EUR 23012 EN - 2007

Project HORIZONTAL Validation Reporton total organic carbon

Validation of a horizontal standard for the determination of total organic carbon (TOC) by dry combustion in soils sludge and treated biowaste in a European Intercomparison Exercise

E Sobiecka H van der Sloot K Andersen 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 40201 EUR 23012 EN ISBN 978-92-79-07412-7 ISSN 1018-5593 DOI 10278847924 Luxembourg Office for Official Publications of the European Communities copy European Communities 2007 Reproduction is authorised provided the source is acknowledged Printed in Luxembourg

Project HORIZONTAL Validation Report Validation of a horizontal standard for the determination of total organic carbon (TOC) by dry combustion in soils sludge and treated biowaste in a European Intercomparison Exercise E Sobiecka H Van der Sloot K Andersen 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

Kirsten ANDERSEN DANAK Dyregaringrdsvej 5 B 2740 Skovlunde Denmark

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 soil and biowaste 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 intercomparison exercise This report summarises the work performed in a validation study for the draft standard for the determination of total organic carbon (TOC) in soil sludge and treated bio-waste It further explains the underlying statistical concept for the calculation of reproducibility and repeatability from intercomparison 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

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

MILC Measure Interlaboratory Comparison ndash (online data submission system)

p Number of labs

r Repeatability limit

R Reproducibility limit

sr Repeatability standard deviation

sR Reproducibility standard deviation

TC Technical Committee

TOC Total Organic Carbon

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 TOC 8

121 Samples dispatched for the validation of TOC 8

122 Draft standards to be followed 8

123 Analytical program 8

124 Timing and Submission of data 8

125 Participants 10

13 Summary results and derived performance characteristics 11

14 Annexes 13

5

Introduction to the validation project Project HORIZONTAL is interdisciplinary aiming at a harmonisation and horizontal standardisation of test procedures in particular for sludge 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 a 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 total organic carbon (TOC) are described hereafter

6

11 Statistical concept underlying the validation According to the requirements of the work package concerning data handling and interpretation of the project HORIZONTAL the respective validation intercomparisons should be evaluated according to ISO 5725-21994 In particular repeatability and reproducibility of the draft standard should be determined 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 work program 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 exercises For each parameter investigated at least 10 laboratories should be nominated to participate The same laboratories should analyse different parameters as far as possible Due to the complexity of analysis and the respective workload of the laboratories it was decided to propose six materials for the validation of the TOC draft standard Each laboratory received two bottles of each material and was requested to perform 6 independent analyses per material1 (3 per bottle) using the draft standard method The 6 analyses 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 was permitted but had to be reported Likewise the different materials could 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 had 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 was set and should 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 The draft standard was made available to the laboratories on the Project Horizontal homepage Each laboratory was requested to provide the signed statements on cooperation as given in Annex 1

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 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

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

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 TOC

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

bull Compost 1 A compost material from Vienna bull Compost 2 A compost material from Germany bull Sewage Sludge 1 A mixed sewage sludge from Essen Germany bull Sewage Sludge 2 A mixed municipal sludge from North Rhine Westphalia

Germany bull Soil 4 A sludge amended soil from Hohenheim Germany bull Soil 5 An agricultural soil from Reading UK

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

122 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 httpwwwecnnldocssocietyhorizontalTOC_standard_for_validationpdf

123 Analytical program Two bottles had to be analysed for each of the six materials and each bottle had to be analysed independently three times 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 dry matter correction was free for each participant

124 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

9

submission of results has been set for TOC to the 31st of January 2007 Alternatively the participants were allowed to submit data electronically as Excel sheet using Email All data were treated in a confidential way Any presentation hereafter refers 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 provided a 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

125 Participants The following table lists the participating organizations and entities in the validation exercise for the horizontal TOC standard

bull Austria o barbara - Engineering Consulting Research amp Service GmbH o Federal Research and Training Centre for Forests Natural Hazards and

Landscape o NUA Umweltanalytik GmbH o Oumlsterreichische Agentur fuumlr Gesundheit und Ernaumlhrungssicherheit o Universitaumlt fuumlr Bodenkultur Wien o Shimadzu Europa GmbH o Umweltbundesamt o University of Natural resources and Applied Life Sciences

bull Belgium o VITO

bull France o INERIS o CEMAGREF - UR QELY o INRA - Laboratoire dAnalyse des Sols

bull Germany o ALBO-tec Technologiezentrum Fuumlr Analytik und Bodenmechanik GmbH

bull Norway o Norwegian Institute for Water Research

bull The Netherlands o ALCONTROL BV o Analytico Milieu B V

11

13 Summary results and derived performance characteristics The result of the various statistical evaluation according to ISO 5725-2 including outlier tests calculation of repeatability and reproducibility standard deviations can be found in Annex 3 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 The calculated average values the repeatability standard deviation (sr) and the reproducibility standard deviation (sR) are given in Table 1 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 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 total organic carbon (TOC) by dry combustion in treated biowaste sludge and soil All concentrations are expressed in gkg dry matter

Matrix Parameter Mean sr sR r R p Outliers Total number of data

No of

LOD

Sludge 1 TOC 272 17 59 13 45 13 2 62 0 Sludge 2 TOC 220 21 50 13 31 12 2 58 0

Compost 1 TOC 246 25 43 17 30 13 2 58 0 Compost 2 TOC 154 59 96 25 41 13 2 64 0

Soil 4 TOC 164 26 52 12 24 12 3 62 0 Soil 5 TOC 210 52 82 30 48 10 3 54 0

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

13

14 Annexes Annex 1 Model questionnaire to be filled by the participating laboratories Annex 2 Report on the validation materials used Annex 3 Statistical calculations Annex 4 Data submitted

14

14

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

15

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

16

Annex 3

Statistical calculations

Unit gkg

Mandels k statistics(Compost 1 - TOC)Mandels h statistics(Compost 1 - TOC)

Sample Compost 1 Compost 1 - TOC -- Mean PARM = 2463 [gkg]

Element TOC

General calcparmT1= 142643E+04T2= 351264E+06T3= 58T4= 292T5= 16501E+03

n= variabelp= 13

N-table= 5

Mandels statistics End ResultLAB 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

69L 1960000 64265 4 -235 352 Fail - - 69L - - -502735L 2291667 1674 6 -081 009 2291667 16741 6 5 -171066L 2377425 8552 4 -041 047 2377425 85518 4 3 -85346L 2395000 4796 4 -033 026 2395000 47958 4 3 -67756L 2401227 3133 6 -030 017 2401227 31330 6 5 -61432L 2415000 9713 4 -024 053 2415000 97125 4 3 -47770L 2435100 - 1 -014 2435100 - 1 -27616L 2440000 6033 6 -012 033 2440000 60332 6 5 -22745L 2503800 11759 6 018 064 2503800 117589 6 5 41136L 2514416 3994 3 023 022 2514416 39937 3 2 51765L 2537333 5216 3 033 029 2537333 52157 3 2 74744L 2555667 2783 6 042 015 2555667 27826 6 5 9309L 2568167 1356 6 048 007 2568167 13556 6 5 105530L 2580000 2000 3 053 011 2580000 20000 3 2 117334L 3013269 9580 6 255 053 Fail - - 34L - - 5506

Totgem 246587 9632 gkg 1-level 232 (176) 13 2462677 (34L 69L) 13 12Totstd= 21507 16070 5-level 186 (152) 2

68RESULTS Mean = 24626770 gkg

Repeatability variance S2r = 3666797Repeatability std Sr = 605541 --gt 246 r = 169551Between lab variance S2L = 7715586Reproducibility var S2R = 11382383Reproducibility std SR = 1066882 --gt 433 R = 298727Remarks 2 Labs rejected (34L 69L)

000 050 100 150 200 250 300 350 400

k-values

69L

35L

66L

46L

56L

32L

70L

16L

45L

36L

65L

44L

9L

30L

34L

Mandels k statistics(Compost 1 - TOC)

-600 -400 -200 00 200 400 600

Deviation from Mean

69L

35L

66L

46L

56L

32L

70L

16L

45L

36L

65L

44L

9L

30L

34L

Labo

rato

ries

Compost 1 - TOC -- Mean PARM = 2463 [gkg]

-300 -200 -100 000 100 200 300

h-values

69L

66L

56L

70L

45L

65L

9L

34L

Labo

rato

ries

Mandels h statistics(Compost 1 - TOC)

Compost 1-TOC

Unit gkg

Mandels k statistics(Compost 2 - TOC)Mandels h statistics(Compost 2 - TOC)

Sample Compost 2 Compost 2 - TOC -- Mean PARM = 1542 [gkg]

Element TOC

General calcparmT1= 994897E+03T2= 155556E+06T3= 64T4= 346T5= 41738E+03

n= variabelp= 13

N-table= 5

Mandels statistics End ResultLAB 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

45L 1326733 5665 6 -100 042 Fail 1326733 56646 6 5 -215046L 1355000 24365 4 -089 181 Fail - - 46L - - -186736L 1381949 5407 3 -078 040 Fail 1381949 54070 3 2 -159870L 1414120 - 1 -066 Fail 1414120 - 1 -127616L 1428333 5565 6 -061 041 1428333 55648 6 5 -113466L 1485550 7805 4 -039 058 1485550 78047 4 3 -56232L 1532500 5377 4 -021 040 1532500 53774 4 3 -09219L 1576833 10138 6 -004 075 1576833 101381 6 5 3519L 1582333 6166 6 -002 046 1582333 61659 6 5 40656L 1594432 4046 6 003 030 1594432 40463 6 5 52744L 1653000 3651 6 025 027 1653000 36508 6 5 111334L 1655127 13717 6 026 102 1655127 137168 6 5 113434L 1655127 13717 6 026 102 1655127 137168 6 5 113465L 1756500 16295 4 065 121 Fail 1756500 162949 4 3 214869L 2415000 30687 4 316 228 Fail - - 69L - - 8733

Totgem 158750 10900 gkg 1-level 232 (176) 13 1541734 (46L 69L) 13 12Totstd= 26187 8164 5-level 186 (152) 2

72RESULTS Mean = 15417337 gkg

Repeatability variance S2r = 8183950Repeatability std Sr = 904652 --gt 587 r = 253303Between lab variance S2L = 13631046Reproducibility var S2R = 21814995Reproducibility std SR = 1476990 --gt 958 R = 413557Remarks 2 Labs rejected (46L 69L)

000 050 100 150 200 250

k-values

45L

46L

36L

70L

16L

66L

32L

19L

9L

56L

44L

34L

34L

65L

69L

Mandels k statistics(Compost 2 - TOC)

-400 -200 00 200 400 600 800 1000

Deviation from Mean

45L

46L

36L

70L

16L

66L

32L

19L

9L

56L

44L

34L

34L

65L

69L

Labo

rato

ries

Compost 2 - TOC -- Mean PARM = 1542 [gkg]

-100 000 100 200 300 400

h-values

45L

36L

16L

32L

9L

44L

34L

69L

Labo

rato

ries

Mandels h statistics(Compost 2 - TOC)

Compost 2-TOC

Unit gkg

Mandels k statistics(Sludge 1 - TOC)Mandels h statistics(Sludge 1 - TOC)

Sample Sludge 1 Sludge 1 - TOC -- Mean PARM = 2721 [gkg]

Element TOC

General calcparmT1= 169626E+04T2= 465445E+06T3= 62T4= 326T5= 10312E+03

n= variabelp= 13

N-table= 5

Mandels statistics End ResultLAB 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

69L 233000 2362 4 -347 037 Fail - - 69L - - -2488046L 2312500 2062 4 -040 032 Fail 2312500 20616 4 3 -408565L 2615500 1708 4 004 026 2615500 17078 4 3 -105566L 2627200 8268 4 006 128 2627200 82678 4 3 -93836L 2664041 4976 3 011 077 2664041 49758 3 2 -56935L 2671500 3533 6 013 055 2671500 35331 6 5 -49556L 2692298 0874 6 016 014 Fail 2692298 08738 6 5 -28732L 2717500 6185 4 019 096 Fail 2717500 61847 4 3 -03519L 2753333 7819 6 025 121 Fail 2753333 78189 6 5 32470L 2814600 - 1 034 Fail 2814600 - 1 9369L 2853667 0398 6 039 006 Fail 2853667 03983 6 5 132716L 2860000 1673 6 040 026 Fail 2860000 16733 6 5 139045L 2884433 7033 6 044 109 Fail 2884433 70331 6 5 163544L 2906167 1129 6 047 017 Fail 2906167 11286 6 5 185234L 3186874 17674 6 089 274 Fail - - 34L - - 4659

Totgem 258617 4692 gkg 1-level 232 (176) 13 2720980 (34L 69L) 13 12Totstd= 67800 4610 5-level 186 (152) 2

72RESULTS Mean = 27209799 gkg

Repeatability variance S2r = 2104538Repeatability std Sr = 458752 --gt 169 r = 128451Between lab variance S2L = 23618387Reproducibility var S2R = 25722925Reproducibility std SR = 1603837 --gt 589 R = 449074Remarks 2 Labs rejected (34L 69L)

000 050 100 150 200 250 300

k-values

69L

46L

65L

66L

36L

35L

56L

32L

19L

70L

9L

16L

45L

44L

34L

Mandels k statistics(Sludge 1 - TOC)

-2500 -2000 -1500 -1000 -500 00 500

Deviation from Mean

69L

46L

65L

66L

36L

35L

56L

32L

19L

70L

9L

16L

45L

44L

34L

Labo

rato

ries

Sludge 1 - TOC -- Mean PARM = 2721 [gkg]

-400 -300 -200 -100 000 100

h-values

69L

65L

36L

56L

19L

9L

45L

34L

Labo

rato

ries

Mandels h statistics(Sludge 1 - TOC)

Sludge 1-TOC

68 Unit gkg

Mandels k statistics(Sludge 2 - TOC)Mandels h statistics(Sludge 2 - TOC)

Sample Sludge 2 Sludge 2 - TOC -- Mean PARM = 2207 [gkg]

Element TOC

General calcparmT1= 128601E+04T2= 285689E+06T3= 58T4= 310T5= 97826E+02

n= variabelp= 12

N-table= 5

Mandels statistics End ResultLAB 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

46L 182500 0500 4 -333 008 Fail - - 46L - - -2024466L 2029475 5267 4 -012 084 2029475 52674 4 3 -177436L 2072609 2222 3 -005 035 2072609 22222 3 2 -134365L 2084750 3865 4 -002 062 2084750 38647 4 3 -122135L 2140333 3119 6 007 050 2140333 31194 6 5 -66556L 2188021 1282 6 015 020 2188021 12822 6 5 -18819L 2223667 7916 6 022 126 Fail 2223667 79157 6 5 16832L 2242500 3096 4 025 049 Fail 2242500 30957 4 3 35645L 2266600 8322 6 029 132 Fail 2266600 83216 6 5 59770L 2272460 - 1 030 Fail 2272460 - 1 65616L 2291667 3869 6 033 062 Fail 2291667 38687 6 5 84844L 2302667 1546 6 035 025 Fail 2302667 15462 6 5 9589L 2367667 1296 6 047 021 Fail 2367667 12956 6 5 160834L 2718591 17124 6 108 273 Fail - - 34L - - 5117

Totgem 209882 4571 gkg 1-level 230 (176) 12 2206868 (34L 46L) 12 11Totstd= 57628 4485 5-level 185 (151) 2

68RESULTS Mean = 22068679 gkg

Repeatability variance S2r = 2126659Repeatability std Sr = 461157 --gt 209 r = 129124Between lab variance S2L = 9960432Reproducibility var S2R = 12087091Reproducibility std SR = 1099413 --gt 498 R = 307836Remarks 2 Labs rejected (34L 46L)

000 050 100 150 200 250 300

k-values

46L

66L

36L

65L

35L

56L

19L

32L

45L

70L

16L

44L

9L

34L

Mandels k statistics(Sludge 2 - TOC)

-2500 -2000 -1500 -1000 -500 00 500 1000

Deviation from Mean

46L

66L

36L

65L

35L

56L

19L

32L

45L

70L

16L

44L

9L

34L

Labo

rato

ries

Sludge 2 - TOC -- Mean PARM = 2207 [gkg]

-400 -300 -200 -100 000 100 200

h-values

46L

66L

36L

65L

35L

56L

19L

32L

45L

70L

16L

44L

9L

34L

Labo

rato

ries

Mandels h statistics(Sludge 2 - TOC)

Sludge 2-TOC

Unit gkg

Mandels k statistics(Soil 4 - TOC)Mandels h statistics(Soil 4 - TOC)

Sample Soil 4 Soil 4 - TOC -- Mean PARM = 1641 [gkg]

Element TOC

General calcparmT1= 102171E+03T2= 168700E+04T3= 62T4= 338T5= 94040E+00

n= variabelp= 12

N-table= 5

Mandels statistics End ResultLAB 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

36L 147161 0470 3 -036 068 Fail 147161 04702 3 2 -16965L 155250 0591 4 -032 085 Fail 155250 05909 4 3 -08844L 157900 0115 6 -031 017 Fail 157900 01152 6 5 -06232L 159250 0359 4 -031 052 Fail 159250 03594 4 3 -0489L 160500 0315 6 -030 045 Fail 160500 03146 6 5 -03656L 164927 0113 6 -028 016 Fail 164927 01127 6 5 00835L 165000 0261 6 -028 038 Fail 165000 02608 6 5 00919L 166667 0505 6 -027 073 Fail 166667 05046 6 5 02645L 168850 0763 6 -026 110 Fail 168850 07628 6 5 04816L 173333 0516 6 -024 074 Fail 173333 05164 6 5 09334L 174761 0346 6 -024 050 Fail 174761 03462 6 5 10730L 175333 0473 3 -024 068 Fail 175333 04726 3 2 11366L 189375 2035 4 -017 294 Fail - - 66L - - 25346L 227500 0500 4 000 072 - - 46L - - 63470L 1040400 - 1 360 Fail - - 70L - - 8763

Totgem 22841 0526 gkg 1-level 232 (176) 12 164078 (46L 66L70L) 12 11Totstd= 22541 0469 5-level 186 (152) 3

71RESULTS Mean = 1640777 gkg

Repeatability variance S2r = 018808Repeatability std Sr = 043368 --gt 264 r = 12143Between lab variance S2L = 054747Reproducibility var S2R = 073555Reproducibility std SR = 085764 --gt 523 R = 24014Remarks 3 Labs rejected (46L 66L70L)

000 050 100 150 200 250 300

k-values

36L

65L

44L

32L

9L

56L

35L

19L

45L

16L

34L

30L

66L

46L

70L

Mandels k statistics(Soil 4 - TOC)

-100 00 100 200 300 400 500 600 700 800 900

Deviation from Mean

36L

65L

44L

32L

9L

56L

35L

19L

45L

16L

34L

30L

66L

46L

70L

Labo

rato

ries

Soil 4 - TOC -- Mean PARM = 1641 [gkg]

-100 000 100 200 300 400

h-values

36L

44L

9L

35L

45L

34L

66L

70L

Labo

rato

ries

Mandels h statistics(Soil 4 - TOC)

Soil 4-TOC

Unit gkg

Mandels k statistics(Soil 5 - TOC)Mandels h statistics(Soil 5 - TOC)

Sample Soil 5 Soil 5 - TOC -- Mean PARM = 2102 [gkg]

Element TOC

General calcparmT1= 113661E+03T2= 240201E+04T3= 54T4= 300T5= 51756E+01

n= variabelp= 10

N-table= 5

Mandels statistics End ResultLAB 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

44L 164383 14708 6 -036 325 Fail - - 44L - - -45865L 181250 0830 4 -033 018 Fail 181250 08302 4 3 -29045L 200317 1116 6 -029 025 Fail 200317 11163 6 5 -09935L 201833 1828 6 -029 040 Fail 201833 18280 6 5 -08432L 203250 0585 4 -029 013 Fail 203250 05852 4 3 -07016L 209000 0959 6 -028 021 Fail 209000 09592 6 5 -0129L 211667 0427 6 -027 009 Fail 211667 04274 6 5 01556L 214030 0887 6 -027 020 Fail 214030 08868 6 5 03819L 216000 0795 6 -026 018 Fail 216000 07950 6 5 05834L 226009 1308 6 -024 029 Fail 226009 13076 6 5 15836L 228783 4310 3 -024 095 Fail - - 36L - - 18666L 238750 1234 4 -022 027 Fail 238750 12340 4 3 28570L 2213900 - 1 333 Fail - - 70L - - 20037

Totgem 36224 2416 gkg 1-level 227 (175) 10 210211 (36L44L 70L) 10 9Totstd= 55669 4003 5-level 184 (151) 3

64RESULTS Mean = 2102106 gkg

Repeatability variance S2r = 117627Repeatability std Sr = 108456 --gt 516 r = 30368Between lab variance S2L = 176699Reproducibility var S2R = 294326Reproducibility std SR = 171559 --gt 816 R = 48037Remarks 3 Labs rejected (36L44L 70L)

000 050 100 150 200 250 300 350

k-values

44L

65L

45L

35L

32L

16L

9L

56L

19L

34L

36L

66L

70L

Mandels k statistics(Soil 5 - TOC)

-500 00 500 1000 1500 2000 2500

Deviation from Mean

44L

65L

45L

35L

32L

16L

9L

56L

19L

34L

36L

66L

70L

Labo

rato

ries

Soil 5 - TOC -- Mean PARM = 2102 [gkg]

-100 000 100 200 300 400

h-values

44L

65L

45L

35L

32L

16L

9L

56L

19L

34L

36L

66L

70L

Labo

rato

ries

Mandels h statistics(Soil 5 - TOC)

Soil 5-TOC

17

Annex 4

Raw data submitted

Sample Compost 1 Sample Compost 2 Sample Sewage Sludge 1Element TOC [gkg] Element TOC [gkg] Element TOC [gkg]

