00002 12L 0002212L 00002 12L 0002112L 00002

Sample Soil 3 Sample Soil 3 Sample Soil 3Element PBD 197 Element PBD 203 Element PBD 209

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00006 46L 00011 4L 0091046L 00013 46L 00017 4L 0150046L 00011 46L 00015 4L 0120046L 00013 46L 00018 4L 0160012L 00090 64L 00013 44L 0337012L 00056 64L 00014 44L 0281012L 00033 64L 00016 44L 0287012L 00032 64L 00015 44L 02540

12L 00055 46L 0230012L 00041 46L 0220012L 00027 46L 0150012L 00026 46L 01900

64L 0438164L 0401664L 0414464L 0449812L 0367112L 0397812L 0409112L 03838

Sample Soil 3 26L 0102Element PBD 183 26L 0131

LAB PARM [mgkg]46L 0000746L 0000846L 0005846L 0000764L 0000264L 0000364L 0000364L 0000312L 0001512L 0001112L 0000712L 00007

European Commission EUR 23003 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on polybrominated diphenylethers Author(s) E Sobiecka H van der Sloot D Barcelo B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 68 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07403-5 Abstract Project HORIZONTAL is interdisciplinary aiming at a harmonisation and horizontal standardisation of test procedures in particular for sludge soils and biowastes In the context of this standardization project a series of draft technical specification were designed upon an extensive desk study fine-tuned after expert consultations and finally validated in international intercomparisons exercise This report summarises the work performed within the validation study of the draft standard for the determination of polybrominated diphenylethers (PBDE) in soils sludge and treated bio-waste using gas-chromatography method with mass selective detection (GC-MS) It further explains the underlying statistical concept for the calculation of reproducibility and repeatability from intercomparisons data In addition all single values results of the statistical evaluation as well as background information on the validation materials used are described and explained

The mission of the JRC is to provide customer-driven scientific and technical support for the conception development implementation and monitoring of EU policies As a service of the European Commission the JRC functions as a reference centre of science and technology for the Union Close to the policy-making process it serves the common interest of the Member States while being independent of special interests whether private or national

LB

-NA

-23003-EN

-C

19

Annex 4

Raw data submitted

Sample Compost1 Sample Compost 1 Sample Compost 1Element PBD 99 Element PBD 100 Element PBD 153

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]4L 00021 10L 00008 44L 000504L 00024 10L 00008 44L 000604L 00014 10L 00007 44L 000504L 00020 10L 00011 46L 00004

10L 00029 46L 00007 46L 0001210L 00027 46L 00012 46L 0000410L 00032 46L 00009 46L 0000946L 00025 46L 00007 12L 0000446L 00052 12L 00008 12L 0000846L 00029 12L 00012 12L 0000446L 00026 12L 00008 12L 0000712L 00026 12L 00014 26L 0000512L 00043 26L 00007 26L 0000512L 00026 26L 0000612L 0004726L 0002626L 00024

Sample Compost 1 Sample Compost 1 Sample Compost 1Element PBD 154 Element PBD 183 Element PBD 196

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]4L 00010 46L 00002 46L 00011

46L 00003 46L 00024 46L 0000846L 00007 46L 00021 12L 0000246L 00003 46L 00003 12L 0000346L 00004 12L 00003 12L 0000112L 00003 12L 00011 12L 0000212L 00005 12L 0000312L 00031 12L 0000312L 00006

Sample Compost 1 Sample Compost 1 Sample Compost 1Element PBD 197 Element PBD 203 Element PBD 209

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00002 46L 00010 4L 0004146L 00023 12L 00002 4L 0008946L 00022 12L 00003 44L 0041012L 00004 12L 00002 44L 0084012L 00006 12L 00002 44L 0064012L 00003 44L 0040012L 00004 12L 00079

12L 0007312L 0006512L 0009326L 0004926L 00049

Sample Compost 1Element PBD 47

LAB PARM [mgkg]26L 0003826L 00039

Element PBD 99 Element PBD 47 Element PBD 209LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]

4L 00170 10L 00210 4L 010004L 00200 10L 00220 4L 018004L 00170 10L 00210 4L 012004L 00190 46L 00300 4L 0220010L 00280 46L 00280 46L 0210010L 00300 46L 00250 46L 0200010L 00290 46L 00260 64L 0351846L 00340 64L 00059 64L 0363846L 00330 64L 00057 64L 0364546L 00300 64L 00062 64L 0350846L 00310 64L 00060 12L 0220964L 00194 12L 00191 12L 0177164L 00154 12L 00187 12L 0292264L 00185 12L 00190 12L 0164664L 00159 12L 00186 26L 0329712L 00242 26L 00666 26L 0300012L 00223 26L 0033212L 0022112L 0022226L 0024626L 00400

Element PBD 203 Element PBD 197 Element PBD 196LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00022 46L 00027 46L 0002446L 00014 46L 00024 46L 0002264L 00036 12L 00161 64L 0005864L 00058 12L 00060 64L 0006512L 00063 12L 00061 12L 0004812L 00034 12L 00036 12L 0002512L 00038 12L 0003212L 00027 12L 00022

Element PBD 183 Element PBD 154 Element PBD 153LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00049 4L 00020 4L 0002246L 00035 4L 00022 4L 0002446L 00036 4L 00020 4L 0002246L 00034 46L 00025 4L 0002664L 00027 46L 00025 46L 0004064L 00023 46L 00025 46L 0004264L 00024 46L 00023 46L 0003564L 00020 64L 00034 46L 0003812L 00230 64L 00023 64L 0007412L 00032 64L 00017 64L 0004712L 00031 64L 00011 64L 0004612L 00030 12L 00030 64L 0003026L 00007 12L 00021 12L 0006526L 00008 12L 00021 12L 00029

12L 00021 12L 0003226L 00015 12L 0002926L 00019 26L 00039

26L 00040

Element PBD 100LAB PARM [mgkg]

4L 000384L 000414L 000374L 00038

38L 0219038L 0220038L 0208038L 0220010L 0004410L 0005010L 0004310L 0004646L 0005746L 0005946L 0005346L 0005312L 0004312L 0004512L 0004312L 0004326L 0006226L 00057

Sample Soil 3 Sample Soil 3 Sample Soil 3Element PBD 99 Element PBD 47 Element PBD 100

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]10L 00016 10L 00011 10L 0000310L 00019 10L 00010 10L 0000410L 00013 10L 00012 10L 0000410L 00019 46L 00007 10L 0000246L 00025 46L 00022 46L 0000246L 00025 46L 00005 46L 0000646L 00008 46L 00007 46L 0000246L 00011 12L 00010 46L 0000264L 00005 12L 00017 3L 29100064L 00005 12L 00010 3L 32000064L 00006 12L 00009 26L 0000564L 00007 26L 00007 26L 0000512L 00012 26L 0000712L 0001312L 0001312L 0001226L 0000526L 00006

Sample Soil 3 Sample Soil 3 Sample Soil 3Element PBD 153 Element PBD 154 Element PBD 196

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]44L 00050 4L 00010 46L 0000744L 00050 46L 00001 46L 0001146L 00002 46L 00002 46L 0000846L 00003 46L 00001 46L 0001146L 00002 46L 00002 64L 0002646L 00002 64L 00001 64L 0002664L 00001 64L 00001 64L 0002964L 00001 64L 00001 64L 0003464L 00001 64L 00002 12L 0004564L 00002 12L 00003 12L 00032

12L 00002 12L 0002212L 00002 12L 0002112L 00002

Sample Soil 3 Sample Soil 3 Sample Soil 3Element PBD 197 Element PBD 203 Element PBD 209

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00006 46L 00011 4L 0091046L 00013 46L 00017 4L 0150046L 00011 46L 00015 4L 0120046L 00013 46L 00018 4L 0160012L 00090 64L 00013 44L 0337012L 00056 64L 00014 44L 0281012L 00033 64L 00016 44L 0287012L 00032 64L 00015 44L 02540

12L 00055 46L 0230012L 00041 46L 0220012L 00027 46L 0150012L 00026 46L 01900

64L 0438164L 0401664L 0414464L 0449812L 0367112L 0397812L 0409112L 03838

Sample Soil 3 26L 0102Element PBD 183 26L 0131

LAB PARM [mgkg]46L 0000746L 0000846L 0005846L 0000764L 0000264L 0000364L 0000364L 0000312L 0001512L 0001112L 0000712L 00007

European Commission EUR 23003 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on polybrominated diphenylethers Author(s) E Sobiecka H van der Sloot D Barcelo B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 68 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07403-5 Abstract Project HORIZONTAL is interdisciplinary aiming at a harmonisation and horizontal standardisation of test procedures in particular for sludge soils and biowastes In the context of this standardization project a series of draft technical specification were designed upon an extensive desk study fine-tuned after expert consultations and finally validated in international intercomparisons exercise This report summarises the work performed within the validation study of the draft standard for the determination of polybrominated diphenylethers (PBDE) in soils sludge and treated bio-waste using gas-chromatography method with mass selective detection (GC-MS) It further explains the underlying statistical concept for the calculation of reproducibility and repeatability from intercomparisons data In addition all single values results of the statistical evaluation as well as background information on the validation materials used are described and explained

The mission of the JRC is to provide customer-driven scientific and technical support for the conception development implementation and monitoring of EU policies As a service of the European Commission the JRC functions as a reference centre of science and technology for the Union Close to the policy-making process it serves the common interest of the Member States while being independent of special interests whether private or national

LB

-NA

-23003-EN

-C

Sample Compost1 Sample Compost 1 Sample Compost 1Element PBD 99 Element PBD 100 Element PBD 153

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]4L 00021 10L 00008 44L 000504L 00024 10L 00008 44L 000604L 00014 10L 00007 44L 000504L 00020 10L 00011 46L 00004