LAB PARM LAB PARM LAB PARM30L 2600 19L 1691 19L 286730L 2580 19L 1634 19L 281430L 2560 19L 1619 19L 276934L 2969 19L 1604 19L 272034L 2936 19L 1499 19L 268834L 2958 19L 1414 19L 266234L 2994 34L 1527 34L 315234L 3199 34L 1622 34L 314934L 3024 34L 1519 34L 343035L 2306 34L 1753 34L 336535L 2300 34L 1636 34L 304235L 2298 34L 1874 34L 298335L 2296 35L 1506 35L 270735L 2291 35L 1312 35L 270335L 2259 35L 1294 35L 268836L 2546 35L 1279 35L 267436L 2527 35L 1191 35L 263136L 2470 35L 1177 35L 262644L 2583 36L 1418 36L 271344L 2581 36L 1408 36L 266544L 2578 36L 1320 36L 261444L 2539 44L 1719 44L 292044L 2528 44L 1664 44L 291644L 2525 44L 1654 44L 291245L 2658 44L 1637 44L 290045L 2600 44L 1624 44L 289645L 2546 44L 1620 44L 289345L 2461 45L 1428 45L 297645L 2409 45L 1325 45L 295245L 2350 45L 1323 45L 288546L 2460 45L 1321 45L 286646L 2400 45L 1309 45L 284046L 2370 45L 1253 45L 278746L 2350 46L 1580 46L 233056L 2436 46L 1550 46L 233056L 2435 46L 1170 46L 230056L 2405 46L 1120 46L 229056L 2397 56L 1642 56L 270256L 2375 56L 1626 56L 270156L 2358 56L 1622 56L 269465L 2587 56L 1571 56L 269365L 2542 56L 1561 56L 268465L 2483 56L 1545 56L 268066L 2454 65L 1933 65L 264166L 2429 65L 1838 65L 260966L 2365 65L 1693 65L 260766L 2262 65L 1562 65L 260569L 2730 66L 1561 66L 270169L 2250 66L 1545 66L 267469L 1440 66L 1420 66L 261969L 1420 66L 1417 66L 251470L 2435 69L 2700 69L 2639L 2594 69L 2660 69L 2409L 2570 69L 2170 69L 2199L 2565 69L 2130 69L 2109L 2563 70L 1414 70L 28159L 2562 9L 1644 9L 28579L 2555 9L 1641 9L 2856

32L 2290 9L 1602 9L 285532L 2390 9L 1589 9L 285532L 2510 9L 1526 9L 285332L 2470 9L 1492 9L 284616L 2380 32L 1470 32L 265016L 2530 32L 1520 32L 271016L 2400 32L 1540 32L 271016L 2500 32L 1600 32L 280016L 2420 16L 1400 16L 284016L 2410 16L 1440 16L 2840

16L 1470 16L 286016L 1510 16L 287016L 1360 16L 287016L 1390 16L 2880

Sample Sewage Sludge 2 Sample Soil 4 Sample Soil 5Element TOC [gkg] Element TOC [gkg] Element TOC [gkg]

LAB PARM LAB PARM LAB PARM19L 2308 19L 1720 19L 225019L 2303 19L 1700 19L 223019L 2239 19L 1690 19L 221019L 2204 19L 1670 19L 211019L 2192 19L 1640 19L 210019L 2096 19L 1580 19L 206034L 2631 30L 1790 34L 244334L 2471 30L 1770 34L 233434L 2977 30L 1700 34L 231534L 2785 34L 1740 34L 222134L 2780 34L 1692 34L 217634L 2668 34L 1727 34L 207335L 2179 34L 1767 35L 233035L 2160 34L 1777 35L 208035L 2158 34L 1783 35L 201035L 2132 35L 1700 35L 198035L 2119 35L 1650 35L 193035L 2094 35L 1650 35L 178036L 2096 35L 1640 36L 254036L 2069 35L 1630 36L 253436L 2052 35L 1630 36L 179044L 2325 36L 1500 44L 302144L 2309 36L 1497 44L 298244L 2307 36L 1417 44L 295644L 2305 44L 1594 44L 30744L 2287 44L 1587 44L 30044L 2283 44L 1584 44L 29745L 2331 44L 1574 45L 214945L 2327 44L 1573 45L 209245L 2308 44L 1562 45L 203345L 2287 45L 1827 45L 197145L 2234 45L 1709 45L 193345L 2113 45L 1666 45L 184146L 190 45L 1665 56L 223746L 180 45L 1664 56L 222246L 180 45L 1600 56L 220346L 180 46L 2300 56L 206956L 2204 46L 2300 56L 206856L 2197 46L 2300 56L 204456L 2193 46L 2200 65L 192056L 2185 56L 1668 65L 182056L 2183 56L 1654 65L 179056L 2167 56L 1653 65L 172065L 2136 56L 1643 66L 254365L 2091 56L 1639 66L 242465L 2065 56L 1638 66L 232165L 2047 65L 1630 66L 226266L 2105 65L 1560 70L 2213966L 2022 65L 1530 9L 218066L 2009 65L 1490 9L 214066L 1983 66L 2179 9L 213070L 2272 66L 1900 9L 21109L 2385 66L 1762 9L 20709L 2377 66L 1734 9L 20709L 2375 70L 10404 32L 20509L 2359 9L 1640 32L 21009L 2356 9L 1640 32L 20209L 2354 9L 1610 32L 1960

32L 2240 9L 1590 16L 210032L 2260 9L 1590 16L 220032L 2200 9L 1560 16L 220032L 2270 32L 1640 16L 206016L 2300 32L 1600 16L 197016L 2310 32L 1560 16L 201016L 2350 32L 157016L 2260 16L 170016L 2290 16L 180016L 2240 16L 1700

16L 180016L 170016L 1700

European Commission EUR 23012 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on total organic carbon Author(s) E Sobiecka H van der Sloot K Andersen B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 50 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07412-7 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 total organic carbon (TOC) in soils sludge and treated bio-waste 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

-23012-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 40201 EUR 23012 EN ISBN 978-92-79-07412-7 ISSN 1018-5593 DOI 10278847924 Luxembourg Office for Official Publications of the European Communities copy European Communities 2007 Reproduction is authorised provided the source is acknowledged Printed in Luxembourg

Project HORIZONTAL Validation Report Validation of a horizontal standard for the determination of total organic carbon (TOC) by dry combustion in soils sludge and treated biowaste in a European Intercomparison Exercise E Sobiecka H Van der Sloot K Andersen 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

Kirsten ANDERSEN DANAK Dyregaringrdsvej 5 B 2740 Skovlunde Denmark

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 soil and biowaste 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 intercomparison exercise This report summarises the work performed in a validation study for the draft standard for the determination of total organic carbon (TOC) in soil sludge and treated bio-waste It further explains the underlying statistical concept for the calculation of reproducibility and repeatability from intercomparison 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

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

MILC Measure Interlaboratory Comparison ndash (online data submission system)

p Number of labs

r Repeatability limit

R Reproducibility limit

sr Repeatability standard deviation

sR Reproducibility standard deviation

TC Technical Committee

TOC Total Organic Carbon

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 TOC 8

121 Samples dispatched for the validation of TOC 8

122 Draft standards to be followed 8

123 Analytical program 8

124 Timing and Submission of data 8

125 Participants 10

13 Summary results and derived performance characteristics 11

14 Annexes 13

5

Introduction to the validation project Project HORIZONTAL is interdisciplinary aiming at a harmonisation and horizontal standardisation of test procedures in particular for sludge 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 a 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 total organic carbon (TOC) are described hereafter

6

11 Statistical concept underlying the validation According to the requirements of the work package concerning data handling and interpretation of the project HORIZONTAL the respective validation intercomparisons should be evaluated according to ISO 5725-21994 In particular repeatability and reproducibility of the draft standard should be determined 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 work program 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 exercises For each parameter investigated at least 10 laboratories should be nominated to participate The same laboratories should analyse different parameters as far as possible Due to the complexity of analysis and the respective workload of the laboratories it was decided to propose six materials for the validation of the TOC draft standard Each laboratory received two bottles of each material and was requested to perform 6 independent analyses per material1 (3 per bottle) using the draft standard method The 6 analyses 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 was permitted but had to be reported Likewise the different materials could 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 had 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 was set and should 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 The draft standard was made available to the laboratories on the Project Horizontal homepage Each laboratory was requested to provide the signed statements on cooperation as given in Annex 1

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 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

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

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 TOC

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

bull Compost 1 A compost material from Vienna bull Compost 2 A compost material from Germany bull Sewage Sludge 1 A mixed sewage sludge from Essen Germany bull Sewage Sludge 2 A mixed municipal sludge from North Rhine Westphalia

Germany bull Soil 4 A sludge amended soil from Hohenheim Germany bull Soil 5 An agricultural soil from Reading UK

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

122 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 httpwwwecnnldocssocietyhorizontalTOC_standard_for_validationpdf

123 Analytical program Two bottles had to be analysed for each of the six materials and each bottle had to be analysed independently three times 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 dry matter correction was free for each participant

124 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

9

submission of results has been set for TOC to the 31st of January 2007 Alternatively the participants were allowed to submit data electronically as Excel sheet using Email All data were treated in a confidential way Any presentation hereafter refers 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 provided a 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

125 Participants The following table lists the participating organizations and entities in the validation exercise for the horizontal TOC standard

bull Austria o barbara - Engineering Consulting Research amp Service GmbH o Federal Research and Training Centre for Forests Natural Hazards and

Landscape o NUA Umweltanalytik GmbH o Oumlsterreichische Agentur fuumlr Gesundheit und Ernaumlhrungssicherheit o Universitaumlt fuumlr Bodenkultur Wien o Shimadzu Europa GmbH o Umweltbundesamt o University of Natural resources and Applied Life Sciences

bull Belgium o VITO

bull France o INERIS o CEMAGREF - UR QELY o INRA - Laboratoire dAnalyse des Sols

bull Germany o ALBO-tec Technologiezentrum Fuumlr Analytik und Bodenmechanik GmbH

bull Norway o Norwegian Institute for Water Research

bull The Netherlands o ALCONTROL BV o Analytico Milieu B V

11

13 Summary results and derived performance characteristics The result of the various statistical evaluation according to ISO 5725-2 including outlier tests calculation of repeatability and reproducibility standard deviations can be found in Annex 3 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 The calculated average values the repeatability standard deviation (sr) and the reproducibility standard deviation (sR) are given in Table 1 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 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 total organic carbon (TOC) by dry combustion in treated biowaste sludge and soil All concentrations are expressed in gkg dry matter

Matrix Parameter Mean sr sR r R p Outliers Total number of data

No of

LOD

Sludge 1 TOC 272 17 59 13 45 13 2 62 0 Sludge 2 TOC 220 21 50 13 31 12 2 58 0

Compost 1 TOC 246 25 43 17 30 13 2 58 0 Compost 2 TOC 154 59 96 25 41 13 2 64 0

Soil 4 TOC 164 26 52 12 24 12 3 62 0 Soil 5 TOC 210 52 82 30 48 10 3 54 0

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

13

14 Annexes Annex 1 Model questionnaire to be filled by the participating laboratories Annex 2 Report on the validation materials used Annex 3 Statistical calculations Annex 4 Data submitted

14

14

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

15

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

16

Annex 3

Statistical calculations

Unit gkg

Mandels k statistics(Compost 1 - TOC)Mandels h statistics(Compost 1 - TOC)

Sample Compost 1 Compost 1 - TOC -- Mean PARM = 2463 [gkg]

Element TOC

General calcparmT1= 142643E+04T2= 351264E+06T3= 58T4= 292T5= 16501E+03

n= variabelp= 13

N-table= 5

Mandels statistics End ResultLAB 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

69L 1960000 64265 4 -235 352 Fail - - 69L - - -502735L 2291667 1674 6 -081 009 2291667 16741 6 5 -171066L 2377425 8552 4 -041 047 2377425 85518 4 3 -85346L 2395000 4796 4 -033 026 2395000 47958 4 3 -67756L 2401227 3133 6 -030 017 2401227 31330 6 5 -61432L 2415000 9713 4 -024 053 2415000 97125 4 3 -47770L 2435100 - 1 -014 2435100 - 1 -27616L 2440000 6033 6 -012 033 2440000 60332 6 5 -22745L 2503800 11759 6 018 064 2503800 117589 6 5 41136L 2514416 3994 3 023 022 2514416 39937 3 2 51765L 2537333 5216 3 033 029 2537333 52157 3 2 74744L 2555667 2783 6 042 015 2555667 27826 6 5 9309L 2568167 1356 6 048 007 2568167 13556 6 5 105530L 2580000 2000 3 053 011 2580000 20000 3 2 117334L 3013269 9580 6 255 053 Fail - - 34L - - 5506

Totgem 246587 9632 gkg 1-level 232 (176) 13 2462677 (34L 69L) 13 12Totstd= 21507 16070 5-level 186 (152) 2

68RESULTS Mean = 24626770 gkg

Repeatability variance S2r = 3666797Repeatability std Sr = 605541 --gt 246 r = 169551Between lab variance S2L = 7715586Reproducibility var S2R = 11382383Reproducibility std SR = 1066882 --gt 433 R = 298727Remarks 2 Labs rejected (34L 69L)

000 050 100 150 200 250 300 350 400

k-values

69L

35L

66L

46L

56L

32L

70L

16L

45L

36L

65L

44L

9L

30L

34L

Mandels k statistics(Compost 1 - TOC)

-600 -400 -200 00 200 400 600

Deviation from Mean

69L

35L

66L

46L

56L

32L

70L

16L

45L

36L

65L

44L

9L

30L

34L

Labo

rato

ries

Compost 1 - TOC -- Mean PARM = 2463 [gkg]

-300 -200 -100 000 100 200 300

h-values

69L

66L

56L

70L

45L

65L

9L

34L

Labo

rato

ries

Mandels h statistics(Compost 1 - TOC)

Compost 1-TOC

Unit gkg

Mandels k statistics(Compost 2 - TOC)Mandels h statistics(Compost 2 - TOC)

Sample Compost 2 Compost 2 - TOC -- Mean PARM = 1542 [gkg]

Element TOC

General calcparmT1= 994897E+03T2= 155556E+06T3= 64T4= 346T5= 41738E+03

n= variabelp= 13

N-table= 5

Mandels statistics End ResultLAB 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

45L 1326733 5665 6 -100 042 Fail 1326733 56646 6 5 -215046L 1355000 24365 4 -089 181 Fail - - 46L - - -186736L 1381949 5407 3 -078 040 Fail 1381949 54070 3 2 -159870L 1414120 - 1 -066 Fail 1414120 - 1 -127616L 1428333 5565 6 -061 041 1428333 55648 6 5 -113466L 1485550 7805 4 -039 058 1485550 78047 4 3 -56232L 1532500 5377 4 -021 040 1532500 53774 4 3 -09219L 1576833 10138 6 -004 075 1576833 101381 6 5 3519L 1582333 6166 6 -002 046 1582333 61659 6 5 40656L 1594432 4046 6 003 030 1594432 40463 6 5 52744L 1653000 3651 6 025 027 1653000 36508 6 5 111334L 1655127 13717 6 026 102 1655127 137168 6 5 113434L 1655127 13717 6 026 102 1655127 137168 6 5 113465L 1756500 16295 4 065 121 Fail 1756500 162949 4 3 214869L 2415000 30687 4 316 228 Fail - - 69L - - 8733

Totgem 158750 10900 gkg 1-level 232 (176) 13 1541734 (46L 69L) 13 12Totstd= 26187 8164 5-level 186 (152) 2

72RESULTS Mean = 15417337 gkg

Repeatability variance S2r = 8183950Repeatability std Sr = 904652 --gt 587 r = 253303Between lab variance S2L = 13631046Reproducibility var S2R = 21814995Reproducibility std SR = 1476990 --gt 958 R = 413557Remarks 2 Labs rejected (46L 69L)

000 050 100 150 200 250

k-values

45L

46L

36L

70L

16L

66L

32L

19L

9L

56L

44L

34L

34L

65L

69L

Mandels k statistics(Compost 2 - TOC)

-400 -200 00 200 400 600 800 1000

Deviation from Mean

45L

46L

36L

70L

16L

66L

32L

19L

9L

56L

44L

34L

34L

65L

69L

Labo

rato

ries

Compost 2 - TOC -- Mean PARM = 1542 [gkg]

-100 000 100 200 300 400

h-values

45L

36L

16L

32L

9L

44L

34L

69L

Labo

rato

ries

Mandels h statistics(Compost 2 - TOC)

Compost 2-TOC

Unit gkg

Mandels k statistics(Sludge 1 - TOC)Mandels h statistics(Sludge 1 - TOC)

Sample Sludge 1 Sludge 1 - TOC -- Mean PARM = 2721 [gkg]

Element TOC

General calcparmT1= 169626E+04T2= 465445E+06T3= 62T4= 326T5= 10312E+03

n= variabelp= 13

N-table= 5

Mandels statistics End ResultLAB 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

69L 233000 2362 4 -347 037 Fail - - 69L - - -2488046L 2312500 2062 4 -040 032 Fail 2312500 20616 4 3 -408565L 2615500 1708 4 004 026 2615500 17078 4 3 -105566L 2627200 8268 4 006 128 2627200 82678 4 3 -93836L 2664041 4976 3 011 077 2664041 49758 3 2 -56935L 2671500 3533 6 013 055 2671500 35331 6 5 -49556L 2692298 0874 6 016 014 Fail 2692298 08738 6 5 -28732L 2717500 6185 4 019 096 Fail 2717500 61847 4 3 -03519L 2753333 7819 6 025 121 Fail 2753333 78189 6 5 32470L 2814600 - 1 034 Fail 2814600 - 1 9369L 2853667 0398 6 039 006 Fail 2853667 03983 6 5 132716L 2860000 1673 6 040 026 Fail 2860000 16733 6 5 139045L 2884433 7033 6 044 109 Fail 2884433 70331 6 5 163544L 2906167 1129 6 047 017 Fail 2906167 11286 6 5 185234L 3186874 17674 6 089 274 Fail - - 34L - - 4659

Totgem 258617 4692 gkg 1-level 232 (176) 13 2720980 (34L 69L) 13 12Totstd= 67800 4610 5-level 186 (152) 2

72RESULTS Mean = 27209799 gkg

Repeatability variance S2r = 2104538Repeatability std Sr = 458752 --gt 169 r = 128451Between lab variance S2L = 23618387Reproducibility var S2R = 25722925Reproducibility std SR = 1603837 --gt 589 R = 449074Remarks 2 Labs rejected (34L 69L)

000 050 100 150 200 250 300

k-values

69L

46L

65L

66L

36L

35L

56L

32L

19L

70L

9L

16L

45L

44L

34L

Mandels k statistics(Sludge 1 - TOC)

-2500 -2000 -1500 -1000 -500 00 500

Deviation from Mean

69L

46L

65L

66L

36L

35L

56L

32L

19L

70L

9L

16L

45L

44L

34L

Labo

rato

ries

Sludge 1 - TOC -- Mean PARM = 2721 [gkg]

-400 -300 -200 -100 000 100

h-values

69L

65L

36L

56L

19L

9L

45L

34L

Labo

rato

ries

Mandels h statistics(Sludge 1 - TOC)

Sludge 1-TOC

68 Unit gkg

Mandels k statistics(Sludge 2 - TOC)Mandels h statistics(Sludge 2 - TOC)

Sample Sludge 2 Sludge 2 - TOC -- Mean PARM = 2207 [gkg]

Element TOC

General calcparmT1= 128601E+04T2= 285689E+06T3= 58T4= 310T5= 97826E+02

n= variabelp= 12

N-table= 5

Mandels statistics End ResultLAB 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

46L 182500 0500 4 -333 008 Fail - - 46L - - -2024466L 2029475 5267 4 -012 084 2029475 52674 4 3 -177436L 2072609 2222 3 -005 035 2072609 22222 3 2 -134365L 2084750 3865 4 -002 062 2084750 38647 4 3 -122135L 2140333 3119 6 007 050 2140333 31194 6 5 -66556L 2188021 1282 6 015 020 2188021 12822 6 5 -18819L 2223667 7916 6 022 126 Fail 2223667 79157 6 5 16832L 2242500 3096 4 025 049 Fail 2242500 30957 4 3 35645L 2266600 8322 6 029 132 Fail 2266600 83216 6 5 59770L 2272460 - 1 030 Fail 2272460 - 1 65616L 2291667 3869 6 033 062 Fail 2291667 38687 6 5 84844L 2302667 1546 6 035 025 Fail 2302667 15462 6 5 9589L 2367667 1296 6 047 021 Fail 2367667 12956 6 5 160834L 2718591 17124 6 108 273 Fail - - 34L - - 5117

Totgem 209882 4571 gkg 1-level 230 (176) 12 2206868 (34L 46L) 12 11Totstd= 57628 4485 5-level 185 (151) 2

68RESULTS Mean = 22068679 gkg

Repeatability variance S2r = 2126659Repeatability std Sr = 461157 --gt 209 r = 129124Between lab variance S2L = 9960432Reproducibility var S2R = 12087091Reproducibility std SR = 1099413 --gt 498 R = 307836Remarks 2 Labs rejected (34L 46L)

000 050 100 150 200 250 300

k-values

46L

66L

36L

65L

35L

56L

19L

32L

45L

70L

16L

44L

9L

34L

Mandels k statistics(Sludge 2 - TOC)

-2500 -2000 -1500 -1000 -500 00 500 1000

Deviation from Mean

46L

66L

36L

65L

35L

56L

19L

32L

45L

70L

16L

44L

9L

34L

Labo

rato

ries

Sludge 2 - TOC -- Mean PARM = 2207 [gkg]

-400 -300 -200 -100 000 100 200

h-values

46L

66L

36L

65L

35L

56L

19L

32L

45L

70L

16L

44L

9L

34L

Labo

rato

ries

Mandels h statistics(Sludge 2 - TOC)

Sludge 2-TOC

Unit gkg

Mandels k statistics(Soil 4 - TOC)Mandels h statistics(Soil 4 - TOC)

Sample Soil 4 Soil 4 - TOC -- Mean PARM = 1641 [gkg]

Element TOC

General calcparmT1= 102171E+03T2= 168700E+04T3= 62T4= 338T5= 94040E+00

n= variabelp= 12

N-table= 5

Mandels statistics End ResultLAB 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

36L 147161 0470 3 -036 068 Fail 147161 04702 3 2 -16965L 155250 0591 4 -032 085 Fail 155250 05909 4 3 -08844L 157900 0115 6 -031 017 Fail 157900 01152 6 5 -06232L 159250 0359 4 -031 052 Fail 159250 03594 4 3 -0489L 160500 0315 6 -030 045 Fail 160500 03146 6 5 -03656L 164927 0113 6 -028 016 Fail 164927 01127 6 5 00835L 165000 0261 6 -028 038 Fail 165000 02608 6 5 00919L 166667 0505 6 -027 073 Fail 166667 05046 6 5 02645L 168850 0763 6 -026 110 Fail 168850 07628 6 5 04816L 173333 0516 6 -024 074 Fail 173333 05164 6 5 09334L 174761 0346 6 -024 050 Fail 174761 03462 6 5 10730L 175333 0473 3 -024 068 Fail 175333 04726 3 2 11366L 189375 2035 4 -017 294 Fail - - 66L - - 25346L 227500 0500 4 000 072 - - 46L - - 63470L 1040400 - 1 360 Fail - - 70L - - 8763

Totgem 22841 0526 gkg 1-level 232 (176) 12 164078 (46L 66L70L) 12 11Totstd= 22541 0469 5-level 186 (152) 3

71RESULTS Mean = 1640777 gkg

Repeatability variance S2r = 018808Repeatability std Sr = 043368 --gt 264 r = 12143Between lab variance S2L = 054747Reproducibility var S2R = 073555Reproducibility std SR = 085764 --gt 523 R = 24014Remarks 3 Labs rejected (46L 66L70L)

000 050 100 150 200 250 300

k-values

36L

65L

44L

32L

9L

56L

35L

19L

45L

16L

34L

30L

66L

46L

70L

Mandels k statistics(Soil 4 - TOC)

-100 00 100 200 300 400 500 600 700 800 900

Deviation from Mean

36L

65L

44L

32L

9L

56L

35L

19L

45L

16L

34L

30L

66L

46L

70L

Labo

rato

ries

Soil 4 - TOC -- Mean PARM = 1641 [gkg]

-100 000 100 200 300 400

h-values

36L

44L

9L

35L

45L

34L

66L

70L

Labo

rato

ries

Mandels h statistics(Soil 4 - TOC)

Soil 4-TOC

Unit gkg

Mandels k statistics(Soil 5 - TOC)Mandels h statistics(Soil 5 - TOC)

Sample Soil 5 Soil 5 - TOC -- Mean PARM = 2102 [gkg]

Element TOC

General calcparmT1= 113661E+03T2= 240201E+04T3= 54T4= 300T5= 51756E+01

n= variabelp= 10

N-table= 5

Mandels statistics End ResultLAB 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

44L 164383 14708 6 -036 325 Fail - - 44L - - -45865L 181250 0830 4 -033 018 Fail 181250 08302 4 3 -29045L 200317 1116 6 -029 025 Fail 200317 11163 6 5 -09935L 201833 1828 6 -029 040 Fail 201833 18280 6 5 -08432L 203250 0585 4 -029 013 Fail 203250 05852 4 3 -07016L 209000 0959 6 -028 021 Fail 209000 09592 6 5 -0129L 211667 0427 6 -027 009 Fail 211667 04274 6 5 01556L 214030 0887 6 -027 020 Fail 214030 08868 6 5 03819L 216000 0795 6 -026 018 Fail 216000 07950 6 5 05834L 226009 1308 6 -024 029 Fail 226009 13076 6 5 15836L 228783 4310 3 -024 095 Fail - - 36L - - 18666L 238750 1234 4 -022 027 Fail 238750 12340 4 3 28570L 2213900 - 1 333 Fail - - 70L - - 20037

Totgem 36224 2416 gkg 1-level 227 (175) 10 210211 (36L44L 70L) 10 9Totstd= 55669 4003 5-level 184 (151) 3

64RESULTS Mean = 2102106 gkg

Repeatability variance S2r = 117627Repeatability std Sr = 108456 --gt 516 r = 30368Between lab variance S2L = 176699Reproducibility var S2R = 294326Reproducibility std SR = 171559 --gt 816 R = 48037Remarks 3 Labs rejected (36L44L 70L)

000 050 100 150 200 250 300 350

k-values

44L

65L

45L

35L

32L

16L

9L

56L

19L

34L

36L

66L

70L

Mandels k statistics(Soil 5 - TOC)

-500 00 500 1000 1500 2000 2500

Deviation from Mean

44L

65L

45L

35L

32L

16L

9L

56L

19L

34L

36L

66L

70L

Labo

rato

ries

Soil 5 - TOC -- Mean PARM = 2102 [gkg]

-100 000 100 200 300 400

h-values

44L

65L

45L

35L

32L

16L

9L

56L

19L

34L

36L

66L

70L

Labo

rato

ries

Mandels h statistics(Soil 5 - TOC)

Soil 5-TOC

17

Annex 4

Raw data submitted

Sample Compost 1 Sample Compost 2 Sample Sewage Sludge 1Element TOC [gkg] Element TOC [gkg] Element TOC [gkg]

LAB PARM LAB PARM LAB PARM30L 2600 19L 1691 19L 286730L 2580 19L 1634 19L 281430L 2560 19L 1619 19L 276934L 2969 19L 1604 19L 272034L 2936 19L 1499 19L 268834L 2958 19L 1414 19L 266234L 2994 34L 1527 34L 315234L 3199 34L 1622 34L 314934L 3024 34L 1519 34L 343035L 2306 34L 1753 34L 336535L 2300 34L 1636 34L 304235L 2298 34L 1874 34L 298335L 2296 35L 1506 35L 270735L 2291 35L 1312 35L 270335L 2259 35L 1294 35L 268836L 2546 35L 1279 35L 267436L 2527 35L 1191 35L 263136L 2470 35L 1177 35L 262644L 2583 36L 1418 36L 271344L 2581 36L 1408 36L 266544L 2578 36L 1320 36L 261444L 2539 44L 1719 44L 292044L 2528 44L 1664 44L 291644L 2525 44L 1654 44L 291245L 2658 44L 1637 44L 290045L 2600 44L 1624 44L 289645L 2546 44L 1620 44L 289345L 2461 45L 1428 45L 297645L 2409 45L 1325 45L 295245L 2350 45L 1323 45L 288546L 2460 45L 1321 45L 286646L 2400 45L 1309 45L 284046L 2370 45L 1253 45L 278746L 2350 46L 1580 46L 233056L 2436 46L 1550 46L 233056L 2435 46L 1170 46L 230056L 2405 46L 1120 46L 229056L 2397 56L 1642 56L 270256L 2375 56L 1626 56L 270156L 2358 56L 1622 56L 269465L 2587 56L 1571 56L 269365L 2542 56L 1561 56L 268465L 2483 56L 1545 56L 268066L 2454 65L 1933 65L 264166L 2429 65L 1838 65L 260966L 2365 65L 1693 65L 260766L 2262 65L 1562 65L 260569L 2730 66L 1561 66L 270169L 2250 66L 1545 66L 267469L 1440 66L 1420 66L 261969L 1420 66L 1417 66L 251470L 2435 69L 2700 69L 2639L 2594 69L 2660 69L 2409L 2570 69L 2170 69L 2199L 2565 69L 2130 69L 2109L 2563 70L 1414 70L 28159L 2562 9L 1644 9L 28579L 2555 9L 1641 9L 2856

32L 2290 9L 1602 9L 285532L 2390 9L 1589 9L 285532L 2510 9L 1526 9L 285332L 2470 9L 1492 9L 284616L 2380 32L 1470 32L 265016L 2530 32L 1520 32L 271016L 2400 32L 1540 32L 271016L 2500 32L 1600 32L 280016L 2420 16L 1400 16L 284016L 2410 16L 1440 16L 2840

16L 1470 16L 286016L 1510 16L 287016L 1360 16L 287016L 1390 16L 2880

Sample Sewage Sludge 2 Sample Soil 4 Sample Soil 5Element TOC [gkg] Element TOC [gkg] Element TOC [gkg]

LAB PARM LAB PARM LAB PARM19L 2308 19L 1720 19L 225019L 2303 19L 1700 19L 223019L 2239 19L 1690 19L 221019L 2204 19L 1670 19L 211019L 2192 19L 1640 19L 210019L 2096 19L 1580 19L 206034L 2631 30L 1790 34L 244334L 2471 30L 1770 34L 233434L 2977 30L 1700 34L 231534L 2785 34L 1740 34L 222134L 2780 34L 1692 34L 217634L 2668 34L 1727 34L 207335L 2179 34L 1767 35L 233035L 2160 34L 1777 35L 208035L 2158 34L 1783 35L 201035L 2132 35L 1700 35L 198035L 2119 35L 1650 35L 193035L 2094 35L 1650 35L 178036L 2096 35L 1640 36L 254036L 2069 35L 1630 36L 253436L 2052 35L 1630 36L 179044L 2325 36L 1500 44L 302144L 2309 36L 1497 44L 298244L 2307 36L 1417 44L 295644L 2305 44L 1594 44L 30744L 2287 44L 1587 44L 30044L 2283 44L 1584 44L 29745L 2331 44L 1574 45L 214945L 2327 44L 1573 45L 209245L 2308 44L 1562 45L 203345L 2287 45L 1827 45L 197145L 2234 45L 1709 45L 193345L 2113 45L 1666 45L 184146L 190 45L 1665 56L 223746L 180 45L 1664 56L 222246L 180 45L 1600 56L 220346L 180 46L 2300 56L 206956L 2204 46L 2300 56L 206856L 2197 46L 2300 56L 204456L 2193 46L 2200 65L 192056L 2185 56L 1668 65L 182056L 2183 56L 1654 65L 179056L 2167 56L 1653 65L 172065L 2136 56L 1643 66L 254365L 2091 56L 1639 66L 242465L 2065 56L 1638 66L 232165L 2047 65L 1630 66L 226266L 2105 65L 1560 70L 2213966L 2022 65L 1530 9L 218066L 2009 65L 1490 9L 214066L 1983 66L 2179 9L 213070L 2272 66L 1900 9L 21109L 2385 66L 1762 9L 20709L 2377 66L 1734 9L 20709L 2375 70L 10404 32L 20509L 2359 9L 1640 32L 21009L 2356 9L 1640 32L 20209L 2354 9L 1610 32L 1960

32L 2240 9L 1590 16L 210032L 2260 9L 1590 16L 220032L 2200 9L 1560 16L 220032L 2270 32L 1640 16L 206016L 2300 32L 1600 16L 197016L 2310 32L 1560 16L 201016L 2350 32L 157016L 2260 16L 170016L 2290 16L 180016L 2240 16L 1700

16L 180016L 170016L 1700

European Commission EUR 23012 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on total organic carbon Author(s) E Sobiecka H van der Sloot K Andersen B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 50 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07412-7 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 total organic carbon (TOC) in soils sludge and treated bio-waste 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

-23012-EN

-C

Project HORIZONTAL Validation Report Validation of a horizontal standard for the determination of total organic carbon (TOC) by dry combustion in soils sludge and treated biowaste in a European Intercomparison Exercise E Sobiecka H Van der Sloot K Andersen 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

Kirsten ANDERSEN DANAK Dyregaringrdsvej 5 B 2740 Skovlunde Denmark

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 soil and biowaste 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 intercomparison exercise This report summarises the work performed in a validation study for the draft standard for the determination of total organic carbon (TOC) in soil sludge and treated bio-waste It further explains the underlying statistical concept for the calculation of reproducibility and repeatability from intercomparison 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

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

MILC Measure Interlaboratory Comparison ndash (online data submission system)

p Number of labs

r Repeatability limit

R Reproducibility limit

sr Repeatability standard deviation

sR Reproducibility standard deviation

TC Technical Committee

TOC Total Organic Carbon

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 TOC 8

121 Samples dispatched for the validation of TOC 8

122 Draft standards to be followed 8

123 Analytical program 8

124 Timing and Submission of data 8

125 Participants 10

13 Summary results and derived performance characteristics 11

14 Annexes 13

5

Introduction to the validation project Project HORIZONTAL is interdisciplinary aiming at a harmonisation and horizontal standardisation of test procedures in particular for sludge 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 a 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 total organic carbon (TOC) are described hereafter

6

11 Statistical concept underlying the validation According to the requirements of the work package concerning data handling and interpretation of the project HORIZONTAL the respective validation intercomparisons should be evaluated according to ISO 5725-21994 In particular repeatability and reproducibility of the draft standard should be determined 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 work program 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 exercises For each parameter investigated at least 10 laboratories should be nominated to participate The same laboratories should analyse different parameters as far as possible Due to the complexity of analysis and the respective workload of the laboratories it was decided to propose six materials for the validation of the TOC draft standard Each laboratory received two bottles of each material and was requested to perform 6 independent analyses per material1 (3 per bottle) using the draft standard method The 6 analyses 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 was permitted but had to be reported Likewise the different materials could 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 had 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 was set and should 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 The draft standard was made available to the laboratories on the Project Horizontal homepage Each laboratory was requested to provide the signed statements on cooperation as given in Annex 1

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 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

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

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 TOC

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

bull Compost 1 A compost material from Vienna bull Compost 2 A compost material from Germany bull Sewage Sludge 1 A mixed sewage sludge from Essen Germany bull Sewage Sludge 2 A mixed municipal sludge from North Rhine Westphalia

Germany bull Soil 4 A sludge amended soil from Hohenheim Germany bull Soil 5 An agricultural soil from Reading UK

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

122 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 httpwwwecnnldocssocietyhorizontalTOC_standard_for_validationpdf

123 Analytical program Two bottles had to be analysed for each of the six materials and each bottle had to be analysed independently three times 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 dry matter correction was free for each participant

124 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

9

submission of results has been set for TOC to the 31st of January 2007 Alternatively the participants were allowed to submit data electronically as Excel sheet using Email All data were treated in a confidential way Any presentation hereafter refers 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 provided a 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

125 Participants The following table lists the participating organizations and entities in the validation exercise for the horizontal TOC standard

bull Austria o barbara - Engineering Consulting Research amp Service GmbH o Federal Research and Training Centre for Forests Natural Hazards and

Landscape o NUA Umweltanalytik GmbH o Oumlsterreichische Agentur fuumlr Gesundheit und Ernaumlhrungssicherheit o Universitaumlt fuumlr Bodenkultur Wien o Shimadzu Europa GmbH o Umweltbundesamt o University of Natural resources and Applied Life Sciences

bull Belgium o VITO

bull France o INERIS o CEMAGREF - UR QELY o INRA - Laboratoire dAnalyse des Sols

bull Germany o ALBO-tec Technologiezentrum Fuumlr Analytik und Bodenmechanik GmbH

bull Norway o Norwegian Institute for Water Research

bull The Netherlands o ALCONTROL BV o Analytico Milieu B V

11

13 Summary results and derived performance characteristics The result of the various statistical evaluation according to ISO 5725-2 including outlier tests calculation of repeatability and reproducibility standard deviations can be found in Annex 3 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 The calculated average values the repeatability standard deviation (sr) and the reproducibility standard deviation (sR) are given in Table 1 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 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 total organic carbon (TOC) by dry combustion in treated biowaste sludge and soil All concentrations are expressed in gkg dry matter

Matrix Parameter Mean sr sR r R p Outliers Total number of data

No of

LOD

Sludge 1 TOC 272 17 59 13 45 13 2 62 0 Sludge 2 TOC 220 21 50 13 31 12 2 58 0

Compost 1 TOC 246 25 43 17 30 13 2 58 0 Compost 2 TOC 154 59 96 25 41 13 2 64 0

Soil 4 TOC 164 26 52 12 24 12 3 62 0 Soil 5 TOC 210 52 82 30 48 10 3 54 0

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

13

14 Annexes Annex 1 Model questionnaire to be filled by the participating laboratories Annex 2 Report on the validation materials used Annex 3 Statistical calculations Annex 4 Data submitted

14

14

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

15

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

16

Annex 3

Statistical calculations

Unit gkg

Mandels k statistics(Compost 1 - TOC)Mandels h statistics(Compost 1 - TOC)

Sample Compost 1 Compost 1 - TOC -- Mean PARM = 2463 [gkg]

Element TOC

General calcparmT1= 142643E+04T2= 351264E+06T3= 58T4= 292T5= 16501E+03

n= variabelp= 13

N-table= 5

Mandels statistics End ResultLAB 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

69L 1960000 64265 4 -235 352 Fail - - 69L - - -502735L 2291667 1674 6 -081 009 2291667 16741 6 5 -171066L 2377425 8552 4 -041 047 2377425 85518 4 3 -85346L 2395000 4796 4 -033 026 2395000 47958 4 3 -67756L 2401227 3133 6 -030 017 2401227 31330 6 5 -61432L 2415000 9713 4 -024 053 2415000 97125 4 3 -47770L 2435100 - 1 -014 2435100 - 1 -27616L 2440000 6033 6 -012 033 2440000 60332 6 5 -22745L 2503800 11759 6 018 064 2503800 117589 6 5 41136L 2514416 3994 3 023 022 2514416 39937 3 2 51765L 2537333 5216 3 033 029 2537333 52157 3 2 74744L 2555667 2783 6 042 015 2555667 27826 6 5 9309L 2568167 1356 6 048 007 2568167 13556 6 5 105530L 2580000 2000 3 053 011 2580000 20000 3 2 117334L 3013269 9580 6 255 053 Fail - - 34L - - 5506

Totgem 246587 9632 gkg 1-level 232 (176) 13 2462677 (34L 69L) 13 12Totstd= 21507 16070 5-level 186 (152) 2

68RESULTS Mean = 24626770 gkg

Repeatability variance S2r = 3666797Repeatability std Sr = 605541 --gt 246 r = 169551Between lab variance S2L = 7715586Reproducibility var S2R = 11382383Reproducibility std SR = 1066882 --gt 433 R = 298727Remarks 2 Labs rejected (34L 69L)

000 050 100 150 200 250 300 350 400

k-values

69L

35L

66L

46L

56L

32L

70L

16L

45L

36L

65L

44L

9L

30L

34L

Mandels k statistics(Compost 1 - TOC)

-600 -400 -200 00 200 400 600

Deviation from Mean

69L

35L

66L

46L

56L

32L

70L

16L

45L

36L

65L

44L

9L

30L

34L

Labo

rato

ries

Compost 1 - TOC -- Mean PARM = 2463 [gkg]

-300 -200 -100 000 100 200 300

h-values

69L

66L

56L

70L

45L

65L

9L

34L

Labo

rato

ries

Mandels h statistics(Compost 1 - TOC)

Compost 1-TOC

Unit gkg

Mandels k statistics(Compost 2 - TOC)Mandels h statistics(Compost 2 - TOC)

Sample Compost 2 Compost 2 - TOC -- Mean PARM = 1542 [gkg]

Element TOC

General calcparmT1= 994897E+03T2= 155556E+06T3= 64T4= 346T5= 41738E+03

n= variabelp= 13

N-table= 5

Mandels statistics End ResultLAB 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

45L 1326733 5665 6 -100 042 Fail 1326733 56646 6 5 -215046L 1355000 24365 4 -089 181 Fail - - 46L - - -186736L 1381949 5407 3 -078 040 Fail 1381949 54070 3 2 -159870L 1414120 - 1 -066 Fail 1414120 - 1 -127616L 1428333 5565 6 -061 041 1428333 55648 6 5 -113466L 1485550 7805 4 -039 058 1485550 78047 4 3 -56232L 1532500 5377 4 -021 040 1532500 53774 4 3 -09219L 1576833 10138 6 -004 075 1576833 101381 6 5 3519L 1582333 6166 6 -002 046 1582333 61659 6 5 40656L 1594432 4046 6 003 030 1594432 40463 6 5 52744L 1653000 3651 6 025 027 1653000 36508 6 5 111334L 1655127 13717 6 026 102 1655127 137168 6 5 113434L 1655127 13717 6 026 102 1655127 137168 6 5 113465L 1756500 16295 4 065 121 Fail 1756500 162949 4 3 214869L 2415000 30687 4 316 228 Fail - - 69L - - 8733

Totgem 158750 10900 gkg 1-level 232 (176) 13 1541734 (46L 69L) 13 12Totstd= 26187 8164 5-level 186 (152) 2

72RESULTS Mean = 15417337 gkg

Repeatability variance S2r = 8183950Repeatability std Sr = 904652 --gt 587 r = 253303Between lab variance S2L = 13631046Reproducibility var S2R = 21814995Reproducibility std SR = 1476990 --gt 958 R = 413557Remarks 2 Labs rejected (46L 69L)

000 050 100 150 200 250

k-values

45L

46L

36L

70L

16L

66L

32L

19L

9L

56L

44L

34L

34L

65L

69L

Mandels k statistics(Compost 2 - TOC)

-400 -200 00 200 400 600 800 1000

Deviation from Mean

45L

46L

36L

70L

16L

66L

32L

19L

9L

56L

44L

34L

34L

65L

69L

Labo

rato

ries

Compost 2 - TOC -- Mean PARM = 1542 [gkg]

-100 000 100 200 300 400

h-values

45L

36L

16L

32L

9L

44L

34L

69L

Labo

rato

ries

Mandels h statistics(Compost 2 - TOC)

Compost 2-TOC

Unit gkg

Mandels k statistics(Sludge 1 - TOC)Mandels h statistics(Sludge 1 - TOC)

Sample Sludge 1 Sludge 1 - TOC -- Mean PARM = 2721 [gkg]

Element TOC

General calcparmT1= 169626E+04T2= 465445E+06T3= 62T4= 326T5= 10312E+03

n= variabelp= 13

N-table= 5

Mandels statistics End ResultLAB 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