10L 00029 46L 00007 46L 0001210L 00027 46L 00012 46L 0000410L 00032 46L 00009 46L 0000946L 00025 46L 00007 12L 0000446L 00052 12L 00008 12L 0000846L 00029 12L 00012 12L 0000446L 00026 12L 00008 12L 0000712L 00026 12L 00014 26L 0000512L 00043 26L 00007 26L 0000512L 00026 26L 0000612L 0004726L 0002626L 00024

Sample Compost 1 Sample Compost 1 Sample Compost 1Element PBD 154 Element PBD 183 Element PBD 196

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]4L 00010 46L 00002 46L 00011

46L 00003 46L 00024 46L 0000846L 00007 46L 00021 12L 0000246L 00003 46L 00003 12L 0000346L 00004 12L 00003 12L 0000112L 00003 12L 00011 12L 0000212L 00005 12L 0000312L 00031 12L 0000312L 00006

Sample Compost 1 Sample Compost 1 Sample Compost 1Element PBD 197 Element PBD 203 Element PBD 209

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00002 46L 00010 4L 0004146L 00023 12L 00002 4L 0008946L 00022 12L 00003 44L 0041012L 00004 12L 00002 44L 0084012L 00006 12L 00002 44L 0064012L 00003 44L 0040012L 00004 12L 00079

12L 0007312L 0006512L 0009326L 0004926L 00049

Sample Compost 1Element PBD 47

LAB PARM [mgkg]26L 0003826L 00039

Element PBD 99 Element PBD 47 Element PBD 209LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]

4L 00170 10L 00210 4L 010004L 00200 10L 00220 4L 018004L 00170 10L 00210 4L 012004L 00190 46L 00300 4L 0220010L 00280 46L 00280 46L 0210010L 00300 46L 00250 46L 0200010L 00290 46L 00260 64L 0351846L 00340 64L 00059 64L 0363846L 00330 64L 00057 64L 0364546L 00300 64L 00062 64L 0350846L 00310 64L 00060 12L 0220964L 00194 12L 00191 12L 0177164L 00154 12L 00187 12L 0292264L 00185 12L 00190 12L 0164664L 00159 12L 00186 26L 0329712L 00242 26L 00666 26L 0300012L 00223 26L 0033212L 0022112L 0022226L 0024626L 00400

Element PBD 203 Element PBD 197 Element PBD 196LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00022 46L 00027 46L 0002446L 00014 46L 00024 46L 0002264L 00036 12L 00161 64L 0005864L 00058 12L 00060 64L 0006512L 00063 12L 00061 12L 0004812L 00034 12L 00036 12L 0002512L 00038 12L 0003212L 00027 12L 00022

Element PBD 183 Element PBD 154 Element PBD 153LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00049 4L 00020 4L 0002246L 00035 4L 00022 4L 0002446L 00036 4L 00020 4L 0002246L 00034 46L 00025 4L 0002664L 00027 46L 00025 46L 0004064L 00023 46L 00025 46L 0004264L 00024 46L 00023 46L 0003564L 00020 64L 00034 46L 0003812L 00230 64L 00023 64L 0007412L 00032 64L 00017 64L 0004712L 00031 64L 00011 64L 0004612L 00030 12L 00030 64L 0003026L 00007 12L 00021 12L 0006526L 00008 12L 00021 12L 00029

12L 00021 12L 0003226L 00015 12L 0002926L 00019 26L 00039

26L 00040

Element PBD 100LAB PARM [mgkg]

4L 000384L 000414L 000374L 00038

38L 0219038L 0220038L 0208038L 0220010L 0004410L 0005010L 0004310L 0004646L 0005746L 0005946L 0005346L 0005312L 0004312L 0004512L 0004312L 0004326L 0006226L 00057

Sample Soil 3 Sample Soil 3 Sample Soil 3Element PBD 99 Element PBD 47 Element PBD 100

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]10L 00016 10L 00011 10L 0000310L 00019 10L 00010 10L 0000410L 00013 10L 00012 10L 0000410L 00019 46L 00007 10L 0000246L 00025 46L 00022 46L 0000246L 00025 46L 00005 46L 0000646L 00008 46L 00007 46L 0000246L 00011 12L 00010 46L 0000264L 00005 12L 00017 3L 29100064L 00005 12L 00010 3L 32000064L 00006 12L 00009 26L 0000564L 00007 26L 00007 26L 0000512L 00012 26L 0000712L 0001312L 0001312L 0001226L 0000526L 00006

Sample Soil 3 Sample Soil 3 Sample Soil 3Element PBD 153 Element PBD 154 Element PBD 196

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]44L 00050 4L 00010 46L 0000744L 00050 46L 00001 46L 0001146L 00002 46L 00002 46L 0000846L 00003 46L 00001 46L 0001146L 00002 46L 00002 64L 0002646L 00002 64L 00001 64L 0002664L 00001 64L 00001 64L 0002964L 00001 64L 00001 64L 0003464L 00001 64L 00002 12L 0004564L 00002 12L 00003 12L 00032

12L 00002 12L 0002212L 00002 12L 0002112L 00002

Sample Soil 3 Sample Soil 3 Sample Soil 3Element PBD 197 Element PBD 203 Element PBD 209