69L 233000 2362 4 -347 037 Fail - - 69L - - -2488046L 2312500 2062 4 -040 032 Fail 2312500 20616 4 3 -408565L 2615500 1708 4 004 026 2615500 17078 4 3 -105566L 2627200 8268 4 006 128 2627200 82678 4 3 -93836L 2664041 4976 3 011 077 2664041 49758 3 2 -56935L 2671500 3533 6 013 055 2671500 35331 6 5 -49556L 2692298 0874 6 016 014 Fail 2692298 08738 6 5 -28732L 2717500 6185 4 019 096 Fail 2717500 61847 4 3 -03519L 2753333 7819 6 025 121 Fail 2753333 78189 6 5 32470L 2814600 - 1 034 Fail 2814600 - 1 9369L 2853667 0398 6 039 006 Fail 2853667 03983 6 5 132716L 2860000 1673 6 040 026 Fail 2860000 16733 6 5 139045L 2884433 7033 6 044 109 Fail 2884433 70331 6 5 163544L 2906167 1129 6 047 017 Fail 2906167 11286 6 5 185234L 3186874 17674 6 089 274 Fail - - 34L - - 4659

Totgem 258617 4692 gkg 1-level 232 (176) 13 2720980 (34L 69L) 13 12Totstd= 67800 4610 5-level 186 (152) 2

72RESULTS Mean = 27209799 gkg

Repeatability variance S2r = 2104538Repeatability std Sr = 458752 --gt 169 r = 128451Between lab variance S2L = 23618387Reproducibility var S2R = 25722925Reproducibility std SR = 1603837 --gt 589 R = 449074Remarks 2 Labs rejected (34L 69L)

000 050 100 150 200 250 300

k-values

69L

46L

65L

66L

36L

35L

56L

32L

19L

70L

9L

16L

45L

44L

34L

Mandels k statistics(Sludge 1 - TOC)

-2500 -2000 -1500 -1000 -500 00 500

Deviation from Mean

69L

46L

65L

66L

36L

35L

56L

32L

19L

70L

9L

16L

45L

44L

34L

Labo

rato

ries

Sludge 1 - TOC -- Mean PARM = 2721 [gkg]

-400 -300 -200 -100 000 100

h-values

69L

65L

36L

56L

19L

9L

45L

34L

Labo

rato

ries

Mandels h statistics(Sludge 1 - TOC)

Sludge 1-TOC

68 Unit gkg

Mandels k statistics(Sludge 2 - TOC)Mandels h statistics(Sludge 2 - TOC)

Sample Sludge 2 Sludge 2 - TOC -- Mean PARM = 2207 [gkg]

Element TOC

General calcparmT1= 128601E+04T2= 285689E+06T3= 58T4= 310T5= 97826E+02

n= variabelp= 12

N-table= 5

Mandels statistics End ResultLAB 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

46L 182500 0500 4 -333 008 Fail - - 46L - - -2024466L 2029475 5267 4 -012 084 2029475 52674 4 3 -177436L 2072609 2222 3 -005 035 2072609 22222 3 2 -134365L 2084750 3865 4 -002 062 2084750 38647 4 3 -122135L 2140333 3119 6 007 050 2140333 31194 6 5 -66556L 2188021 1282 6 015 020 2188021 12822 6 5 -18819L 2223667 7916 6 022 126 Fail 2223667 79157 6 5 16832L 2242500 3096 4 025 049 Fail 2242500 30957 4 3 35645L 2266600 8322 6 029 132 Fail 2266600 83216 6 5 59770L 2272460 - 1 030 Fail 2272460 - 1 65616L 2291667 3869 6 033 062 Fail 2291667 38687 6 5 84844L 2302667 1546 6 035 025 Fail 2302667 15462 6 5 9589L 2367667 1296 6 047 021 Fail 2367667 12956 6 5 160834L 2718591 17124 6 108 273 Fail - - 34L - - 5117

Totgem 209882 4571 gkg 1-level 230 (176) 12 2206868 (34L 46L) 12 11Totstd= 57628 4485 5-level 185 (151) 2

68RESULTS Mean = 22068679 gkg

Repeatability variance S2r = 2126659Repeatability std Sr = 461157 --gt 209 r = 129124Between lab variance S2L = 9960432Reproducibility var S2R = 12087091Reproducibility std SR = 1099413 --gt 498 R = 307836Remarks 2 Labs rejected (34L 46L)

000 050 100 150 200 250 300

k-values

46L

66L

36L

65L

35L

56L

19L

32L

45L

70L

16L

44L

9L

34L

Mandels k statistics(Sludge 2 - TOC)

-2500 -2000 -1500 -1000 -500 00 500 1000

Deviation from Mean

46L

66L

36L

65L

35L

56L

19L

32L

45L

70L

16L

44L

9L

34L

Labo

rato

ries

Sludge 2 - TOC -- Mean PARM = 2207 [gkg]

-400 -300 -200 -100 000 100 200

h-values

46L

66L

36L

65L

35L

56L

19L

32L

45L

70L

16L

44L

9L

34L

Labo

rato

ries

Mandels h statistics(Sludge 2 - TOC)

Sludge 2-TOC

Unit gkg

Mandels k statistics(Soil 4 - TOC)Mandels h statistics(Soil 4 - TOC)

Sample Soil 4 Soil 4 - TOC -- Mean PARM = 1641 [gkg]

Element TOC

General calcparmT1= 102171E+03T2= 168700E+04T3= 62T4= 338T5= 94040E+00

n= variabelp= 12

N-table= 5

Mandels statistics End ResultLAB 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

36L 147161 0470 3 -036 068 Fail 147161 04702 3 2 -16965L 155250 0591 4 -032 085 Fail 155250 05909 4 3 -08844L 157900 0115 6 -031 017 Fail 157900 01152 6 5 -06232L 159250 0359 4 -031 052 Fail 159250 03594 4 3 -0489L 160500 0315 6 -030 045 Fail 160500 03146 6 5 -03656L 164927 0113 6 -028 016 Fail 164927 01127 6 5 00835L 165000 0261 6 -028 038 Fail 165000 02608 6 5 00919L 166667 0505 6 -027 073 Fail 166667 05046 6 5 02645L 168850 0763 6 -026 110 Fail 168850 07628 6 5 04816L 173333 0516 6 -024 074 Fail 173333 05164 6 5 09334L 174761 0346 6 -024 050 Fail 174761 03462 6 5 10730L 175333 0473 3 -024 068 Fail 175333 04726 3 2 11366L 189375 2035 4 -017 294 Fail - - 66L - - 25346L 227500 0500 4 000 072 - - 46L - - 63470L 1040400 - 1 360 Fail - - 70L - - 8763

Totgem 22841 0526 gkg 1-level 232 (176) 12 164078 (46L 66L70L) 12 11Totstd= 22541 0469 5-level 186 (152) 3

71RESULTS Mean = 1640777 gkg

Repeatability variance S2r = 018808Repeatability std Sr = 043368 --gt 264 r = 12143Between lab variance S2L = 054747Reproducibility var S2R = 073555Reproducibility std SR = 085764 --gt 523 R = 24014Remarks 3 Labs rejected (46L 66L70L)

000 050 100 150 200 250 300

k-values

36L

65L

44L

32L

9L

56L

35L

19L

45L

16L

34L

30L

66L

46L

70L

Mandels k statistics(Soil 4 - TOC)

-100 00 100 200 300 400 500 600 700 800 900

Deviation from Mean

36L

65L

44L

32L

9L

56L

35L

19L

45L

16L

34L

30L

66L

46L

70L

Labo

rato

ries

Soil 4 - TOC -- Mean PARM = 1641 [gkg]

-100 000 100 200 300 400

h-values

36L

44L

9L

35L

45L

34L

66L

70L

Labo

rato

ries

Mandels h statistics(Soil 4 - TOC)

Soil 4-TOC

Unit gkg

Mandels k statistics(Soil 5 - TOC)Mandels h statistics(Soil 5 - TOC)

Sample Soil 5 Soil 5 - TOC -- Mean PARM = 2102 [gkg]

Element TOC

General calcparmT1= 113661E+03T2= 240201E+04T3= 54T4= 300T5= 51756E+01

n= variabelp= 10

N-table= 5

Mandels statistics End ResultLAB 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

44L 164383 14708 6 -036 325 Fail - - 44L - - -45865L 181250 0830 4 -033 018 Fail 181250 08302 4 3 -29045L 200317 1116 6 -029 025 Fail 200317 11163 6 5 -09935L 201833 1828 6 -029 040 Fail 201833 18280 6 5 -08432L 203250 0585 4 -029 013 Fail 203250 05852 4 3 -07016L 209000 0959 6 -028 021 Fail 209000 09592 6 5 -0129L 211667 0427 6 -027 009 Fail 211667 04274 6 5 01556L 214030 0887 6 -027 020 Fail 214030 08868 6 5 03819L 216000 0795 6 -026 018 Fail 216000 07950 6 5 05834L 226009 1308 6 -024 029 Fail 226009 13076 6 5 15836L 228783 4310 3 -024 095 Fail - - 36L - - 18666L 238750 1234 4 -022 027 Fail 238750 12340 4 3 28570L 2213900 - 1 333 Fail - - 70L - - 20037

Totgem 36224 2416 gkg 1-level 227 (175) 10 210211 (36L44L 70L) 10 9Totstd= 55669 4003 5-level 184 (151) 3

64RESULTS Mean = 2102106 gkg

Repeatability variance S2r = 117627Repeatability std Sr = 108456 --gt 516 r = 30368Between lab variance S2L = 176699Reproducibility var S2R = 294326Reproducibility std SR = 171559 --gt 816 R = 48037Remarks 3 Labs rejected (36L44L 70L)

000 050 100 150 200 250 300 350

k-values

44L

65L

45L

35L

32L

16L

9L

56L

19L

34L

36L

66L

70L

Mandels k statistics(Soil 5 - TOC)

-500 00 500 1000 1500 2000 2500

Deviation from Mean

44L

65L

45L

35L

32L

16L

9L

56L

19L

34L

36L

66L

70L

Labo

rato

ries

Soil 5 - TOC -- Mean PARM = 2102 [gkg]

-100 000 100 200 300 400

h-values

44L

65L

45L

35L

32L

16L

9L

56L

19L

34L

36L

66L

70L

Labo

rato

ries

Mandels h statistics(Soil 5 - TOC)

Soil 5-TOC

17

Annex 4

Raw data submitted

Sample Compost 1 Sample Compost 2 Sample Sewage Sludge 1Element TOC [gkg] Element TOC [gkg] Element TOC [gkg]

LAB PARM LAB PARM LAB PARM30L 2600 19L 1691 19L 286730L 2580 19L 1634 19L 281430L 2560 19L 1619 19L 276934L 2969 19L 1604 19L 272034L 2936 19L 1499 19L 268834L 2958 19L 1414 19L 266234L 2994 34L 1527 34L 315234L 3199 34L 1622 34L 314934L 3024 34L 1519 34L 343035L 2306 34L 1753 34L 336535L 2300 34L 1636 34L 304235L 2298 34L 1874 34L 298335L 2296 35L 1506 35L 270735L 2291 35L 1312 35L 270335L 2259 35L 1294 35L 268836L 2546 35L 1279 35L 267436L 2527 35L 1191 35L 263136L 2470 35L 1177 35L 262644L 2583 36L 1418 36L 271344L 2581 36L 1408 36L 266544L 2578 36L 1320 36L 261444L 2539 44L 1719 44L 292044L 2528 44L 1664 44L 291644L 2525 44L 1654 44L 291245L 2658 44L 1637 44L 290045L 2600 44L 1624 44L 289645L 2546 44L 1620 44L 289345L 2461 45L 1428 45L 297645L 2409 45L 1325 45L 295245L 2350 45L 1323 45L 288546L 2460 45L 1321 45L 286646L 2400 45L 1309 45L 284046L 2370 45L 1253 45L 278746L 2350 46L 1580 46L 233056L 2436 46L 1550 46L 233056L 2435 46L 1170 46L 230056L 2405 46L 1120 46L 229056L 2397 56L 1642 56L 270256L 2375 56L 1626 56L 270156L 2358 56L 1622 56L 269465L 2587 56L 1571 56L 269365L 2542 56L 1561 56L 268465L 2483 56L 1545 56L 268066L 2454 65L 1933 65L 264166L 2429 65L 1838 65L 260966L 2365 65L 1693 65L 260766L 2262 65L 1562 65L 260569L 2730 66L 1561 66L 270169L 2250 66L 1545 66L 267469L 1440 66L 1420 66L 261969L 1420 66L 1417 66L 251470L 2435 69L 2700 69L 2639L 2594 69L 2660 69L 2409L 2570 69L 2170 69L 2199L 2565 69L 2130 69L 2109L 2563 70L 1414 70L 28159L 2562 9L 1644 9L 28579L 2555 9L 1641 9L 2856

32L 2290 9L 1602 9L 285532L 2390 9L 1589 9L 285532L 2510 9L 1526 9L 285332L 2470 9L 1492 9L 284616L 2380 32L 1470 32L 265016L 2530 32L 1520 32L 271016L 2400 32L 1540 32L 271016L 2500 32L 1600 32L 280016L 2420 16L 1400 16L 284016L 2410 16L 1440 16L 2840

16L 1470 16L 286016L 1510 16L 287016L 1360 16L 287016L 1390 16L 2880

Sample Sewage Sludge 2 Sample Soil 4 Sample Soil 5Element TOC [gkg] Element TOC [gkg] Element TOC [gkg]

LAB PARM LAB PARM LAB PARM19L 2308 19L 1720 19L 225019L 2303 19L 1700 19L 223019L 2239 19L 1690 19L 221019L 2204 19L 1670 19L 211019L 2192 19L 1640 19L 210019L 2096 19L 1580 19L 206034L 2631 30L 1790 34L 244334L 2471 30L 1770 34L 233434L 2977 30L 1700 34L 231534L 2785 34L 1740 34L 222134L 2780 34L 1692 34L 217634L 2668 34L 1727 34L 207335L 2179 34L 1767 35L 233035L 2160 34L 1777 35L 208035L 2158 34L 1783 35L 201035L 2132 35L 1700 35L 198035L 2119 35L 1650 35L 193035L 2094 35L 1650 35L 178036L 2096 35L 1640 36L 254036L 2069 35L 1630 36L 253436L 2052 35L 1630 36L 179044L 2325 36L 1500 44L 302144L 2309 36L 1497 44L 298244L 2307 36L 1417 44L 295644L 2305 44L 1594 44L 30744L 2287 44L 1587 44L 30044L 2283 44L 1584 44L 29745L 2331 44L 1574 45L 214945L 2327 44L 1573 45L 209245L 2308 44L 1562 45L 203345L 2287 45L 1827 45L 197145L 2234 45L 1709 45L 193345L 2113 45L 1666 45L 184146L 190 45L 1665 56L 223746L 180 45L 1664 56L 222246L 180 45L 1600 56L 220346L 180 46L 2300 56L 206956L 2204 46L 2300 56L 206856L 2197 46L 2300 56L 204456L 2193 46L 2200 65L 192056L 2185 56L 1668 65L 182056L 2183 56L 1654 65L 179056L 2167 56L 1653 65L 172065L 2136 56L 1643 66L 254365L 2091 56L 1639 66L 242465L 2065 56L 1638 66L 232165L 2047 65L 1630 66L 226266L 2105 65L 1560 70L 2213966L 2022 65L 1530 9L 218066L 2009 65L 1490 9L 214066L 1983 66L 2179 9L 213070L 2272 66L 1900 9L 21109L 2385 66L 1762 9L 20709L 2377 66L 1734 9L 20709L 2375 70L 10404 32L 20509L 2359 9L 1640 32L 21009L 2356 9L 1640 32L 20209L 2354 9L 1610 32L 1960

32L 2240 9L 1590 16L 210032L 2260 9L 1590 16L 220032L 2200 9L 1560 16L 220032L 2270 32L 1640 16L 206016L 2300 32L 1600 16L 197016L 2310 32L 1560 16L 201016L 2350 32L 157016L 2260 16L 170016L 2290 16L 180016L 2240 16L 1700

16L 180016L 170016L 1700

European Commission EUR 23012 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on total organic carbon Author(s) E Sobiecka H van der Sloot K Andersen B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 50 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07412-7 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 total organic carbon (TOC) in soils sludge and treated bio-waste 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

-23012-EN

-C

Summary Project HORIZONTAL is interdisciplinary aiming at a harmonisation and horizontal standardisation of test procedures in particular for sludge soil and biowaste 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 intercomparison exercise This report summarises the work performed in a validation study for the draft standard for the determination of total organic carbon (TOC) in soil sludge and treated bio-waste It further explains the underlying statistical concept for the calculation of reproducibility and repeatability from intercomparison 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

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

MILC Measure Interlaboratory Comparison ndash (online data submission system)

p Number of labs

r Repeatability limit

R Reproducibility limit

sr Repeatability standard deviation

sR Reproducibility standard deviation

TC Technical Committee

TOC Total Organic Carbon

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 TOC 8

121 Samples dispatched for the validation of TOC 8

122 Draft standards to be followed 8

123 Analytical program 8

124 Timing and Submission of data 8

125 Participants 10

13 Summary results and derived performance characteristics 11

14 Annexes 13

5

Introduction to the validation project Project HORIZONTAL is interdisciplinary aiming at a harmonisation and horizontal standardisation of test procedures in particular for sludge 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 a 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 total organic carbon (TOC) are described hereafter

6

11 Statistical concept underlying the validation According to the requirements of the work package concerning data handling and interpretation of the project HORIZONTAL the respective validation intercomparisons should be evaluated according to ISO 5725-21994 In particular repeatability and reproducibility of the draft standard should be determined 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 work program 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 exercises For each parameter investigated at least 10 laboratories should be nominated to participate The same laboratories should analyse different parameters as far as possible Due to the complexity of analysis and the respective workload of the laboratories it was decided to propose six materials for the validation of the TOC draft standard Each laboratory received two bottles of each material and was requested to perform 6 independent analyses per material1 (3 per bottle) using the draft standard method The 6 analyses 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 was permitted but had to be reported Likewise the different materials could 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 had 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 was set and should 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 The draft standard was made available to the laboratories on the Project Horizontal homepage Each laboratory was requested to provide the signed statements on cooperation as given in Annex 1

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 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

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

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 TOC

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

bull Compost 1 A compost material from Vienna bull Compost 2 A compost material from Germany bull Sewage Sludge 1 A mixed sewage sludge from Essen Germany bull Sewage Sludge 2 A mixed municipal sludge from North Rhine Westphalia

Germany bull Soil 4 A sludge amended soil from Hohenheim Germany bull Soil 5 An agricultural soil from Reading UK

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

122 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 httpwwwecnnldocssocietyhorizontalTOC_standard_for_validationpdf

123 Analytical program Two bottles had to be analysed for each of the six materials and each bottle had to be analysed independently three times 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 dry matter correction was free for each participant

124 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

9

submission of results has been set for TOC to the 31st of January 2007 Alternatively the participants were allowed to submit data electronically as Excel sheet using Email All data were treated in a confidential way Any presentation hereafter refers 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 provided a 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

125 Participants The following table lists the participating organizations and entities in the validation exercise for the horizontal TOC standard

bull Austria o barbara - Engineering Consulting Research amp Service GmbH o Federal Research and Training Centre for Forests Natural Hazards and

Landscape o NUA Umweltanalytik GmbH o Oumlsterreichische Agentur fuumlr Gesundheit und Ernaumlhrungssicherheit o Universitaumlt fuumlr Bodenkultur Wien o Shimadzu Europa GmbH o Umweltbundesamt o University of Natural resources and Applied Life Sciences

bull Belgium o VITO

bull France o INERIS o CEMAGREF - UR QELY o INRA - Laboratoire dAnalyse des Sols

bull Germany o ALBO-tec Technologiezentrum Fuumlr Analytik und Bodenmechanik GmbH

bull Norway o Norwegian Institute for Water Research

bull The Netherlands o ALCONTROL BV o Analytico Milieu B V

11

13 Summary results and derived performance characteristics The result of the various statistical evaluation according to ISO 5725-2 including outlier tests calculation of repeatability and reproducibility standard deviations can be found in Annex 3 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 The calculated average values the repeatability standard deviation (sr) and the reproducibility standard deviation (sR) are given in Table 1 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 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 total organic carbon (TOC) by dry combustion in treated biowaste sludge and soil All concentrations are expressed in gkg dry matter

Matrix Parameter Mean sr sR r R p Outliers Total number of data

No of

LOD

Sludge 1 TOC 272 17 59 13 45 13 2 62 0 Sludge 2 TOC 220 21 50 13 31 12 2 58 0

Compost 1 TOC 246 25 43 17 30 13 2 58 0 Compost 2 TOC 154 59 96 25 41 13 2 64 0

Soil 4 TOC 164 26 52 12 24 12 3 62 0 Soil 5 TOC 210 52 82 30 48 10 3 54 0

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

13

14 Annexes Annex 1 Model questionnaire to be filled by the participating laboratories Annex 2 Report on the validation materials used Annex 3 Statistical calculations Annex 4 Data submitted

14

14

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

15

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

16

Annex 3

Statistical calculations

Unit gkg

Mandels k statistics(Compost 1 - TOC)Mandels h statistics(Compost 1 - TOC)

Sample Compost 1 Compost 1 - TOC -- Mean PARM = 2463 [gkg]

Element TOC

General calcparmT1= 142643E+04T2= 351264E+06T3= 58T4= 292T5= 16501E+03

n= variabelp= 13

N-table= 5

Mandels statistics End ResultLAB 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

69L 1960000 64265 4 -235 352 Fail - - 69L - - -502735L 2291667 1674 6 -081 009 2291667 16741 6 5 -171066L 2377425 8552 4 -041 047 2377425 85518 4 3 -85346L 2395000 4796 4 -033 026 2395000 47958 4 3 -67756L 2401227 3133 6 -030 017 2401227 31330 6 5 -61432L 2415000 9713 4 -024 053 2415000 97125 4 3 -47770L 2435100 - 1 -014 2435100 - 1 -27616L 2440000 6033 6 -012 033 2440000 60332 6 5 -22745L 2503800 11759 6 018 064 2503800 117589 6 5 41136L 2514416 3994 3 023 022 2514416 39937 3 2 51765L 2537333 5216 3 033 029 2537333 52157 3 2 74744L 2555667 2783 6 042 015 2555667 27826 6 5 9309L 2568167 1356 6 048 007 2568167 13556 6 5 105530L 2580000 2000 3 053 011 2580000 20000 3 2 117334L 3013269 9580 6 255 053 Fail - - 34L - - 5506

Totgem 246587 9632 gkg 1-level 232 (176) 13 2462677 (34L 69L) 13 12Totstd= 21507 16070 5-level 186 (152) 2

68RESULTS Mean = 24626770 gkg

Repeatability variance S2r = 3666797Repeatability std Sr = 605541 --gt 246 r = 169551Between lab variance S2L = 7715586Reproducibility var S2R = 11382383Reproducibility std SR = 1066882 --gt 433 R = 298727Remarks 2 Labs rejected (34L 69L)

000 050 100 150 200 250 300 350 400

k-values

69L

35L

66L

46L

56L

32L

70L

16L

45L

36L

65L

44L

9L

30L

34L

Mandels k statistics(Compost 1 - TOC)

-600 -400 -200 00 200 400 600

Deviation from Mean

69L

35L

66L

46L

56L

32L

70L

16L

45L

36L

65L

44L

9L

30L

34L

Labo

rato

ries

Compost 1 - TOC -- Mean PARM = 2463 [gkg]

-300 -200 -100 000 100 200 300

h-values

69L

66L

56L

70L

45L

65L

9L

34L

Labo

rato

ries

Mandels h statistics(Compost 1 - TOC)

Compost 1-TOC

Unit gkg

Mandels k statistics(Compost 2 - TOC)Mandels h statistics(Compost 2 - TOC)

Sample Compost 2 Compost 2 - TOC -- Mean PARM = 1542 [gkg]

Element TOC

General calcparmT1= 994897E+03T2= 155556E+06T3= 64T4= 346T5= 41738E+03

n= variabelp= 13

N-table= 5

Mandels statistics End ResultLAB 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

45L 1326733 5665 6 -100 042 Fail 1326733 56646 6 5 -215046L 1355000 24365 4 -089 181 Fail - - 46L - - -186736L 1381949 5407 3 -078 040 Fail 1381949 54070 3 2 -159870L 1414120 - 1 -066 Fail 1414120 - 1 -127616L 1428333 5565 6 -061 041 1428333 55648 6 5 -113466L 1485550 7805 4 -039 058 1485550 78047 4 3 -56232L 1532500 5377 4 -021 040 1532500 53774 4 3 -09219L 1576833 10138 6 -004 075 1576833 101381 6 5 3519L 1582333 6166 6 -002 046 1582333 61659 6 5 40656L 1594432 4046 6 003 030 1594432 40463 6 5 52744L 1653000 3651 6 025 027 1653000 36508 6 5 111334L 1655127 13717 6 026 102 1655127 137168 6 5 113434L 1655127 13717 6 026 102 1655127 137168 6 5 113465L 1756500 16295 4 065 121 Fail 1756500 162949 4 3 214869L 2415000 30687 4 316 228 Fail - - 69L - - 8733

Totgem 158750 10900 gkg 1-level 232 (176) 13 1541734 (46L 69L) 13 12Totstd= 26187 8164 5-level 186 (152) 2

72RESULTS Mean = 15417337 gkg

Repeatability variance S2r = 8183950Repeatability std Sr = 904652 --gt 587 r = 253303Between lab variance S2L = 13631046Reproducibility var S2R = 21814995Reproducibility std SR = 1476990 --gt 958 R = 413557Remarks 2 Labs rejected (46L 69L)

000 050 100 150 200 250

k-values

45L

46L

36L

70L

16L

66L

32L

19L

9L

56L

44L

34L

34L

65L

69L

Mandels k statistics(Compost 2 - TOC)

-400 -200 00 200 400 600 800 1000

Deviation from Mean

45L

46L

36L

70L

16L

66L

32L

19L

9L

56L

44L

34L

34L

65L

69L

Labo

rato

ries

Compost 2 - TOC -- Mean PARM = 1542 [gkg]

-100 000 100 200 300 400

h-values

45L

36L

16L

32L

9L

44L

34L

69L

Labo

rato

ries

Mandels h statistics(Compost 2 - TOC)

Compost 2-TOC

Unit gkg

Mandels k statistics(Sludge 1 - TOC)Mandels h statistics(Sludge 1 - TOC)

Sample Sludge 1 Sludge 1 - TOC -- Mean PARM = 2721 [gkg]

Element TOC

General calcparmT1= 169626E+04T2= 465445E+06T3= 62T4= 326T5= 10312E+03

n= variabelp= 13

N-table= 5

Mandels statistics End ResultLAB 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

69L 233000 2362 4 -347 037 Fail - - 69L - - -2488046L 2312500 2062 4 -040 032 Fail 2312500 20616 4 3 -408565L 2615500 1708 4 004 026 2615500 17078 4 3 -105566L 2627200 8268 4 006 128 2627200 82678 4 3 -93836L 2664041 4976 3 011 077 2664041 49758 3 2 -56935L 2671500 3533 6 013 055 2671500 35331 6 5 -49556L 2692298 0874 6 016 014 Fail 2692298 08738 6 5 -28732L 2717500 6185 4 019 096 Fail 2717500 61847 4 3 -03519L 2753333 7819 6 025 121 Fail 2753333 78189 6 5 32470L 2814600 - 1 034 Fail 2814600 - 1 9369L 2853667 0398 6 039 006 Fail 2853667 03983 6 5 132716L 2860000 1673 6 040 026 Fail 2860000 16733 6 5 139045L 2884433 7033 6 044 109 Fail 2884433 70331 6 5 163544L 2906167 1129 6 047 017 Fail 2906167 11286 6 5 185234L 3186874 17674 6 089 274 Fail - - 34L - - 4659

Totgem 258617 4692 gkg 1-level 232 (176) 13 2720980 (34L 69L) 13 12Totstd= 67800 4610 5-level 186 (152) 2

72RESULTS Mean = 27209799 gkg

Repeatability variance S2r = 2104538Repeatability std Sr = 458752 --gt 169 r = 128451Between lab variance S2L = 23618387Reproducibility var S2R = 25722925Reproducibility std SR = 1603837 --gt 589 R = 449074Remarks 2 Labs rejected (34L 69L)

000 050 100 150 200 250 300

k-values

69L

46L

65L

66L

36L

35L

56L

32L

19L

70L

9L

16L

45L

44L

34L

Mandels k statistics(Sludge 1 - TOC)

-2500 -2000 -1500 -1000 -500 00 500

Deviation from Mean

69L

46L

65L

66L

36L

35L

56L

32L

19L

70L

9L

16L

45L

44L

34L

Labo

rato

ries

Sludge 1 - TOC -- Mean PARM = 2721 [gkg]

-400 -300 -200 -100 000 100

h-values

69L

65L

36L

56L

19L

9L

45L

34L

Labo

rato

ries

Mandels h statistics(Sludge 1 - TOC)

Sludge 1-TOC

68 Unit gkg

Mandels k statistics(Sludge 2 - TOC)Mandels h statistics(Sludge 2 - TOC)

Sample Sludge 2 Sludge 2 - TOC -- Mean PARM = 2207 [gkg]

Element TOC

General calcparmT1= 128601E+04T2= 285689E+06T3= 58T4= 310T5= 97826E+02

n= variabelp= 12

N-table= 5

Mandels statistics End ResultLAB 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

46L 182500 0500 4 -333 008 Fail - - 46L - - -2024466L 2029475 5267 4 -012 084 2029475 52674 4 3 -177436L 2072609 2222 3 -005 035 2072609 22222 3 2 -134365L 2084750 3865 4 -002 062 2084750 38647 4 3 -122135L 2140333 3119 6 007 050 2140333 31194 6 5 -66556L 2188021 1282 6 015 020 2188021 12822 6 5 -18819L 2223667 7916 6 022 126 Fail 2223667 79157 6 5 16832L 2242500 3096 4 025 049 Fail 2242500 30957 4 3 35645L 2266600 8322 6 029 132 Fail 2266600 83216 6 5 59770L 2272460 - 1 030 Fail 2272460 - 1 65616L 2291667 3869 6 033 062 Fail 2291667 38687 6 5 84844L 2302667 1546 6 035 025 Fail 2302667 15462 6 5 9589L 2367667 1296 6 047 021 Fail 2367667 12956 6 5 160834L 2718591 17124 6 108 273 Fail - - 34L - - 5117

Totgem 209882 4571 gkg 1-level 230 (176) 12 2206868 (34L 46L) 12 11Totstd= 57628 4485 5-level 185 (151) 2

68RESULTS Mean = 22068679 gkg

Repeatability variance S2r = 2126659Repeatability std Sr = 461157 --gt 209 r = 129124Between lab variance S2L = 9960432Reproducibility var S2R = 12087091Reproducibility std SR = 1099413 --gt 498 R = 307836Remarks 2 Labs rejected (34L 46L)

000 050 100 150 200 250 300

k-values

46L

66L

36L

65L

35L

56L

19L

32L

45L

70L

16L

44L

9L

34L

Mandels k statistics(Sludge 2 - TOC)

-2500 -2000 -1500 -1000 -500 00 500 1000

Deviation from Mean

46L

66L

36L

65L

35L

56L

19L

32L

45L

70L

16L

44L

9L

34L

Labo

rato

ries

Sludge 2 - TOC -- Mean PARM = 2207 [gkg]

-400 -300 -200 -100 000 100 200

h-values

46L

66L

36L

65L

35L

56L

19L

32L

45L

70L

16L

44L

9L

34L

Labo

rato

ries

Mandels h statistics(Sludge 2 - TOC)

Sludge 2-TOC

Unit gkg

Mandels k statistics(Soil 4 - TOC)Mandels h statistics(Soil 4 - TOC)

Sample Soil 4 Soil 4 - TOC -- Mean PARM = 1641 [gkg]

Element TOC

General calcparmT1= 102171E+03T2= 168700E+04T3= 62T4= 338T5= 94040E+00

n= variabelp= 12

N-table= 5

Mandels statistics End ResultLAB 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

36L 147161 0470 3 -036 068 Fail 147161 04702 3 2 -16965L 155250 0591 4 -032 085 Fail 155250 05909 4 3 -08844L 157900 0115 6 -031 017 Fail 157900 01152 6 5 -06232L 159250 0359 4 -031 052 Fail 159250 03594 4 3 -0489L 160500 0315 6 -030 045 Fail 160500 03146 6 5 -03656L 164927 0113 6 -028 016 Fail 164927 01127 6 5 00835L 165000 0261 6 -028 038 Fail 165000 02608 6 5 00919L 166667 0505 6 -027 073 Fail 166667 05046 6 5 02645L 168850 0763 6 -026 110 Fail 168850 07628 6 5 04816L 173333 0516 6 -024 074 Fail 173333 05164 6 5 09334L 174761 0346 6 -024 050 Fail 174761 03462 6 5 10730L 175333 0473 3 -024 068 Fail 175333 04726 3 2 11366L 189375 2035 4 -017 294 Fail - - 66L - - 25346L 227500 0500 4 000 072 - - 46L - - 63470L 1040400 - 1 360 Fail - - 70L - - 8763

Totgem 22841 0526 gkg 1-level 232 (176) 12 164078 (46L 66L70L) 12 11Totstd= 22541 0469 5-level 186 (152) 3

71RESULTS Mean = 1640777 gkg

Repeatability variance S2r = 018808Repeatability std Sr = 043368 --gt 264 r = 12143Between lab variance S2L = 054747Reproducibility var S2R = 073555Reproducibility std SR = 085764 --gt 523 R = 24014Remarks 3 Labs rejected (46L 66L70L)

000 050 100 150 200 250 300

k-values

36L

65L

44L

32L

9L

56L

35L

19L

45L

16L

34L

30L

66L

46L

70L

Mandels k statistics(Soil 4 - TOC)

-100 00 100 200 300 400 500 600 700 800 900

Deviation from Mean

36L

65L

44L

32L

9L

56L

35L

19L

45L

16L

34L

30L

66L

46L

70L

Labo

rato

ries

Soil 4 - TOC -- Mean PARM = 1641 [gkg]

-100 000 100 200 300 400

h-values

36L

44L

9L

35L

45L

34L

66L

70L

Labo

rato

ries

Mandels h statistics(Soil 4 - TOC)

Soil 4-TOC

Unit gkg

Mandels k statistics(Soil 5 - TOC)Mandels h statistics(Soil 5 - TOC)

Sample Soil 5 Soil 5 - TOC -- Mean PARM = 2102 [gkg]

Element TOC

General calcparmT1= 113661E+03T2= 240201E+04T3= 54T4= 300T5= 51756E+01

n= variabelp= 10

N-table= 5

Mandels statistics End ResultLAB 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

44L 164383 14708 6 -036 325 Fail - - 44L - - -45865L 181250 0830 4 -033 018 Fail 181250 08302 4 3 -29045L 200317 1116 6 -029 025 Fail 200317 11163 6 5 -09935L 201833 1828 6 -029 040 Fail 201833 18280 6 5 -08432L 203250 0585 4 -029 013 Fail 203250 05852 4 3 -07016L 209000 0959 6 -028 021 Fail 209000 09592 6 5 -0129L 211667 0427 6 -027 009 Fail 211667 04274 6 5 01556L 214030 0887 6 -027 020 Fail 214030 08868 6 5 03819L 216000 0795 6 -026 018 Fail 216000 07950 6 5 05834L 226009 1308 6 -024 029 Fail 226009 13076 6 5 15836L 228783 4310 3 -024 095 Fail - - 36L - - 18666L 238750 1234 4 -022 027 Fail 238750 12340 4 3 28570L 2213900 - 1 333 Fail - - 70L - - 20037

Totgem 36224 2416 gkg 1-level 227 (175) 10 210211 (36L44L 70L) 10 9Totstd= 55669 4003 5-level 184 (151) 3

64RESULTS Mean = 2102106 gkg

Repeatability variance S2r = 117627Repeatability std Sr = 108456 --gt 516 r = 30368Between lab variance S2L = 176699Reproducibility var S2R = 294326Reproducibility std SR = 171559 --gt 816 R = 48037Remarks 3 Labs rejected (36L44L 70L)

000 050 100 150 200 250 300 350

k-values

44L

65L

45L

35L

32L

16L

9L

56L

19L

34L

36L

66L

70L

Mandels k statistics(Soil 5 - TOC)

-500 00 500 1000 1500 2000 2500

Deviation from Mean

44L

65L

45L

35L

32L

16L

9L

56L

19L

34L

36L

66L

70L

Labo

rato

ries

Soil 5 - TOC -- Mean PARM = 2102 [gkg]

-100 000 100 200 300 400

h-values

44L

65L

45L

35L

32L

16L

9L

56L

19L

34L

36L

66L

70L

Labo

rato

ries

Mandels h statistics(Soil 5 - TOC)

Soil 5-TOC

17

Annex 4

Raw data submitted

Sample Compost 1 Sample Compost 2 Sample Sewage Sludge 1Element TOC [gkg] Element TOC [gkg] Element TOC [gkg]

LAB PARM LAB PARM LAB PARM30L 2600 19L 1691 19L 286730L 2580 19L 1634 19L 281430L 2560 19L 1619 19L 276934L 2969 19L 1604 19L 272034L 2936 19L 1499 19L 268834L 2958 19L 1414 19L 266234L 2994 34L 1527 34L 315234L 3199 34L 1622 34L 314934L 3024 34L 1519 34L 343035L 2306 34L 1753 34L 336535L 2300 34L 1636 34L 304235L 2298 34L 1874 34L 298335L 2296 35L 1506 35L 270735L 2291 35L 1312 35L 270335L 2259 35L 1294 35L 268836L 2546 35L 1279 35L 267436L 2527 35L 1191 35L 263136L 2470 35L 1177 35L 262644L 2583 36L 1418 36L 271344L 2581 36L 1408 36L 266544L 2578 36L 1320 36L 261444L 2539 44L 1719 44L 292044L 2528 44L 1664 44L 291644L 2525 44L 1654 44L 291245L 2658 44L 1637 44L 290045L 2600 44L 1624 44L 289645L 2546 44L 1620 44L 289345L 2461 45L 1428 45L 297645L 2409 45L 1325 45L 295245L 2350 45L 1323 45L 288546L 2460 45L 1321 45L 286646L 2400 45L 1309 45L 284046L 2370 45L 1253 45L 278746L 2350 46L 1580 46L 233056L 2436 46L 1550 46L 233056L 2435 46L 1170 46L 230056L 2405 46L 1120 46L 229056L 2397 56L 1642 56L 270256L 2375 56L 1626 56L 270156L 2358 56L 1622 56L 269465L 2587 56L 1571 56L 269365L 2542 56L 1561 56L 268465L 2483 56L 1545 56L 268066L 2454 65L 1933 65L 264166L 2429 65L 1838 65L 260966L 2365 65L 1693 65L 260766L 2262 65L 1562 65L 260569L 2730 66L 1561 66L 270169L 2250 66L 1545 66L 267469L 1440 66L 1420 66L 261969L 1420 66L 1417 66L 251470L 2435 69L 2700 69L 2639L 2594 69L 2660 69L 2409L 2570 69L 2170 69L 2199L 2565 69L 2130 69L 2109L 2563 70L 1414 70L 28159L 2562 9L 1644 9L 28579L 2555 9L 1641 9L 2856

32L 2290 9L 1602 9L 285532L 2390 9L 1589 9L 285532L 2510 9L 1526 9L 285332L 2470 9L 1492 9L 284616L 2380 32L 1470 32L 265016L 2530 32L 1520 32L 271016L 2400 32L 1540 32L 271016L 2500 32L 1600 32L 280016L 2420 16L 1400 16L 284016L 2410 16L 1440 16L 2840

16L 1470 16L 286016L 1510 16L 287016L 1360 16L 287016L 1390 16L 2880

Sample Sewage Sludge 2 Sample Soil 4 Sample Soil 5Element TOC [gkg] Element TOC [gkg] Element TOC [gkg]

LAB PARM LAB PARM LAB PARM19L 2308 19L 1720 19L 225019L 2303 19L 1700 19L 223019L 2239 19L 1690 19L 221019L 2204 19L 1670 19L 211019L 2192 19L 1640 19L 210019L 2096 19L 1580 19L 206034L 2631 30L 1790 34L 244334L 2471 30L 1770 34L 233434L 2977 30L 1700 34L 231534L 2785 34L 1740 34L 222134L 2780 34L 1692 34L 217634L 2668 34L 1727 34L 207335L 2179 34L 1767 35L 233035L 2160 34L 1777 35L 208035L 2158 34L 1783 35L 201035L 2132 35L 1700 35L 198035L 2119 35L 1650 35L 193035L 2094 35L 1650 35L 178036L 2096 35L 1640 36L 254036L 2069 35L 1630 36L 253436L 2052 35L 1630 36L 179044L 2325 36L 1500 44L 302144L 2309 36L 1497 44L 298244L 2307 36L 1417 44L 295644L 2305 44L 1594 44L 30744L 2287 44L 1587 44L 30044L 2283 44L 1584 44L 29745L 2331 44L 1574 45L 214945L 2327 44L 1573 45L 209245L 2308 44L 1562 45L 203345L 2287 45L 1827 45L 197145L 2234 45L 1709 45L 193345L 2113 45L 1666 45L 184146L 190 45L 1665 56L 223746L 180 45L 1664 56L 222246L 180 45L 1600 56L 220346L 180 46L 2300 56L 206956L 2204 46L 2300 56L 206856L 2197 46L 2300 56L 204456L 2193 46L 2200 65L 192056L 2185 56L 1668 65L 182056L 2183 56L 1654 65L 179056L 2167 56L 1653 65L 172065L 2136 56L 1643 66L 254365L 2091 56L 1639 66L 242465L 2065 56L 1638 66L 232165L 2047 65L 1630 66L 226266L 2105 65L 1560 70L 2213966L 2022 65L 1530 9L 218066L 2009 65L 1490 9L 214066L 1983 66L 2179 9L 213070L 2272 66L 1900 9L 21109L 2385 66L 1762 9L 20709L 2377 66L 1734 9L 20709L 2375 70L 10404 32L 20509L 2359 9L 1640 32L 21009L 2356 9L 1640 32L 20209L 2354 9L 1610 32L 1960

32L 2240 9L 1590 16L 210032L 2260 9L 1590 16L 220032L 2200 9L 1560 16L 220032L 2270 32L 1640 16L 206016L 2300 32L 1600 16L 197016L 2310 32L 1560 16L 201016L 2350 32L 157016L 2260 16L 170016L 2290 16L 180016L 2240 16L 1700

16L 180016L 170016L 1700

European Commission EUR 23012 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on total organic carbon Author(s) E Sobiecka H van der Sloot K Andersen B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 50 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07412-7 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 total organic carbon (TOC) in soils sludge and treated bio-waste 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

-23012-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

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

MILC Measure Interlaboratory Comparison ndash (online data submission system)

p Number of labs

r Repeatability limit

R Reproducibility limit

sr Repeatability standard deviation

sR Reproducibility standard deviation

TC Technical Committee

TOC Total Organic Carbon

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 TOC 8

121 Samples dispatched for the validation of TOC 8

122 Draft standards to be followed 8

123 Analytical program 8

124 Timing and Submission of data 8

125 Participants 10

13 Summary results and derived performance characteristics 11

14 Annexes 13

5

Introduction to the validation project Project HORIZONTAL is interdisciplinary aiming at a harmonisation and horizontal standardisation of test procedures in particular for sludge 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 a 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 total organic carbon (TOC) are described hereafter