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00006 46L 00011 4L 0091046L 00013 46L 00017 4L 0150046L 00011 46L 00015 4L 0120046L 00013 46L 00018 4L 0160012L 00090 64L 00013 44L 0337012L 00056 64L 00014 44L 0281012L 00033 64L 00016 44L 0287012L 00032 64L 00015 44L 02540

12L 00055 46L 0230012L 00041 46L 0220012L 00027 46L 0150012L 00026 46L 01900

64L 0438164L 0401664L 0414464L 0449812L 0367112L 0397812L 0409112L 03838

Sample Soil 3 26L 0102Element PBD 183 26L 0131

LAB PARM [mgkg]46L 0000746L 0000846L 0005846L 0000764L 0000264L 0000364L 0000364L 0000312L 0001512L 0001112L 0000712L 00007

European Commission EUR 23003 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on polybrominated diphenylethers Author(s) E Sobiecka H van der Sloot D Barcelo B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 68 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07403-5 Abstract Project HORIZONTAL is interdisciplinary aiming at a harmonisation and horizontal standardisation of test procedures in particular for sludge soils and biowastes In the context of this standardization project a series of draft technical specification were designed upon an extensive desk study fine-tuned after expert consultations and finally validated in international intercomparisons exercise This report summarises the work performed within the validation study of the draft standard for the determination of polybrominated diphenylethers (PBDE) in soils sludge and treated bio-waste using gas-chromatography method with mass selective detection (GC-MS) It further explains the underlying statistical concept for the calculation of reproducibility and repeatability from intercomparisons data In addition all single values results of the statistical evaluation as well as background information on the validation materials used are described and explained

The mission of the JRC is to provide customer-driven scientific and technical support for the conception development implementation and monitoring of EU policies As a service of the European Commission the JRC functions as a reference centre of science and technology for the Union Close to the policy-making process it serves the common interest of the Member States while being independent of special interests whether private or national

LB

-NA

-23003-EN

-C

Sample Compost 1 Sample Compost 1 Sample Compost 1Element PBD 197 Element PBD 203 Element PBD 209

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00002 46L 00010 4L 0004146L 00023 12L 00002 4L 0008946L 00022 12L 00003 44L 0041012L 00004 12L 00002 44L 0084012L 00006 12L 00002 44L 0064012L 00003 44L 0040012L 00004 12L 00079

12L 0007312L 0006512L 0009326L 0004926L 00049

Sample Compost 1Element PBD 47

LAB PARM [mgkg]26L 0003826L 00039

Element PBD 99 Element PBD 47 Element PBD 209LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]

4L 00170 10L 00210 4L 010004L 00200 10L 00220 4L 018004L 00170 10L 00210 4L 012004L 00190 46L 00300 4L 0220010L 00280 46L 00280 46L 0210010L 00300 46L 00250 46L 0200010L 00290 46L 00260 64L 0351846L 00340 64L 00059 64L 0363846L 00330 64L 00057 64L 0364546L 00300 64L 00062 64L 0350846L 00310 64L 00060 12L 0220964L 00194 12L 00191 12L 0177164L 00154 12L 00187 12L 0292264L 00185 12L 00190 12L 0164664L 00159 12L 00186 26L 0329712L 00242 26L 00666 26L 0300012L 00223 26L 0033212L 0022112L 0022226L 0024626L 00400

Element PBD 203 Element PBD 197 Element PBD 196LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00022 46L 00027 46L 0002446L 00014 46L 00024 46L 0002264L 00036 12L 00161 64L 0005864L 00058 12L 00060 64L 0006512L 00063 12L 00061 12L 0004812L 00034 12L 00036 12L 0002512L 00038 12L 0003212L 00027 12L 00022

Element PBD 183 Element PBD 154 Element PBD 153LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00049 4L 00020 4L 0002246L 00035 4L 00022 4L 0002446L 00036 4L 00020 4L 0002246L 00034 46L 00025 4L 0002664L 00027 46L 00025 46L 0004064L 00023 46L 00025 46L 0004264L 00024 46L 00023 46L 0003564L 00020 64L 00034 46L 0003812L 00230 64L 00023 64L 0007412L 00032 64L 00017 64L 0004712L 00031 64L 00011 64L 0004612L 00030 12L 00030 64L 0003026L 00007 12L 00021 12L 0006526L 00008 12L 00021 12L 00029

12L 00021 12L 0003226L 00015 12L 0002926L 00019 26L 00039

26L 00040

Element PBD 100LAB PARM [mgkg]

4L 000384L 000414L 000374L 00038

38L 0219038L 0220038L 0208038L 0220010L 0004410L 0005010L 0004310L 0004646L 0005746L 0005946L 0005346L 0005312L 0004312L 0004512L 0004312L 0004326L 0006226L 00057

Sample Soil 3 Sample Soil 3 Sample Soil 3Element PBD 99 Element PBD 47 Element PBD 100

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]10L 00016 10L 00011 10L 0000310L 00019 10L 00010 10L 0000410L 00013 10L 00012 10L 0000410L 00019 46L 00007 10L 0000246L 00025 46L 00022 46L 0000246L 00025 46L 00005 46L 0000646L 00008 46L 00007 46L 0000246L 00011 12L 00010 46L 0000264L 00005 12L 00017 3L 29100064L 00005 12L 00010 3L 32000064L 00006 12L 00009 26L 0000564L 00007 26L 00007 26L 0000512L 00012 26L 0000712L 0001312L 0001312L 0001226L 0000526L 00006

Sample Soil 3 Sample Soil 3 Sample Soil 3Element PBD 153 Element PBD 154 Element PBD 196

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]44L 00050 4L 00010 46L 0000744L 00050 46L 00001 46L 0001146L 00002 46L 00002 46L 0000846L 00003 46L 00001 46L 0001146L 00002 46L 00002 64L 0002646L 00002 64L 00001 64L 0002664L 00001 64L 00001 64L 0002964L 00001 64L 00001 64L 0003464L 00001 64L 00002 12L 0004564L 00002 12L 00003 12L 00032

12L 00002 12L 0002212L 00002 12L 0002112L 00002

Sample Soil 3 Sample Soil 3 Sample Soil 3Element PBD 197 Element PBD 203 Element PBD 209

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00006 46L 00011 4L 0091046L 00013 46L 00017 4L 0150046L 00011 46L 00015 4L 0120046L 00013 46L 00018 4L 0160012L 00090 64L 00013 44L 0337012L 00056 64L 00014 44L 0281012L 00033 64L 00016 44L 0287012L 00032 64L 00015 44L 02540

12L 00055 46L 0230012L 00041 46L 0220012L 00027 46L 0150012L 00026 46L 01900

64L 0438164L 0401664L 0414464L 0449812L 0367112L 0397812L 0409112L 03838

Sample Soil 3 26L 0102Element PBD 183 26L 0131

LAB PARM [mgkg]46L 0000746L 0000846L 0005846L 0000764L 0000264L 0000364L 0000364L 0000312L 0001512L 0001112L 0000712L 00007

European Commission EUR 23003 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on polybrominated diphenylethers Author(s) E Sobiecka H van der Sloot D Barcelo B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 68 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07403-5 Abstract Project HORIZONTAL is interdisciplinary aiming at a harmonisation and horizontal standardisation of test procedures in particular for sludge soils and biowastes In the context of this standardization project a series of draft technical specification were designed upon an extensive desk study fine-tuned after expert consultations and finally validated in international intercomparisons exercise This report summarises the work performed within the validation study of the draft standard for the determination of polybrominated diphenylethers (PBDE) in soils sludge and treated bio-waste using gas-chromatography method with mass selective detection (GC-MS) It further explains the underlying statistical concept for the calculation of reproducibility and repeatability from intercomparisons data In addition all single values results of the statistical evaluation as well as background information on the validation materials used are described and explained

The mission of the JRC is to provide customer-driven scientific and technical support for the conception development implementation and monitoring of EU policies As a service of the European Commission the JRC functions as a reference centre of science and technology for the Union Close to the policy-making process it serves the common interest of the Member States while being independent of special interests whether private or national

LB

-NA

-23003-EN

-C

Element PBD 99 Element PBD 47 Element PBD 209LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]

4L 00170 10L 00210 4L 010004L 00200 10L 00220 4L 018004L 00170 10L 00210 4L 012004L 00190 46L 00300 4L 0220010L 00280 46L 00280 46L 0210010L 00300 46L 00250 46L 0200010L 00290 46L 00260 64L 0351846L 00340 64L 00059 64L 0363846L 00330 64L 00057 64L 0364546L 00300 64L 00062 64L 0350846L 00310 64L 00060 12L 0220964L 00194 12L 00191 12L 0177164L 00154 12L 00187 12L 0292264L 00185 12L 00190 12L 0164664L 00159 12L 00186 26L 0329712L 00242 26L 00666 26L 0300012L 00223 26L 0033212L 0022112L 0022226L 0024626L 00400

Element PBD 203 Element PBD 197 Element PBD 196LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00022 46L 00027 46L 0002446L 00014 46L 00024 46L 0002264L 00036 12L 00161 64L 0005864L 00058 12L 00060 64L 0006512L 00063 12L 00061 12L 0004812L 00034 12L 00036 12L 0002512L 00038 12L 0003212L 00027 12L 00022

Element PBD 183 Element PBD 154 Element PBD 153LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00049 4L 00020 4L 0002246L 00035 4L 00022 4L 0002446L 00036 4L 00020 4L 0002246L 00034 46L 00025 4L 0002664L 00027 46L 00025 46L 0004064L 00023 46L 00025 46L 0004264L 00024 46L 00023 46L 0003564L 00020 64L 00034 46L 0003812L 00230 64L 00023 64L 0007412L 00032 64L 00017 64L 0004712L 00031 64L 00011 64L 0004612L 00030 12L 00030 64L 0003026L 00007 12L 00021 12L 0006526L 00008 12L 00021 12L 00029

12L 00021 12L 0003226L 00015 12L 0002926L 00019 26L 00039

26L 00040

Element PBD 100LAB PARM [mgkg]