6

11 Statistical concept underlying the validation According to the requirements of the work package concerning data handling and interpretation of the project HORIZONTAL the respective validation intercomparisons should be evaluated according to ISO 5725-21994 In particular repeatability and reproducibility of the draft standard should be determined 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 work program 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 exercises For each parameter investigated at least 10 laboratories should be nominated to participate The same laboratories should analyse different parameters as far as possible Due to the complexity of analysis and the respective workload of the laboratories it was decided to propose six materials for the validation of the TOC draft standard Each laboratory received two bottles of each material and was requested to perform 6 independent analyses per material1 (3 per bottle) using the draft standard method The 6 analyses 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 was permitted but had to be reported Likewise the different materials could 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 had 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 was set and should 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 The draft standard was made available to the laboratories on the Project Horizontal homepage Each laboratory was requested to provide the signed statements on cooperation as given in Annex 1

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 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

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

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 TOC

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

bull Compost 1 A compost material from Vienna bull Compost 2 A compost material from Germany bull Sewage Sludge 1 A mixed sewage sludge from Essen Germany bull Sewage Sludge 2 A mixed municipal sludge from North Rhine Westphalia

Germany bull Soil 4 A sludge amended soil from Hohenheim Germany bull Soil 5 An agricultural soil from Reading UK

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

122 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 httpwwwecnnldocssocietyhorizontalTOC_standard_for_validationpdf

123 Analytical program Two bottles had to be analysed for each of the six materials and each bottle had to be analysed independently three times 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 dry matter correction was free for each participant

124 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

9

submission of results has been set for TOC to the 31st of January 2007 Alternatively the participants were allowed to submit data electronically as Excel sheet using Email All data were treated in a confidential way Any presentation hereafter refers 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 provided a 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

125 Participants The following table lists the participating organizations and entities in the validation exercise for the horizontal TOC standard

bull Austria o barbara - Engineering Consulting Research amp Service GmbH o Federal Research and Training Centre for Forests Natural Hazards and

Landscape o NUA Umweltanalytik GmbH o Oumlsterreichische Agentur fuumlr Gesundheit und Ernaumlhrungssicherheit o Universitaumlt fuumlr Bodenkultur Wien o Shimadzu Europa GmbH o Umweltbundesamt o University of Natural resources and Applied Life Sciences

bull Belgium o VITO

bull France o INERIS o CEMAGREF - UR QELY o INRA - Laboratoire dAnalyse des Sols

bull Germany o ALBO-tec Technologiezentrum Fuumlr Analytik und Bodenmechanik GmbH

bull Norway o Norwegian Institute for Water Research

bull The Netherlands o ALCONTROL BV o Analytico Milieu B V

11

13 Summary results and derived performance characteristics The result of the various statistical evaluation according to ISO 5725-2 including outlier tests calculation of repeatability and reproducibility standard deviations can be found in Annex 3 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 The calculated average values the repeatability standard deviation (sr) and the reproducibility standard deviation (sR) are given in Table 1 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 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 total organic carbon (TOC) by dry combustion in treated biowaste sludge and soil All concentrations are expressed in gkg dry matter

Matrix Parameter Mean sr sR r R p Outliers Total number of data

No of

LOD

Sludge 1 TOC 272 17 59 13 45 13 2 62 0 Sludge 2 TOC 220 21 50 13 31 12 2 58 0

Compost 1 TOC 246 25 43 17 30 13 2 58 0 Compost 2 TOC 154 59 96 25 41 13 2 64 0

Soil 4 TOC 164 26 52 12 24 12 3 62 0 Soil 5 TOC 210 52 82 30 48 10 3 54 0

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

13

14 Annexes Annex 1 Model questionnaire to be filled by the participating laboratories Annex 2 Report on the validation materials used Annex 3 Statistical calculations Annex 4 Data submitted

14

14

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

15

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

16

Annex 3

Statistical calculations

Unit gkg

Mandels k statistics(Compost 1 - TOC)Mandels h statistics(Compost 1 - TOC)

Sample Compost 1 Compost 1 - TOC -- Mean PARM = 2463 [gkg]

Element TOC

General calcparmT1= 142643E+04T2= 351264E+06T3= 58T4= 292T5= 16501E+03

n= variabelp= 13

N-table= 5

Mandels statistics End ResultLAB 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

69L 1960000 64265 4 -235 352 Fail - - 69L - - -502735L 2291667 1674 6 -081 009 2291667 16741 6 5 -171066L 2377425 8552 4 -041 047 2377425 85518 4 3 -85346L 2395000 4796 4 -033 026 2395000 47958 4 3 -67756L 2401227 3133 6 -030 017 2401227 31330 6 5 -61432L 2415000 9713 4 -024 053 2415000 97125 4 3 -47770L 2435100 - 1 -014 2435100 - 1 -27616L 2440000 6033 6 -012 033 2440000 60332 6 5 -22745L 2503800 11759 6 018 064 2503800 117589 6 5 41136L 2514416 3994 3 023 022 2514416 39937 3 2 51765L 2537333 5216 3 033 029 2537333 52157 3 2 74744L 2555667 2783 6 042 015 2555667 27826 6 5 9309L 2568167 1356 6 048 007 2568167 13556 6 5 105530L 2580000 2000 3 053 011 2580000 20000 3 2 117334L 3013269 9580 6 255 053 Fail - - 34L - - 5506

Totgem 246587 9632 gkg 1-level 232 (176) 13 2462677 (34L 69L) 13 12Totstd= 21507 16070 5-level 186 (152) 2

68RESULTS Mean = 24626770 gkg

Repeatability variance S2r = 3666797Repeatability std Sr = 605541 --gt 246 r = 169551Between lab variance S2L = 7715586Reproducibility var S2R = 11382383Reproducibility std SR = 1066882 --gt 433 R = 298727Remarks 2 Labs rejected (34L 69L)

000 050 100 150 200 250 300 350 400

k-values

69L

35L

66L

46L

56L

32L

70L

16L

45L

36L

65L

44L

9L

30L

34L

Mandels k statistics(Compost 1 - TOC)

-600 -400 -200 00 200 400 600

Deviation from Mean

69L

35L

66L

46L

56L

32L

70L

16L

45L

36L

65L

44L

9L

30L

34L

Labo

rato

ries

Compost 1 - TOC -- Mean PARM = 2463 [gkg]

-300 -200 -100 000 100 200 300

h-values

69L

66L

56L

70L

45L

65L

9L

34L

Labo

rato

ries

Mandels h statistics(Compost 1 - TOC)

Compost 1-TOC

Unit gkg

Mandels k statistics(Compost 2 - TOC)Mandels h statistics(Compost 2 - TOC)

Sample Compost 2 Compost 2 - TOC -- Mean PARM = 1542 [gkg]

Element TOC

General calcparmT1= 994897E+03T2= 155556E+06T3= 64T4= 346T5= 41738E+03

n= variabelp= 13

N-table= 5

Mandels statistics End ResultLAB 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

45L 1326733 5665 6 -100 042 Fail 1326733 56646 6 5 -215046L 1355000 24365 4 -089 181 Fail - - 46L - - -186736L 1381949 5407 3 -078 040 Fail 1381949 54070 3 2 -159870L 1414120 - 1 -066 Fail 1414120 - 1 -127616L 1428333 5565 6 -061 041 1428333 55648 6 5 -113466L 1485550 7805 4 -039 058 1485550 78047 4 3 -56232L 1532500 5377 4 -021 040 1532500 53774 4 3 -09219L 1576833 10138 6 -004 075 1576833 101381 6 5 3519L 1582333 6166 6 -002 046 1582333 61659 6 5 40656L 1594432 4046 6 003 030 1594432 40463 6 5 52744L 1653000 3651 6 025 027 1653000 36508 6 5 111334L 1655127 13717 6 026 102 1655127 137168 6 5 113434L 1655127 13717 6 026 102 1655127 137168 6 5 113465L 1756500 16295 4 065 121 Fail 1756500 162949 4 3 214869L 2415000 30687 4 316 228 Fail - - 69L - - 8733

Totgem 158750 10900 gkg 1-level 232 (176) 13 1541734 (46L 69L) 13 12Totstd= 26187 8164 5-level 186 (152) 2

72RESULTS Mean = 15417337 gkg

Repeatability variance S2r = 8183950Repeatability std Sr = 904652 --gt 587 r = 253303Between lab variance S2L = 13631046Reproducibility var S2R = 21814995Reproducibility std SR = 1476990 --gt 958 R = 413557Remarks 2 Labs rejected (46L 69L)

000 050 100 150 200 250

k-values

45L

46L

36L

70L

16L

66L

32L

19L

9L

56L

44L

34L

34L

65L

69L

Mandels k statistics(Compost 2 - TOC)

-400 -200 00 200 400 600 800 1000

Deviation from Mean

45L

46L

36L

70L

16L

66L

32L

19L

9L

56L

44L

34L

34L

65L

69L

Labo

rato

ries

Compost 2 - TOC -- Mean PARM = 1542 [gkg]

-100 000 100 200 300 400

h-values

45L

36L

16L

32L

9L

44L

34L

69L

Labo

rato

ries

Mandels h statistics(Compost 2 - TOC)

Compost 2-TOC

Unit gkg

Mandels k statistics(Sludge 1 - TOC)Mandels h statistics(Sludge 1 - TOC)

Sample Sludge 1 Sludge 1 - TOC -- Mean PARM = 2721 [gkg]

Element TOC

General calcparmT1= 169626E+04T2= 465445E+06T3= 62T4= 326T5= 10312E+03

n= variabelp= 13

N-table= 5

Mandels statistics End ResultLAB 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

69L 233000 2362 4 -347 037 Fail - - 69L - - -2488046L 2312500 2062 4 -040 032 Fail 2312500 20616 4 3 -408565L 2615500 1708 4 004 026 2615500 17078 4 3 -105566L 2627200 8268 4 006 128 2627200 82678 4 3 -93836L 2664041 4976 3 011 077 2664041 49758 3 2 -56935L 2671500 3533 6 013 055 2671500 35331 6 5 -49556L 2692298 0874 6 016 014 Fail 2692298 08738 6 5 -28732L 2717500 6185 4 019 096 Fail 2717500 61847 4 3 -03519L 2753333 7819 6 025 121 Fail 2753333 78189 6 5 32470L 2814600 - 1 034 Fail 2814600 - 1 9369L 2853667 0398 6 039 006 Fail 2853667 03983 6 5 132716L 2860000 1673 6 040 026 Fail 2860000 16733 6 5 139045L 2884433 7033 6 044 109 Fail 2884433 70331 6 5 163544L 2906167 1129 6 047 017 Fail 2906167 11286 6 5 185234L 3186874 17674 6 089 274 Fail - - 34L - - 4659

Totgem 258617 4692 gkg 1-level 232 (176) 13 2720980 (34L 69L) 13 12Totstd= 67800 4610 5-level 186 (152) 2

72RESULTS Mean = 27209799 gkg

Repeatability variance S2r = 2104538Repeatability std Sr = 458752 --gt 169 r = 128451Between lab variance S2L = 23618387Reproducibility var S2R = 25722925Reproducibility std SR = 1603837 --gt 589 R = 449074Remarks 2 Labs rejected (34L 69L)

000 050 100 150 200 250 300

k-values

69L

46L

65L

66L

36L

35L

56L

32L

19L

70L

9L

16L

45L

44L

34L

Mandels k statistics(Sludge 1 - TOC)

-2500 -2000 -1500 -1000 -500 00 500

Deviation from Mean

69L

46L

65L

66L

36L

35L

56L

32L

19L

70L

9L

16L

45L

44L

34L

Labo

rato

ries

Sludge 1 - TOC -- Mean PARM = 2721 [gkg]

-400 -300 -200 -100 000 100

h-values

69L

65L

36L

56L

19L

9L

45L

34L

Labo

rato

ries

Mandels h statistics(Sludge 1 - TOC)

Sludge 1-TOC

68 Unit gkg

Mandels k statistics(Sludge 2 - TOC)Mandels h statistics(Sludge 2 - TOC)

Sample Sludge 2 Sludge 2 - TOC -- Mean PARM = 2207 [gkg]

Element TOC

General calcparmT1= 128601E+04T2= 285689E+06T3= 58T4= 310T5= 97826E+02

n= variabelp= 12

N-table= 5

Mandels statistics End ResultLAB 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

46L 182500 0500 4 -333 008 Fail - - 46L - - -2024466L 2029475 5267 4 -012 084 2029475 52674 4 3 -177436L 2072609 2222 3 -005 035 2072609 22222 3 2 -134365L 2084750 3865 4 -002 062 2084750 38647 4 3 -122135L 2140333 3119 6 007 050 2140333 31194 6 5 -66556L 2188021 1282 6 015 020 2188021 12822 6 5 -18819L 2223667 7916 6 022 126 Fail 2223667 79157 6 5 16832L 2242500 3096 4 025 049 Fail 2242500 30957 4 3 35645L 2266600 8322 6 029 132 Fail 2266600 83216 6 5 59770L 2272460 - 1 030 Fail 2272460 - 1 65616L 2291667 3869 6 033 062 Fail 2291667 38687 6 5 84844L 2302667 1546 6 035 025 Fail 2302667 15462 6 5 9589L 2367667 1296 6 047 021 Fail 2367667 12956 6 5 160834L 2718591 17124 6 108 273 Fail - - 34L - - 5117

Totgem 209882 4571 gkg 1-level 230 (176) 12 2206868 (34L 46L) 12 11Totstd= 57628 4485 5-level 185 (151) 2

68RESULTS Mean = 22068679 gkg

Repeatability variance S2r = 2126659Repeatability std Sr = 461157 --gt 209 r = 129124Between lab variance S2L = 9960432Reproducibility var S2R = 12087091Reproducibility std SR = 1099413 --gt 498 R = 307836Remarks 2 Labs rejected (34L 46L)

000 050 100 150 200 250 300

k-values

46L

66L

36L

65L

35L

56L

19L

32L

45L

70L

16L

44L

9L

34L

Mandels k statistics(Sludge 2 - TOC)

-2500 -2000 -1500 -1000 -500 00 500 1000

Deviation from Mean

46L

66L

36L

65L

35L

56L

19L

32L

45L

70L

16L

44L

9L

34L

Labo

rato

ries

Sludge 2 - TOC -- Mean PARM = 2207 [gkg]

-400 -300 -200 -100 000 100 200

h-values

46L

66L

36L

65L

35L

56L

19L

32L

45L

70L

16L

44L

9L

34L

Labo

rato

ries

Mandels h statistics(Sludge 2 - TOC)

Sludge 2-TOC

Unit gkg

Mandels k statistics(Soil 4 - TOC)Mandels h statistics(Soil 4 - TOC)

Sample Soil 4 Soil 4 - TOC -- Mean PARM = 1641 [gkg]

Element TOC

General calcparmT1= 102171E+03T2= 168700E+04T3= 62T4= 338T5= 94040E+00

n= variabelp= 12

N-table= 5

Mandels statistics End ResultLAB 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

36L 147161 0470 3 -036 068 Fail 147161 04702 3 2 -16965L 155250 0591 4 -032 085 Fail 155250 05909 4 3 -08844L 157900 0115 6 -031 017 Fail 157900 01152 6 5 -06232L 159250 0359 4 -031 052 Fail 159250 03594 4 3 -0489L 160500 0315 6 -030 045 Fail 160500 03146 6 5 -03656L 164927 0113 6 -028 016 Fail 164927 01127 6 5 00835L 165000 0261 6 -028 038 Fail 165000 02608 6 5 00919L 166667 0505 6 -027 073 Fail 166667 05046 6 5 02645L 168850 0763 6 -026 110 Fail 168850 07628 6 5 04816L 173333 0516 6 -024 074 Fail 173333 05164 6 5 09334L 174761 0346 6 -024 050 Fail 174761 03462 6 5 10730L 175333 0473 3 -024 068 Fail 175333 04726 3 2 11366L 189375 2035 4 -017 294 Fail - - 66L - - 25346L 227500 0500 4 000 072 - - 46L - - 63470L 1040400 - 1 360 Fail - - 70L - - 8763

Totgem 22841 0526 gkg 1-level 232 (176) 12 164078 (46L 66L70L) 12 11Totstd= 22541 0469 5-level 186 (152) 3

71RESULTS Mean = 1640777 gkg

Repeatability variance S2r = 018808Repeatability std Sr = 043368 --gt 264 r = 12143Between lab variance S2L = 054747Reproducibility var S2R = 073555Reproducibility std SR = 085764 --gt 523 R = 24014Remarks 3 Labs rejected (46L 66L70L)

000 050 100 150 200 250 300

k-values

36L

65L

44L

32L

9L

56L

35L

19L

45L

16L

34L

30L

66L

46L

70L

Mandels k statistics(Soil 4 - TOC)

-100 00 100 200 300 400 500 600 700 800 900

Deviation from Mean

36L

65L

44L

32L

9L

56L

35L

19L

45L

16L

34L

30L

66L

46L

70L

Labo

rato

ries

Soil 4 - TOC -- Mean PARM = 1641 [gkg]

-100 000 100 200 300 400

h-values

36L

44L

9L

35L

45L

34L

66L

70L

Labo

rato

ries

Mandels h statistics(Soil 4 - TOC)

Soil 4-TOC

Unit gkg

Mandels k statistics(Soil 5 - TOC)Mandels h statistics(Soil 5 - TOC)

Sample Soil 5 Soil 5 - TOC -- Mean PARM = 2102 [gkg]

Element TOC

General calcparmT1= 113661E+03T2= 240201E+04T3= 54T4= 300T5= 51756E+01

n= variabelp= 10

N-table= 5

Mandels statistics End ResultLAB 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

44L 164383 14708 6 -036 325 Fail - - 44L - - -45865L 181250 0830 4 -033 018 Fail 181250 08302 4 3 -29045L 200317 1116 6 -029 025 Fail 200317 11163 6 5 -09935L 201833 1828 6 -029 040 Fail 201833 18280 6 5 -08432L 203250 0585 4 -029 013 Fail 203250 05852 4 3 -07016L 209000 0959 6 -028 021 Fail 209000 09592 6 5 -0129L 211667 0427 6 -027 009 Fail 211667 04274 6 5 01556L 214030 0887 6 -027 020 Fail 214030 08868 6 5 03819L 216000 0795 6 -026 018 Fail 216000 07950 6 5 05834L 226009 1308 6 -024 029 Fail 226009 13076 6 5 15836L 228783 4310 3 -024 095 Fail - - 36L - - 18666L 238750 1234 4 -022 027 Fail 238750 12340 4 3 28570L 2213900 - 1 333 Fail - - 70L - - 20037

Totgem 36224 2416 gkg 1-level 227 (175) 10 210211 (36L44L 70L) 10 9Totstd= 55669 4003 5-level 184 (151) 3

64RESULTS Mean = 2102106 gkg

Repeatability variance S2r = 117627Repeatability std Sr = 108456 --gt 516 r = 30368Between lab variance S2L = 176699Reproducibility var S2R = 294326Reproducibility std SR = 171559 --gt 816 R = 48037Remarks 3 Labs rejected (36L44L 70L)

000 050 100 150 200 250 300 350

k-values

44L

65L

45L

35L

32L

16L

9L

56L

19L

34L

36L

66L

70L

Mandels k statistics(Soil 5 - TOC)

-500 00 500 1000 1500 2000 2500

Deviation from Mean

44L

65L

45L

35L

32L

16L

9L

56L

19L

34L

36L

66L

70L

Labo

rato

ries

Soil 5 - TOC -- Mean PARM = 2102 [gkg]

-100 000 100 200 300 400

h-values

44L

65L

45L

35L

32L

16L

9L

56L

19L

34L

36L

66L

70L

Labo

rato

ries

Mandels h statistics(Soil 5 - TOC)

Soil 5-TOC

17

Annex 4

Raw data submitted

Sample Compost 1 Sample Compost 2 Sample Sewage Sludge 1Element TOC [gkg] Element TOC [gkg] Element TOC [gkg]

LAB PARM LAB PARM LAB PARM30L 2600 19L 1691 19L 286730L 2580 19L 1634 19L 281430L 2560 19L 1619 19L 276934L 2969 19L 1604 19L 272034L 2936 19L 1499 19L 268834L 2958 19L 1414 19L 266234L 2994 34L 1527 34L 315234L 3199 34L 1622 34L 314934L 3024 34L 1519 34L 343035L 2306 34L 1753 34L 336535L 2300 34L 1636 34L 304235L 2298 34L 1874 34L 298335L 2296 35L 1506 35L 270735L 2291 35L 1312 35L 270335L 2259 35L 1294 35L 268836L 2546 35L 1279 35L 267436L 2527 35L 1191 35L 263136L 2470 35L 1177 35L 262644L 2583 36L 1418 36L 271344L 2581 36L 1408 36L 266544L 2578 36L 1320 36L 261444L 2539 44L 1719 44L 292044L 2528 44L 1664 44L 291644L 2525 44L 1654 44L 291245L 2658 44L 1637 44L 290045L 2600 44L 1624 44L 289645L 2546 44L 1620 44L 289345L 2461 45L 1428 45L 297645L 2409 45L 1325 45L 295245L 2350 45L 1323 45L 288546L 2460 45L 1321 45L 286646L 2400 45L 1309 45L 284046L 2370 45L 1253 45L 278746L 2350 46L 1580 46L 233056L 2436 46L 1550 46L 233056L 2435 46L 1170 46L 230056L 2405 46L 1120 46L 229056L 2397 56L 1642 56L 270256L 2375 56L 1626 56L 270156L 2358 56L 1622 56L 269465L 2587 56L 1571 56L 269365L 2542 56L 1561 56L 268465L 2483 56L 1545 56L 268066L 2454 65L 1933 65L 264166L 2429 65L 1838 65L 260966L 2365 65L 1693 65L 260766L 2262 65L 1562 65L 260569L 2730 66L 1561 66L 270169L 2250 66L 1545 66L 267469L 1440 66L 1420 66L 261969L 1420 66L 1417 66L 251470L 2435 69L 2700 69L 2639L 2594 69L 2660 69L 2409L 2570 69L 2170 69L 2199L 2565 69L 2130 69L 2109L 2563 70L 1414 70L 28159L 2562 9L 1644 9L 28579L 2555 9L 1641 9L 2856