4L 000384L 000414L 000374L 00038

38L 0219038L 0220038L 0208038L 0220010L 0004410L 0005010L 0004310L 0004646L 0005746L 0005946L 0005346L 0005312L 0004312L 0004512L 0004312L 0004326L 0006226L 00057

Sample Soil 3 Sample Soil 3 Sample Soil 3Element PBD 99 Element PBD 47 Element PBD 100

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]10L 00016 10L 00011 10L 0000310L 00019 10L 00010 10L 0000410L 00013 10L 00012 10L 0000410L 00019 46L 00007 10L 0000246L 00025 46L 00022 46L 0000246L 00025 46L 00005 46L 0000646L 00008 46L 00007 46L 0000246L 00011 12L 00010 46L 0000264L 00005 12L 00017 3L 29100064L 00005 12L 00010 3L 32000064L 00006 12L 00009 26L 0000564L 00007 26L 00007 26L 0000512L 00012 26L 0000712L 0001312L 0001312L 0001226L 0000526L 00006

Sample Soil 3 Sample Soil 3 Sample Soil 3Element PBD 153 Element PBD 154 Element PBD 196

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]44L 00050 4L 00010 46L 0000744L 00050 46L 00001 46L 0001146L 00002 46L 00002 46L 0000846L 00003 46L 00001 46L 0001146L 00002 46L 00002 64L 0002646L 00002 64L 00001 64L 0002664L 00001 64L 00001 64L 0002964L 00001 64L 00001 64L 0003464L 00001 64L 00002 12L 0004564L 00002 12L 00003 12L 00032

12L 00002 12L 0002212L 00002 12L 0002112L 00002

Sample Soil 3 Sample Soil 3 Sample Soil 3Element PBD 197 Element PBD 203 Element PBD 209

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00006 46L 00011 4L 0091046L 00013 46L 00017 4L 0150046L 00011 46L 00015 4L 0120046L 00013 46L 00018 4L 0160012L 00090 64L 00013 44L 0337012L 00056 64L 00014 44L 0281012L 00033 64L 00016 44L 0287012L 00032 64L 00015 44L 02540

12L 00055 46L 0230012L 00041 46L 0220012L 00027 46L 0150012L 00026 46L 01900

64L 0438164L 0401664L 0414464L 0449812L 0367112L 0397812L 0409112L 03838

Sample Soil 3 26L 0102Element PBD 183 26L 0131

LAB PARM [mgkg]46L 0000746L 0000846L 0005846L 0000764L 0000264L 0000364L 0000364L 0000312L 0001512L 0001112L 0000712L 00007

European Commission EUR 23003 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on polybrominated diphenylethers Author(s) E Sobiecka H van der Sloot D Barcelo B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 68 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07403-5 Abstract Project HORIZONTAL is interdisciplinary aiming at a harmonisation and horizontal standardisation of test procedures in particular for sludge soils and biowastes In the context of this standardization project a series of draft technical specification were designed upon an extensive desk study fine-tuned after expert consultations and finally validated in international intercomparisons exercise This report summarises the work performed within the validation study of the draft standard for the determination of polybrominated diphenylethers (PBDE) in soils sludge and treated bio-waste using gas-chromatography method with mass selective detection (GC-MS) It further explains the underlying statistical concept for the calculation of reproducibility and repeatability from intercomparisons data In addition all single values results of the statistical evaluation as well as background information on the validation materials used are described and explained

The mission of the JRC is to provide customer-driven scientific and technical support for the conception development implementation and monitoring of EU policies As a service of the European Commission the JRC functions as a reference centre of science and technology for the Union Close to the policy-making process it serves the common interest of the Member States while being independent of special interests whether private or national

LB

-NA

-23003-EN

-C

Element PBD 183 Element PBD 154 Element PBD 153LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00049 4L 00020 4L 0002246L 00035 4L 00022 4L 0002446L 00036 4L 00020 4L 0002246L 00034 46L 00025 4L 0002664L 00027 46L 00025 46L 0004064L 00023 46L 00025 46L 0004264L 00024 46L 00023 46L 0003564L 00020 64L 00034 46L 0003812L 00230 64L 00023 64L 0007412L 00032 64L 00017 64L 0004712L 00031 64L 00011 64L 0004612L 00030 12L 00030 64L 0003026L 00007 12L 00021 12L 0006526L 00008 12L 00021 12L 00029

12L 00021 12L 0003226L 00015 12L 0002926L 00019 26L 00039

26L 00040

Element PBD 100LAB PARM [mgkg]

4L 000384L 000414L 000374L 00038

38L 0219038L 0220038L 0208038L 0220010L 0004410L 0005010L 0004310L 0004646L 0005746L 0005946L 0005346L 0005312L 0004312L 0004512L 0004312L 0004326L 0006226L 00057

Sample Soil 3 Sample Soil 3 Sample Soil 3Element PBD 99 Element PBD 47 Element PBD 100