32L 2290 9L 1602 9L 285532L 2390 9L 1589 9L 285532L 2510 9L 1526 9L 285332L 2470 9L 1492 9L 284616L 2380 32L 1470 32L 265016L 2530 32L 1520 32L 271016L 2400 32L 1540 32L 271016L 2500 32L 1600 32L 280016L 2420 16L 1400 16L 284016L 2410 16L 1440 16L 2840

16L 1470 16L 286016L 1510 16L 287016L 1360 16L 287016L 1390 16L 2880

Sample Sewage Sludge 2 Sample Soil 4 Sample Soil 5Element TOC [gkg] Element TOC [gkg] Element TOC [gkg]

LAB PARM LAB PARM LAB PARM19L 2308 19L 1720 19L 225019L 2303 19L 1700 19L 223019L 2239 19L 1690 19L 221019L 2204 19L 1670 19L 211019L 2192 19L 1640 19L 210019L 2096 19L 1580 19L 206034L 2631 30L 1790 34L 244334L 2471 30L 1770 34L 233434L 2977 30L 1700 34L 231534L 2785 34L 1740 34L 222134L 2780 34L 1692 34L 217634L 2668 34L 1727 34L 207335L 2179 34L 1767 35L 233035L 2160 34L 1777 35L 208035L 2158 34L 1783 35L 201035L 2132 35L 1700 35L 198035L 2119 35L 1650 35L 193035L 2094 35L 1650 35L 178036L 2096 35L 1640 36L 254036L 2069 35L 1630 36L 253436L 2052 35L 1630 36L 179044L 2325 36L 1500 44L 302144L 2309 36L 1497 44L 298244L 2307 36L 1417 44L 295644L 2305 44L 1594 44L 30744L 2287 44L 1587 44L 30044L 2283 44L 1584 44L 29745L 2331 44L 1574 45L 214945L 2327 44L 1573 45L 209245L 2308 44L 1562 45L 203345L 2287 45L 1827 45L 197145L 2234 45L 1709 45L 193345L 2113 45L 1666 45L 184146L 190 45L 1665 56L 223746L 180 45L 1664 56L 222246L 180 45L 1600 56L 220346L 180 46L 2300 56L 206956L 2204 46L 2300 56L 206856L 2197 46L 2300 56L 204456L 2193 46L 2200 65L 192056L 2185 56L 1668 65L 182056L 2183 56L 1654 65L 179056L 2167 56L 1653 65L 172065L 2136 56L 1643 66L 254365L 2091 56L 1639 66L 242465L 2065 56L 1638 66L 232165L 2047 65L 1630 66L 226266L 2105 65L 1560 70L 2213966L 2022 65L 1530 9L 218066L 2009 65L 1490 9L 214066L 1983 66L 2179 9L 213070L 2272 66L 1900 9L 21109L 2385 66L 1762 9L 20709L 2377 66L 1734 9L 20709L 2375 70L 10404 32L 20509L 2359 9L 1640 32L 21009L 2356 9L 1640 32L 20209L 2354 9L 1610 32L 1960

32L 2240 9L 1590 16L 210032L 2260 9L 1590 16L 220032L 2200 9L 1560 16L 220032L 2270 32L 1640 16L 206016L 2300 32L 1600 16L 197016L 2310 32L 1560 16L 201016L 2350 32L 157016L 2260 16L 170016L 2290 16L 180016L 2240 16L 1700

16L 180016L 170016L 1700

European Commission EUR 23012 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on total organic carbon Author(s) E Sobiecka H van der Sloot K Andersen B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 50 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07412-7 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 total organic carbon (TOC) in soils sludge and treated bio-waste 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

-23012-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 TOC 8

121 Samples dispatched for the validation of TOC 8

122 Draft standards to be followed 8

123 Analytical program 8

124 Timing and Submission of data 8

125 Participants 10

13 Summary results and derived performance characteristics 11

14 Annexes 13

5

Introduction to the validation project Project HORIZONTAL is interdisciplinary aiming at a harmonisation and horizontal standardisation of test procedures in particular for sludge 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 a 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 total organic carbon (TOC) are described hereafter

6

11 Statistical concept underlying the validation According to the requirements of the work package concerning data handling and interpretation of the project HORIZONTAL the respective validation intercomparisons should be evaluated according to ISO 5725-21994 In particular repeatability and reproducibility of the draft standard should be determined 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 work program 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 exercises For each parameter investigated at least 10 laboratories should be nominated to participate The same laboratories should analyse different parameters as far as possible Due to the complexity of analysis and the respective workload of the laboratories it was decided to propose six materials for the validation of the TOC draft standard Each laboratory received two bottles of each material and was requested to perform 6 independent analyses per material1 (3 per bottle) using the draft standard method The 6 analyses 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 was permitted but had to be reported Likewise the different materials could 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 had 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 was set and should 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 The draft standard was made available to the laboratories on the Project Horizontal homepage Each laboratory was requested to provide the signed statements on cooperation as given in Annex 1

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 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

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

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 TOC

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

bull Compost 1 A compost material from Vienna bull Compost 2 A compost material from Germany bull Sewage Sludge 1 A mixed sewage sludge from Essen Germany bull Sewage Sludge 2 A mixed municipal sludge from North Rhine Westphalia

Germany bull Soil 4 A sludge amended soil from Hohenheim Germany bull Soil 5 An agricultural soil from Reading UK

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

122 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 httpwwwecnnldocssocietyhorizontalTOC_standard_for_validationpdf

123 Analytical program Two bottles had to be analysed for each of the six materials and each bottle had to be analysed independently three times 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 dry matter correction was free for each participant

124 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

9

submission of results has been set for TOC to the 31st of January 2007 Alternatively the participants were allowed to submit data electronically as Excel sheet using Email All data were treated in a confidential way Any presentation hereafter refers 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 provided a 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

125 Participants The following table lists the participating organizations and entities in the validation exercise for the horizontal TOC standard

bull Austria o barbara - Engineering Consulting Research amp Service GmbH o Federal Research and Training Centre for Forests Natural Hazards and

Landscape o NUA Umweltanalytik GmbH o Oumlsterreichische Agentur fuumlr Gesundheit und Ernaumlhrungssicherheit o Universitaumlt fuumlr Bodenkultur Wien o Shimadzu Europa GmbH o Umweltbundesamt o University of Natural resources and Applied Life Sciences

bull Belgium o VITO

bull France o INERIS o CEMAGREF - UR QELY o INRA - Laboratoire dAnalyse des Sols

bull Germany o ALBO-tec Technologiezentrum Fuumlr Analytik und Bodenmechanik GmbH

bull Norway o Norwegian Institute for Water Research

bull The Netherlands o ALCONTROL BV o Analytico Milieu B V

11

13 Summary results and derived performance characteristics The result of the various statistical evaluation according to ISO 5725-2 including outlier tests calculation of repeatability and reproducibility standard deviations can be found in Annex 3 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 The calculated average values the repeatability standard deviation (sr) and the reproducibility standard deviation (sR) are given in Table 1 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 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 total organic carbon (TOC) by dry combustion in treated biowaste sludge and soil All concentrations are expressed in gkg dry matter

Matrix Parameter Mean sr sR r R p Outliers Total number of data

No of

LOD

Sludge 1 TOC 272 17 59 13 45 13 2 62 0 Sludge 2 TOC 220 21 50 13 31 12 2 58 0

Compost 1 TOC 246 25 43 17 30 13 2 58 0 Compost 2 TOC 154 59 96 25 41 13 2 64 0

Soil 4 TOC 164 26 52 12 24 12 3 62 0 Soil 5 TOC 210 52 82 30 48 10 3 54 0

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

13

14 Annexes Annex 1 Model questionnaire to be filled by the participating laboratories Annex 2 Report on the validation materials used Annex 3 Statistical calculations Annex 4 Data submitted

14

14

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

15

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

16

Annex 3

Statistical calculations

Unit gkg

Mandels k statistics(Compost 1 - TOC)Mandels h statistics(Compost 1 - TOC)

Sample Compost 1 Compost 1 - TOC -- Mean PARM = 2463 [gkg]

Element TOC

General calcparmT1= 142643E+04T2= 351264E+06T3= 58T4= 292T5= 16501E+03

n= variabelp= 13

N-table= 5

Mandels statistics End ResultLAB 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

69L 1960000 64265 4 -235 352 Fail - - 69L - - -502735L 2291667 1674 6 -081 009 2291667 16741 6 5 -171066L 2377425 8552 4 -041 047 2377425 85518 4 3 -85346L 2395000 4796 4 -033 026 2395000 47958 4 3 -67756L 2401227 3133 6 -030 017 2401227 31330 6 5 -61432L 2415000 9713 4 -024 053 2415000 97125 4 3 -47770L 2435100 - 1 -014 2435100 - 1 -27616L 2440000 6033 6 -012 033 2440000 60332 6 5 -22745L 2503800 11759 6 018 064 2503800 117589 6 5 41136L 2514416 3994 3 023 022 2514416 39937 3 2 51765L 2537333 5216 3 033 029 2537333 52157 3 2 74744L 2555667 2783 6 042 015 2555667 27826 6 5 9309L 2568167 1356 6 048 007 2568167 13556 6 5 105530L 2580000 2000 3 053 011 2580000 20000 3 2 117334L 3013269 9580 6 255 053 Fail - - 34L - - 5506

Totgem 246587 9632 gkg 1-level 232 (176) 13 2462677 (34L 69L) 13 12Totstd= 21507 16070 5-level 186 (152) 2

68RESULTS Mean = 24626770 gkg

Repeatability variance S2r = 3666797Repeatability std Sr = 605541 --gt 246 r = 169551Between lab variance S2L = 7715586Reproducibility var S2R = 11382383Reproducibility std SR = 1066882 --gt 433 R = 298727Remarks 2 Labs rejected (34L 69L)

000 050 100 150 200 250 300 350 400

k-values

69L

35L

66L

46L

56L

32L

70L

16L

45L

36L

65L

44L

9L

30L

34L

Mandels k statistics(Compost 1 - TOC)

-600 -400 -200 00 200 400 600

Deviation from Mean

69L

35L

66L

46L

56L

32L

70L

16L

45L

36L

65L

44L

9L

30L

34L

Labo

rato

ries

Compost 1 - TOC -- Mean PARM = 2463 [gkg]

-300 -200 -100 000 100 200 300

h-values

69L

66L

56L

70L

45L

65L

9L

34L

Labo

rato

ries

Mandels h statistics(Compost 1 - TOC)

Compost 1-TOC

Unit gkg

Mandels k statistics(Compost 2 - TOC)Mandels h statistics(Compost 2 - TOC)

Sample Compost 2 Compost 2 - TOC -- Mean PARM = 1542 [gkg]

Element TOC

General calcparmT1= 994897E+03T2= 155556E+06T3= 64T4= 346T5= 41738E+03

n= variabelp= 13

N-table= 5

Mandels statistics End ResultLAB 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

45L 1326733 5665 6 -100 042 Fail 1326733 56646 6 5 -215046L 1355000 24365 4 -089 181 Fail - - 46L - - -186736L 1381949 5407 3 -078 040 Fail 1381949 54070 3 2 -159870L 1414120 - 1 -066 Fail 1414120 - 1 -127616L 1428333 5565 6 -061 041 1428333 55648 6 5 -113466L 1485550 7805 4 -039 058 1485550 78047 4 3 -56232L 1532500 5377 4 -021 040 1532500 53774 4 3 -09219L 1576833 10138 6 -004 075 1576833 101381 6 5 3519L 1582333 6166 6 -002 046 1582333 61659 6 5 40656L 1594432 4046 6 003 030 1594432 40463 6 5 52744L 1653000 3651 6 025 027 1653000 36508 6 5 111334L 1655127 13717 6 026 102 1655127 137168 6 5 113434L 1655127 13717 6 026 102 1655127 137168 6 5 113465L 1756500 16295 4 065 121 Fail 1756500 162949 4 3 214869L 2415000 30687 4 316 228 Fail - - 69L - - 8733

Totgem 158750 10900 gkg 1-level 232 (176) 13 1541734 (46L 69L) 13 12Totstd= 26187 8164 5-level 186 (152) 2

72RESULTS Mean = 15417337 gkg

Repeatability variance S2r = 8183950Repeatability std Sr = 904652 --gt 587 r = 253303Between lab variance S2L = 13631046Reproducibility var S2R = 21814995Reproducibility std SR = 1476990 --gt 958 R = 413557Remarks 2 Labs rejected (46L 69L)

000 050 100 150 200 250

k-values

45L

46L

36L

70L

16L

66L

32L

19L

9L

56L

44L

34L

34L

65L

69L

Mandels k statistics(Compost 2 - TOC)

-400 -200 00 200 400 600 800 1000

Deviation from Mean

45L

46L

36L

70L

16L

66L

32L

19L

9L

56L

44L

34L

34L

65L

69L

Labo

rato

ries

Compost 2 - TOC -- Mean PARM = 1542 [gkg]

-100 000 100 200 300 400

h-values

45L

36L

16L

32L

9L

44L

34L

69L

Labo

rato

ries

Mandels h statistics(Compost 2 - TOC)

Compost 2-TOC

Unit gkg

Mandels k statistics(Sludge 1 - TOC)Mandels h statistics(Sludge 1 - TOC)

Sample Sludge 1 Sludge 1 - TOC -- Mean PARM = 2721 [gkg]

Element TOC

General calcparmT1= 169626E+04T2= 465445E+06T3= 62T4= 326T5= 10312E+03

n= variabelp= 13

N-table= 5

Mandels statistics End ResultLAB 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

69L 233000 2362 4 -347 037 Fail - - 69L - - -2488046L 2312500 2062 4 -040 032 Fail 2312500 20616 4 3 -408565L 2615500 1708 4 004 026 2615500 17078 4 3 -105566L 2627200 8268 4 006 128 2627200 82678 4 3 -93836L 2664041 4976 3 011 077 2664041 49758 3 2 -56935L 2671500 3533 6 013 055 2671500 35331 6 5 -49556L 2692298 0874 6 016 014 Fail 2692298 08738 6 5 -28732L 2717500 6185 4 019 096 Fail 2717500 61847 4 3 -03519L 2753333 7819 6 025 121 Fail 2753333 78189 6 5 32470L 2814600 - 1 034 Fail 2814600 - 1 9369L 2853667 0398 6 039 006 Fail 2853667 03983 6 5 132716L 2860000 1673 6 040 026 Fail 2860000 16733 6 5 139045L 2884433 7033 6 044 109 Fail 2884433 70331 6 5 163544L 2906167 1129 6 047 017 Fail 2906167 11286 6 5 185234L 3186874 17674 6 089 274 Fail - - 34L - - 4659

Totgem 258617 4692 gkg 1-level 232 (176) 13 2720980 (34L 69L) 13 12Totstd= 67800 4610 5-level 186 (152) 2

72RESULTS Mean = 27209799 gkg

Repeatability variance S2r = 2104538Repeatability std Sr = 458752 --gt 169 r = 128451Between lab variance S2L = 23618387Reproducibility var S2R = 25722925Reproducibility std SR = 1603837 --gt 589 R = 449074Remarks 2 Labs rejected (34L 69L)

000 050 100 150 200 250 300

k-values

69L

46L

65L

66L

36L

35L

56L

32L

19L

70L

9L

16L

45L

44L

34L

Mandels k statistics(Sludge 1 - TOC)

-2500 -2000 -1500 -1000 -500 00 500

Deviation from Mean

69L

46L

65L

66L

36L

35L

56L

32L

19L

70L

9L

16L

45L

44L

34L

Labo

rato

ries

Sludge 1 - TOC -- Mean PARM = 2721 [gkg]

-400 -300 -200 -100 000 100

h-values

69L

65L

36L

56L

19L

9L

45L

34L

Labo

rato

ries

Mandels h statistics(Sludge 1 - TOC)

Sludge 1-TOC

68 Unit gkg

Mandels k statistics(Sludge 2 - TOC)Mandels h statistics(Sludge 2 - TOC)

Sample Sludge 2 Sludge 2 - TOC -- Mean PARM = 2207 [gkg]

Element TOC

General calcparmT1= 128601E+04T2= 285689E+06T3= 58T4= 310T5= 97826E+02

n= variabelp= 12

N-table= 5

Mandels statistics End ResultLAB 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

46L 182500 0500 4 -333 008 Fail - - 46L - - -2024466L 2029475 5267 4 -012 084 2029475 52674 4 3 -177436L 2072609 2222 3 -005 035 2072609 22222 3 2 -134365L 2084750 3865 4 -002 062 2084750 38647 4 3 -122135L 2140333 3119 6 007 050 2140333 31194 6 5 -66556L 2188021 1282 6 015 020 2188021 12822 6 5 -18819L 2223667 7916 6 022 126 Fail 2223667 79157 6 5 16832L 2242500 3096 4 025 049 Fail 2242500 30957 4 3 35645L 2266600 8322 6 029 132 Fail 2266600 83216 6 5 59770L 2272460 - 1 030 Fail 2272460 - 1 65616L 2291667 3869 6 033 062 Fail 2291667 38687 6 5 84844L 2302667 1546 6 035 025 Fail 2302667 15462 6 5 9589L 2367667 1296 6 047 021 Fail 2367667 12956 6 5 160834L 2718591 17124 6 108 273 Fail - - 34L - - 5117

Totgem 209882 4571 gkg 1-level 230 (176) 12 2206868 (34L 46L) 12 11Totstd= 57628 4485 5-level 185 (151) 2

68RESULTS Mean = 22068679 gkg

Repeatability variance S2r = 2126659Repeatability std Sr = 461157 --gt 209 r = 129124Between lab variance S2L = 9960432Reproducibility var S2R = 12087091Reproducibility std SR = 1099413 --gt 498 R = 307836Remarks 2 Labs rejected (34L 46L)

000 050 100 150 200 250 300

k-values

46L

66L

36L

65L

35L

56L

19L

32L

45L

70L

16L

44L

9L

34L

Mandels k statistics(Sludge 2 - TOC)

-2500 -2000 -1500 -1000 -500 00 500 1000

Deviation from Mean

46L

66L

36L

65L

35L

56L

19L

32L

45L

70L

16L

44L

9L

34L

Labo

rato

ries

Sludge 2 - TOC -- Mean PARM = 2207 [gkg]

-400 -300 -200 -100 000 100 200

h-values

46L

66L

36L

65L

35L

56L

19L

32L

45L

70L

16L

44L

9L

34L

Labo

rato

ries

Mandels h statistics(Sludge 2 - TOC)

Sludge 2-TOC

Unit gkg

Mandels k statistics(Soil 4 - TOC)Mandels h statistics(Soil 4 - TOC)

Sample Soil 4 Soil 4 - TOC -- Mean PARM = 1641 [gkg]

Element TOC

General calcparmT1= 102171E+03T2= 168700E+04T3= 62T4= 338T5= 94040E+00

n= variabelp= 12

N-table= 5

Mandels statistics End ResultLAB 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

36L 147161 0470 3 -036 068 Fail 147161 04702 3 2 -16965L 155250 0591 4 -032 085 Fail 155250 05909 4 3 -08844L 157900 0115 6 -031 017 Fail 157900 01152 6 5 -06232L 159250 0359 4 -031 052 Fail 159250 03594 4 3 -0489L 160500 0315 6 -030 045 Fail 160500 03146 6 5 -03656L 164927 0113 6 -028 016 Fail 164927 01127 6 5 00835L 165000 0261 6 -028 038 Fail 165000 02608 6 5 00919L 166667 0505 6 -027 073 Fail 166667 05046 6 5 02645L 168850 0763 6 -026 110 Fail 168850 07628 6 5 04816L 173333 0516 6 -024 074 Fail 173333 05164 6 5 09334L 174761 0346 6 -024 050 Fail 174761 03462 6 5 10730L 175333 0473 3 -024 068 Fail 175333 04726 3 2 11366L 189375 2035 4 -017 294 Fail - - 66L - - 25346L 227500 0500 4 000 072 - - 46L - - 63470L 1040400 - 1 360 Fail - - 70L - - 8763

Totgem 22841 0526 gkg 1-level 232 (176) 12 164078 (46L 66L70L) 12 11Totstd= 22541 0469 5-level 186 (152) 3

71RESULTS Mean = 1640777 gkg

Repeatability variance S2r = 018808Repeatability std Sr = 043368 --gt 264 r = 12143Between lab variance S2L = 054747Reproducibility var S2R = 073555Reproducibility std SR = 085764 --gt 523 R = 24014Remarks 3 Labs rejected (46L 66L70L)

000 050 100 150 200 250 300

k-values

36L

65L

44L

32L

9L

56L

35L

19L

45L

16L

34L

30L

66L

46L

70L

Mandels k statistics(Soil 4 - TOC)

-100 00 100 200 300 400 500 600 700 800 900

Deviation from Mean

36L

65L

44L

32L

9L

56L

35L

19L

45L

16L

34L

30L

66L

46L

70L

Labo

rato

ries

Soil 4 - TOC -- Mean PARM = 1641 [gkg]

-100 000 100 200 300 400

h-values

36L

44L

9L

35L

45L

34L

66L

70L

Labo

rato

ries

Mandels h statistics(Soil 4 - TOC)

Soil 4-TOC

Unit gkg

Mandels k statistics(Soil 5 - TOC)Mandels h statistics(Soil 5 - TOC)

Sample Soil 5 Soil 5 - TOC -- Mean PARM = 2102 [gkg]

Element TOC

General calcparmT1= 113661E+03T2= 240201E+04T3= 54T4= 300T5= 51756E+01

n= variabelp= 10

N-table= 5

Mandels statistics End ResultLAB 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