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]10L 00016 10L 00011 10L 0000310L 00019 10L 00010 10L 0000410L 00013 10L 00012 10L 0000410L 00019 46L 00007 10L 0000246L 00025 46L 00022 46L 0000246L 00025 46L 00005 46L 0000646L 00008 46L 00007 46L 0000246L 00011 12L 00010 46L 0000264L 00005 12L 00017 3L 29100064L 00005 12L 00010 3L 32000064L 00006 12L 00009 26L 0000564L 00007 26L 00007 26L 0000512L 00012 26L 0000712L 0001312L 0001312L 0001226L 0000526L 00006

Sample Soil 3 Sample Soil 3 Sample Soil 3Element PBD 153 Element PBD 154 Element PBD 196

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]44L 00050 4L 00010 46L 0000744L 00050 46L 00001 46L 0001146L 00002 46L 00002 46L 0000846L 00003 46L 00001 46L 0001146L 00002 46L 00002 64L 0002646L 00002 64L 00001 64L 0002664L 00001 64L 00001 64L 0002964L 00001 64L 00001 64L 0003464L 00001 64L 00002 12L 0004564L 00002 12L 00003 12L 00032

12L 00002 12L 0002212L 00002 12L 0002112L 00002

Sample Soil 3 Sample Soil 3 Sample Soil 3Element PBD 197 Element PBD 203 Element PBD 209

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00006 46L 00011 4L 0091046L 00013 46L 00017 4L 0150046L 00011 46L 00015 4L 0120046L 00013 46L 00018 4L 0160012L 00090 64L 00013 44L 0337012L 00056 64L 00014 44L 0281012L 00033 64L 00016 44L 0287012L 00032 64L 00015 44L 02540

12L 00055 46L 0230012L 00041 46L 0220012L 00027 46L 0150012L 00026 46L 01900

64L 0438164L 0401664L 0414464L 0449812L 0367112L 0397812L 0409112L 03838

Sample Soil 3 26L 0102Element PBD 183 26L 0131

LAB PARM [mgkg]46L 0000746L 0000846L 0005846L 0000764L 0000264L 0000364L 0000364L 0000312L 0001512L 0001112L 0000712L 00007

European Commission EUR 23003 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on polybrominated diphenylethers Author(s) E Sobiecka H van der Sloot D Barcelo B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 68 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07403-5 Abstract Project HORIZONTAL is interdisciplinary aiming at a harmonisation and horizontal standardisation of test procedures in particular for sludge soils and biowastes In the context of this standardization project a series of draft technical specification were designed upon an extensive desk study fine-tuned after expert consultations and finally validated in international intercomparisons exercise This report summarises the work performed within the validation study of the draft standard for the determination of polybrominated diphenylethers (PBDE) in soils sludge and treated bio-waste using gas-chromatography method with mass selective detection (GC-MS) It further explains the underlying statistical concept for the calculation of reproducibility and repeatability from intercomparisons data In addition all single values results of the statistical evaluation as well as background information on the validation materials used are described and explained

The mission of the JRC is to provide customer-driven scientific and technical support for the conception development implementation and monitoring of EU policies As a service of the European Commission the JRC functions as a reference centre of science and technology for the Union Close to the policy-making process it serves the common interest of the Member States while being independent of special interests whether private or national

LB

-NA

-23003-EN

-C

Sample Soil 3 Sample Soil 3 Sample Soil 3Element PBD 99 Element PBD 47 Element PBD 100

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]10L 00016 10L 00011 10L 0000310L 00019 10L 00010 10L 0000410L 00013 10L 00012 10L 0000410L 00019 46L 00007 10L 0000246L 00025 46L 00022 46L 0000246L 00025 46L 00005 46L 0000646L 00008 46L 00007 46L 0000246L 00011 12L 00010 46L 0000264L 00005 12L 00017 3L 29100064L 00005 12L 00010 3L 32000064L 00006 12L 00009 26L 0000564L 00007 26L 00007 26L 0000512L 00012 26L 0000712L 0001312L 0001312L 0001226L 0000526L 00006

Sample Soil 3 Sample Soil 3 Sample Soil 3Element PBD 153 Element PBD 154 Element PBD 196

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]44L 00050 4L 00010 46L 0000744L 00050 46L 00001 46L 0001146L 00002 46L 00002 46L 0000846L 00003 46L 00001 46L 0001146L 00002 46L 00002 64L 0002646L 00002 64L 00001 64L 0002664L 00001 64L 00001 64L 0002964L 00001 64L 00001 64L 0003464L 00001 64L 00002 12L 0004564L 00002 12L 00003 12L 00032

12L 00002 12L 0002212L 00002 12L 0002112L 00002

Sample Soil 3 Sample Soil 3 Sample Soil 3Element PBD 197 Element PBD 203 Element PBD 209

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00006 46L 00011 4L 0091046L 00013 46L 00017 4L 0150046L 00011 46L 00015 4L 0120046L 00013 46L 00018 4L 0160012L 00090 64L 00013 44L 0337012L 00056 64L 00014 44L 0281012L 00033 64L 00016 44L 0287012L 00032 64L 00015 44L 02540

12L 00055 46L 0230012L 00041 46L 0220012L 00027 46L 0150012L 00026 46L 01900

64L 0438164L 0401664L 0414464L 0449812L 0367112L 0397812L 0409112L 03838

Sample Soil 3 26L 0102Element PBD 183 26L 0131

LAB PARM [mgkg]46L 0000746L 0000846L 0005846L 0000764L 0000264L 0000364L 0000364L 0000312L 0001512L 0001112L 0000712L 00007

European Commission EUR 23003 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on polybrominated diphenylethers Author(s) E Sobiecka H van der Sloot D Barcelo B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 68 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07403-5 Abstract Project HORIZONTAL is interdisciplinary aiming at a harmonisation and horizontal standardisation of test procedures in particular for sludge soils and biowastes In the context of this standardization project a series of draft technical specification were designed upon an extensive desk study fine-tuned after expert consultations and finally validated in international intercomparisons exercise This report summarises the work performed within the validation study of the draft standard for the determination of polybrominated diphenylethers (PBDE) in soils sludge and treated bio-waste using gas-chromatography method with mass selective detection (GC-MS) It further explains the underlying statistical concept for the calculation of reproducibility and repeatability from intercomparisons data In addition all single values results of the statistical evaluation as well as background information on the validation materials used are described and explained

The mission of the JRC is to provide customer-driven scientific and technical support for the conception development implementation and monitoring of EU policies As a service of the European Commission the JRC functions as a reference centre of science and technology for the Union Close to the policy-making process it serves the common interest of the Member States while being independent of special interests whether private or national

LB

-NA

-23003-EN

-C

Sample Soil 3 Sample Soil 3 Sample Soil 3Element PBD 197 Element PBD 203 Element PBD 209

LAB PARM [mgkg] LAB PARM [mgkg] LAB PARM [mgkg]46L 00006 46L 00011 4L 0091046L 00013 46L 00017 4L 0150046L 00011 46L 00015 4L 0120046L 00013 46L 00018 4L 0160012L 00090 64L 00013 44L 0337012L 00056 64L 00014 44L 0281012L 00033 64L 00016 44L 0287012L 00032 64L 00015 44L 02540

12L 00055 46L 0230012L 00041 46L 0220012L 00027 46L 0150012L 00026 46L 01900

64L 0438164L 0401664L 0414464L 0449812L 0367112L 0397812L 0409112L 03838

Sample Soil 3 26L 0102Element PBD 183 26L 0131

LAB PARM [mgkg]46L 0000746L 0000846L 0005846L 0000764L 0000264L 0000364L 0000364L 0000312L 0001512L 0001112L 0000712L 00007

European Commission EUR 23003 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on polybrominated diphenylethers Author(s) E Sobiecka H van der Sloot D Barcelo B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 68 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07403-5 Abstract Project HORIZONTAL is interdisciplinary aiming at a harmonisation and horizontal standardisation of test procedures in particular for sludge soils and biowastes In the context of this standardization project a series of draft technical specification were designed upon an extensive desk study fine-tuned after expert consultations and finally validated in international intercomparisons exercise This report summarises the work performed within the validation study of the draft standard for the determination of polybrominated diphenylethers (PBDE) in soils sludge and treated bio-waste using gas-chromatography method with mass selective detection (GC-MS) It further explains the underlying statistical concept for the calculation of reproducibility and repeatability from intercomparisons data In addition all single values results of the statistical evaluation as well as background information on the validation materials used are described and explained

The mission of the JRC is to provide customer-driven scientific and technical support for the conception development implementation and monitoring of EU policies As a service of the European Commission the JRC functions as a reference centre of science and technology for the Union Close to the policy-making process it serves the common interest of the Member States while being independent of special interests whether private or national

LB

-NA

-23003-EN

-C

European Commission EUR 23003 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on polybrominated diphenylethers Author(s) E Sobiecka H van der Sloot D Barcelo B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 68 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07403-5 Abstract Project HORIZONTAL is interdisciplinary aiming at a harmonisation and horizontal standardisation of test procedures in particular for sludge soils and biowastes In the context of this standardization project a series of draft technical specification were designed upon an extensive desk study fine-tuned after expert consultations and finally validated in international intercomparisons exercise This report summarises the work performed within the validation study of the draft standard for the determination of polybrominated diphenylethers (PBDE) in soils sludge and treated bio-waste using gas-chromatography method with mass selective detection (GC-MS) It further explains the underlying statistical concept for the calculation of reproducibility and repeatability from intercomparisons data In addition all single values results of the statistical evaluation as well as background information on the validation materials used are described and explained

The mission of the JRC is to provide customer-driven scientific and technical support for the conception development implementation and monitoring of EU policies As a service of the European Commission the JRC functions as a reference centre of science and technology for the Union Close to the policy-making process it serves the common interest of the Member States while being independent of special interests whether private or national

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The mission of the JRC is to provide customer-driven scientific and technical support for the conception development implementation and monitoring of EU policies As a service of the European Commission the JRC functions as a reference centre of science and technology for the Union Close to the policy-making process it serves the common interest of the Member States while being independent of special interests whether private or national

LB

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