44L 164383 14708 6 -036 325 Fail - - 44L - - -45865L 181250 0830 4 -033 018 Fail 181250 08302 4 3 -29045L 200317 1116 6 -029 025 Fail 200317 11163 6 5 -09935L 201833 1828 6 -029 040 Fail 201833 18280 6 5 -08432L 203250 0585 4 -029 013 Fail 203250 05852 4 3 -07016L 209000 0959 6 -028 021 Fail 209000 09592 6 5 -0129L 211667 0427 6 -027 009 Fail 211667 04274 6 5 01556L 214030 0887 6 -027 020 Fail 214030 08868 6 5 03819L 216000 0795 6 -026 018 Fail 216000 07950 6 5 05834L 226009 1308 6 -024 029 Fail 226009 13076 6 5 15836L 228783 4310 3 -024 095 Fail - - 36L - - 18666L 238750 1234 4 -022 027 Fail 238750 12340 4 3 28570L 2213900 - 1 333 Fail - - 70L - - 20037

Totgem 36224 2416 gkg 1-level 227 (175) 10 210211 (36L44L 70L) 10 9Totstd= 55669 4003 5-level 184 (151) 3

64RESULTS Mean = 2102106 gkg

Repeatability variance S2r = 117627Repeatability std Sr = 108456 --gt 516 r = 30368Between lab variance S2L = 176699Reproducibility var S2R = 294326Reproducibility std SR = 171559 --gt 816 R = 48037Remarks 3 Labs rejected (36L44L 70L)

000 050 100 150 200 250 300 350

k-values

44L

65L

45L

35L

32L

16L

9L

56L

19L

34L

36L

66L

70L

Mandels k statistics(Soil 5 - TOC)

-500 00 500 1000 1500 2000 2500

Deviation from Mean

44L

65L

45L

35L

32L

16L

9L

56L

19L

34L

36L

66L

70L

Labo

rato

ries

Soil 5 - TOC -- Mean PARM = 2102 [gkg]

-100 000 100 200 300 400

h-values

44L

65L

45L

35L

32L

16L

9L

56L

19L

34L

36L

66L

70L

Labo

rato

ries

Mandels h statistics(Soil 5 - TOC)

Soil 5-TOC

17

Annex 4

Raw data submitted

Sample Compost 1 Sample Compost 2 Sample Sewage Sludge 1Element TOC [gkg] Element TOC [gkg] Element TOC [gkg]

LAB PARM LAB PARM LAB PARM30L 2600 19L 1691 19L 286730L 2580 19L 1634 19L 281430L 2560 19L 1619 19L 276934L 2969 19L 1604 19L 272034L 2936 19L 1499 19L 268834L 2958 19L 1414 19L 266234L 2994 34L 1527 34L 315234L 3199 34L 1622 34L 314934L 3024 34L 1519 34L 343035L 2306 34L 1753 34L 336535L 2300 34L 1636 34L 304235L 2298 34L 1874 34L 298335L 2296 35L 1506 35L 270735L 2291 35L 1312 35L 270335L 2259 35L 1294 35L 268836L 2546 35L 1279 35L 267436L 2527 35L 1191 35L 263136L 2470 35L 1177 35L 262644L 2583 36L 1418 36L 271344L 2581 36L 1408 36L 266544L 2578 36L 1320 36L 261444L 2539 44L 1719 44L 292044L 2528 44L 1664 44L 291644L 2525 44L 1654 44L 291245L 2658 44L 1637 44L 290045L 2600 44L 1624 44L 289645L 2546 44L 1620 44L 289345L 2461 45L 1428 45L 297645L 2409 45L 1325 45L 295245L 2350 45L 1323 45L 288546L 2460 45L 1321 45L 286646L 2400 45L 1309 45L 284046L 2370 45L 1253 45L 278746L 2350 46L 1580 46L 233056L 2436 46L 1550 46L 233056L 2435 46L 1170 46L 230056L 2405 46L 1120 46L 229056L 2397 56L 1642 56L 270256L 2375 56L 1626 56L 270156L 2358 56L 1622 56L 269465L 2587 56L 1571 56L 269365L 2542 56L 1561 56L 268465L 2483 56L 1545 56L 268066L 2454 65L 1933 65L 264166L 2429 65L 1838 65L 260966L 2365 65L 1693 65L 260766L 2262 65L 1562 65L 260569L 2730 66L 1561 66L 270169L 2250 66L 1545 66L 267469L 1440 66L 1420 66L 261969L 1420 66L 1417 66L 251470L 2435 69L 2700 69L 2639L 2594 69L 2660 69L 2409L 2570 69L 2170 69L 2199L 2565 69L 2130 69L 2109L 2563 70L 1414 70L 28159L 2562 9L 1644 9L 28579L 2555 9L 1641 9L 2856

32L 2290 9L 1602 9L 285532L 2390 9L 1589 9L 285532L 2510 9L 1526 9L 285332L 2470 9L 1492 9L 284616L 2380 32L 1470 32L 265016L 2530 32L 1520 32L 271016L 2400 32L 1540 32L 271016L 2500 32L 1600 32L 280016L 2420 16L 1400 16L 284016L 2410 16L 1440 16L 2840

16L 1470 16L 286016L 1510 16L 287016L 1360 16L 287016L 1390 16L 2880

Sample Sewage Sludge 2 Sample Soil 4 Sample Soil 5Element TOC [gkg] Element TOC [gkg] Element TOC [gkg]

LAB PARM LAB PARM LAB PARM19L 2308 19L 1720 19L 225019L 2303 19L 1700 19L 223019L 2239 19L 1690 19L 221019L 2204 19L 1670 19L 211019L 2192 19L 1640 19L 210019L 2096 19L 1580 19L 206034L 2631 30L 1790 34L 244334L 2471 30L 1770 34L 233434L 2977 30L 1700 34L 231534L 2785 34L 1740 34L 222134L 2780 34L 1692 34L 217634L 2668 34L 1727 34L 207335L 2179 34L 1767 35L 233035L 2160 34L 1777 35L 208035L 2158 34L 1783 35L 201035L 2132 35L 1700 35L 198035L 2119 35L 1650 35L 193035L 2094 35L 1650 35L 178036L 2096 35L 1640 36L 254036L 2069 35L 1630 36L 253436L 2052 35L 1630 36L 179044L 2325 36L 1500 44L 302144L 2309 36L 1497 44L 298244L 2307 36L 1417 44L 295644L 2305 44L 1594 44L 30744L 2287 44L 1587 44L 30044L 2283 44L 1584 44L 29745L 2331 44L 1574 45L 214945L 2327 44L 1573 45L 209245L 2308 44L 1562 45L 203345L 2287 45L 1827 45L 197145L 2234 45L 1709 45L 193345L 2113 45L 1666 45L 184146L 190 45L 1665 56L 223746L 180 45L 1664 56L 222246L 180 45L 1600 56L 220346L 180 46L 2300 56L 206956L 2204 46L 2300 56L 206856L 2197 46L 2300 56L 204456L 2193 46L 2200 65L 192056L 2185 56L 1668 65L 182056L 2183 56L 1654 65L 179056L 2167 56L 1653 65L 172065L 2136 56L 1643 66L 254365L 2091 56L 1639 66L 242465L 2065 56L 1638 66L 232165L 2047 65L 1630 66L 226266L 2105 65L 1560 70L 2213966L 2022 65L 1530 9L 218066L 2009 65L 1490 9L 214066L 1983 66L 2179 9L 213070L 2272 66L 1900 9L 21109L 2385 66L 1762 9L 20709L 2377 66L 1734 9L 20709L 2375 70L 10404 32L 20509L 2359 9L 1640 32L 21009L 2356 9L 1640 32L 20209L 2354 9L 1610 32L 1960

32L 2240 9L 1590 16L 210032L 2260 9L 1590 16L 220032L 2200 9L 1560 16L 220032L 2270 32L 1640 16L 206016L 2300 32L 1600 16L 197016L 2310 32L 1560 16L 201016L 2350 32L 157016L 2260 16L 170016L 2290 16L 180016L 2240 16L 1700

16L 180016L 170016L 1700

European Commission EUR 23012 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on total organic carbon Author(s) E Sobiecka H van der Sloot K Andersen B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 50 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07412-7 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 total organic carbon (TOC) in soils sludge and treated bio-waste 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

-23012-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 sludge 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 a 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 total organic carbon (TOC) are described hereafter

6

11 Statistical concept underlying the validation According to the requirements of the work package concerning data handling and interpretation of the project HORIZONTAL the respective validation intercomparisons should be evaluated according to ISO 5725-21994 In particular repeatability and reproducibility of the draft standard should be determined 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 work program 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 exercises For each parameter investigated at least 10 laboratories should be nominated to participate The same laboratories should analyse different parameters as far as possible Due to the complexity of analysis and the respective workload of the laboratories it was decided to propose six materials for the validation of the TOC draft standard Each laboratory received two bottles of each material and was requested to perform 6 independent analyses per material1 (3 per bottle) using the draft standard method The 6 analyses 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 was permitted but had to be reported Likewise the different materials could 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 had 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 was set and should 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 The draft standard was made available to the laboratories on the Project Horizontal homepage Each laboratory was requested to provide the signed statements on cooperation as given in Annex 1

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 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

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

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 TOC

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

bull Compost 1 A compost material from Vienna bull Compost 2 A compost material from Germany bull Sewage Sludge 1 A mixed sewage sludge from Essen Germany bull Sewage Sludge 2 A mixed municipal sludge from North Rhine Westphalia

Germany bull Soil 4 A sludge amended soil from Hohenheim Germany bull Soil 5 An agricultural soil from Reading UK

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

122 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 httpwwwecnnldocssocietyhorizontalTOC_standard_for_validationpdf

123 Analytical program Two bottles had to be analysed for each of the six materials and each bottle had to be analysed independently three times 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 dry matter correction was free for each participant

124 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

9

submission of results has been set for TOC to the 31st of January 2007 Alternatively the participants were allowed to submit data electronically as Excel sheet using Email All data were treated in a confidential way Any presentation hereafter refers 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 provided a 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

125 Participants The following table lists the participating organizations and entities in the validation exercise for the horizontal TOC standard

bull Austria o barbara - Engineering Consulting Research amp Service GmbH o Federal Research and Training Centre for Forests Natural Hazards and

Landscape o NUA Umweltanalytik GmbH o Oumlsterreichische Agentur fuumlr Gesundheit und Ernaumlhrungssicherheit o Universitaumlt fuumlr Bodenkultur Wien o Shimadzu Europa GmbH o Umweltbundesamt o University of Natural resources and Applied Life Sciences

bull Belgium o VITO

bull France o INERIS o CEMAGREF - UR QELY o INRA - Laboratoire dAnalyse des Sols

bull Germany o ALBO-tec Technologiezentrum Fuumlr Analytik und Bodenmechanik GmbH

bull Norway o Norwegian Institute for Water Research

bull The Netherlands o ALCONTROL BV o Analytico Milieu B V

11

13 Summary results and derived performance characteristics The result of the various statistical evaluation according to ISO 5725-2 including outlier tests calculation of repeatability and reproducibility standard deviations can be found in Annex 3 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 The calculated average values the repeatability standard deviation (sr) and the reproducibility standard deviation (sR) are given in Table 1 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 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 total organic carbon (TOC) by dry combustion in treated biowaste sludge and soil All concentrations are expressed in gkg dry matter

Matrix Parameter Mean sr sR r R p Outliers Total number of data

No of

LOD

Sludge 1 TOC 272 17 59 13 45 13 2 62 0 Sludge 2 TOC 220 21 50 13 31 12 2 58 0

Compost 1 TOC 246 25 43 17 30 13 2 58 0 Compost 2 TOC 154 59 96 25 41 13 2 64 0

Soil 4 TOC 164 26 52 12 24 12 3 62 0 Soil 5 TOC 210 52 82 30 48 10 3 54 0

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

13

14 Annexes Annex 1 Model questionnaire to be filled by the participating laboratories Annex 2 Report on the validation materials used Annex 3 Statistical calculations Annex 4 Data submitted

14

14

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

15

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

16

Annex 3

Statistical calculations

Unit gkg

Mandels k statistics(Compost 1 - TOC)Mandels h statistics(Compost 1 - TOC)

Sample Compost 1 Compost 1 - TOC -- Mean PARM = 2463 [gkg]

Element TOC

General calcparmT1= 142643E+04T2= 351264E+06T3= 58T4= 292T5= 16501E+03

n= variabelp= 13

N-table= 5

Mandels statistics End ResultLAB 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

69L 1960000 64265 4 -235 352 Fail - - 69L - - -502735L 2291667 1674 6 -081 009 2291667 16741 6 5 -171066L 2377425 8552 4 -041 047 2377425 85518 4 3 -85346L 2395000 4796 4 -033 026 2395000 47958 4 3 -67756L 2401227 3133 6 -030 017 2401227 31330 6 5 -61432L 2415000 9713 4 -024 053 2415000 97125 4 3 -47770L 2435100 - 1 -014 2435100 - 1 -27616L 2440000 6033 6 -012 033 2440000 60332 6 5 -22745L 2503800 11759 6 018 064 2503800 117589 6 5 41136L 2514416 3994 3 023 022 2514416 39937 3 2 51765L 2537333 5216 3 033 029 2537333 52157 3 2 74744L 2555667 2783 6 042 015 2555667 27826 6 5 9309L 2568167 1356 6 048 007 2568167 13556 6 5 105530L 2580000 2000 3 053 011 2580000 20000 3 2 117334L 3013269 9580 6 255 053 Fail - - 34L - - 5506

Totgem 246587 9632 gkg 1-level 232 (176) 13 2462677 (34L 69L) 13 12Totstd= 21507 16070 5-level 186 (152) 2

68RESULTS Mean = 24626770 gkg

Repeatability variance S2r = 3666797Repeatability std Sr = 605541 --gt 246 r = 169551Between lab variance S2L = 7715586Reproducibility var S2R = 11382383Reproducibility std SR = 1066882 --gt 433 R = 298727Remarks 2 Labs rejected (34L 69L)

000 050 100 150 200 250 300 350 400

k-values

69L

35L

66L

46L

56L

32L

70L

16L

45L

36L

65L

44L

9L

30L

34L

Mandels k statistics(Compost 1 - TOC)

-600 -400 -200 00 200 400 600

Deviation from Mean

69L

35L

66L

46L

56L

32L

70L

16L

45L

36L

65L

44L

9L

30L

34L

Labo

rato

ries

Compost 1 - TOC -- Mean PARM = 2463 [gkg]

-300 -200 -100 000 100 200 300

h-values

69L

66L

56L

70L

45L

65L

9L

34L

Labo

rato

ries

Mandels h statistics(Compost 1 - TOC)

Compost 1-TOC

Unit gkg

Mandels k statistics(Compost 2 - TOC)Mandels h statistics(Compost 2 - TOC)

Sample Compost 2 Compost 2 - TOC -- Mean PARM = 1542 [gkg]

Element TOC

General calcparmT1= 994897E+03T2= 155556E+06T3= 64T4= 346T5= 41738E+03

n= variabelp= 13

N-table= 5

Mandels statistics End ResultLAB 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

45L 1326733 5665 6 -100 042 Fail 1326733 56646 6 5 -215046L 1355000 24365 4 -089 181 Fail - - 46L - - -186736L 1381949 5407 3 -078 040 Fail 1381949 54070 3 2 -159870L 1414120 - 1 -066 Fail 1414120 - 1 -127616L 1428333 5565 6 -061 041 1428333 55648 6 5 -113466L 1485550 7805 4 -039 058 1485550 78047 4 3 -56232L 1532500 5377 4 -021 040 1532500 53774 4 3 -09219L 1576833 10138 6 -004 075 1576833 101381 6 5 3519L 1582333 6166 6 -002 046 1582333 61659 6 5 40656L 1594432 4046 6 003 030 1594432 40463 6 5 52744L 1653000 3651 6 025 027 1653000 36508 6 5 111334L 1655127 13717 6 026 102 1655127 137168 6 5 113434L 1655127 13717 6 026 102 1655127 137168 6 5 113465L 1756500 16295 4 065 121 Fail 1756500 162949 4 3 214869L 2415000 30687 4 316 228 Fail - - 69L - - 8733

Totgem 158750 10900 gkg 1-level 232 (176) 13 1541734 (46L 69L) 13 12Totstd= 26187 8164 5-level 186 (152) 2

72RESULTS Mean = 15417337 gkg

Repeatability variance S2r = 8183950Repeatability std Sr = 904652 --gt 587 r = 253303Between lab variance S2L = 13631046Reproducibility var S2R = 21814995Reproducibility std SR = 1476990 --gt 958 R = 413557Remarks 2 Labs rejected (46L 69L)

000 050 100 150 200 250

k-values

45L

46L

36L

70L

16L

66L

32L

19L

9L

56L

44L

34L

34L

65L

69L

Mandels k statistics(Compost 2 - TOC)

-400 -200 00 200 400 600 800 1000

Deviation from Mean

45L

46L

36L

70L

16L

66L

32L

19L

9L

56L

44L

34L

34L

65L

69L

Labo

rato

ries

Compost 2 - TOC -- Mean PARM = 1542 [gkg]

-100 000 100 200 300 400

h-values

45L

36L

16L

32L

9L

44L

34L

69L

Labo

rato

ries

Mandels h statistics(Compost 2 - TOC)

Compost 2-TOC

Unit gkg

Mandels k statistics(Sludge 1 - TOC)Mandels h statistics(Sludge 1 - TOC)

Sample Sludge 1 Sludge 1 - TOC -- Mean PARM = 2721 [gkg]

Element TOC

General calcparmT1= 169626E+04T2= 465445E+06T3= 62T4= 326T5= 10312E+03

n= variabelp= 13

N-table= 5

Mandels statistics End ResultLAB 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

69L 233000 2362 4 -347 037 Fail - - 69L - - -2488046L 2312500 2062 4 -040 032 Fail 2312500 20616 4 3 -408565L 2615500 1708 4 004 026 2615500 17078 4 3 -105566L 2627200 8268 4 006 128 2627200 82678 4 3 -93836L 2664041 4976 3 011 077 2664041 49758 3 2 -56935L 2671500 3533 6 013 055 2671500 35331 6 5 -49556L 2692298 0874 6 016 014 Fail 2692298 08738 6 5 -28732L 2717500 6185 4 019 096 Fail 2717500 61847 4 3 -03519L 2753333 7819 6 025 121 Fail 2753333 78189 6 5 32470L 2814600 - 1 034 Fail 2814600 - 1 9369L 2853667 0398 6 039 006 Fail 2853667 03983 6 5 132716L 2860000 1673 6 040 026 Fail 2860000 16733 6 5 139045L 2884433 7033 6 044 109 Fail 2884433 70331 6 5 163544L 2906167 1129 6 047 017 Fail 2906167 11286 6 5 185234L 3186874 17674 6 089 274 Fail - - 34L - - 4659

Totgem 258617 4692 gkg 1-level 232 (176) 13 2720980 (34L 69L) 13 12Totstd= 67800 4610 5-level 186 (152) 2

72RESULTS Mean = 27209799 gkg

Repeatability variance S2r = 2104538Repeatability std Sr = 458752 --gt 169 r = 128451Between lab variance S2L = 23618387Reproducibility var S2R = 25722925Reproducibility std SR = 1603837 --gt 589 R = 449074Remarks 2 Labs rejected (34L 69L)

000 050 100 150 200 250 300

k-values

69L

46L

65L

66L

36L

35L

56L

32L

19L

70L

9L

16L

45L

44L

34L

Mandels k statistics(Sludge 1 - TOC)

-2500 -2000 -1500 -1000 -500 00 500

Deviation from Mean

69L

46L

65L

66L

36L

35L

56L

32L

19L

70L

9L

16L

45L

44L

34L

Labo

rato

ries

Sludge 1 - TOC -- Mean PARM = 2721 [gkg]

-400 -300 -200 -100 000 100

h-values

69L

65L

36L

56L

19L

9L

45L

34L

Labo

rato

ries

Mandels h statistics(Sludge 1 - TOC)

Sludge 1-TOC

68 Unit gkg

Mandels k statistics(Sludge 2 - TOC)Mandels h statistics(Sludge 2 - TOC)

Sample Sludge 2 Sludge 2 - TOC -- Mean PARM = 2207 [gkg]

Element TOC

General calcparmT1= 128601E+04T2= 285689E+06T3= 58T4= 310T5= 97826E+02

n= variabelp= 12

N-table= 5

Mandels statistics End ResultLAB 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

46L 182500 0500 4 -333 008 Fail - - 46L - - -2024466L 2029475 5267 4 -012 084 2029475 52674 4 3 -177436L 2072609 2222 3 -005 035 2072609 22222 3 2 -134365L 2084750 3865 4 -002 062 2084750 38647 4 3 -122135L 2140333 3119 6 007 050 2140333 31194 6 5 -66556L 2188021 1282 6 015 020 2188021 12822 6 5 -18819L 2223667 7916 6 022 126 Fail 2223667 79157 6 5 16832L 2242500 3096 4 025 049 Fail 2242500 30957 4 3 35645L 2266600 8322 6 029 132 Fail 2266600 83216 6 5 59770L 2272460 - 1 030 Fail 2272460 - 1 65616L 2291667 3869 6 033 062 Fail 2291667 38687 6 5 84844L 2302667 1546 6 035 025 Fail 2302667 15462 6 5 9589L 2367667 1296 6 047 021 Fail 2367667 12956 6 5 160834L 2718591 17124 6 108 273 Fail - - 34L - - 5117

Totgem 209882 4571 gkg 1-level 230 (176) 12 2206868 (34L 46L) 12 11Totstd= 57628 4485 5-level 185 (151) 2

68RESULTS Mean = 22068679 gkg

Repeatability variance S2r = 2126659Repeatability std Sr = 461157 --gt 209 r = 129124Between lab variance S2L = 9960432Reproducibility var S2R = 12087091Reproducibility std SR = 1099413 --gt 498 R = 307836Remarks 2 Labs rejected (34L 46L)

000 050 100 150 200 250 300

k-values

46L

66L

36L

65L

35L

56L

19L

32L

45L

70L

16L

44L

9L

34L

Mandels k statistics(Sludge 2 - TOC)

-2500 -2000 -1500 -1000 -500 00 500 1000

Deviation from Mean

46L

66L

36L

65L

35L

56L

19L

32L

45L

70L

16L

44L

9L

34L

Labo

rato

ries

Sludge 2 - TOC -- Mean PARM = 2207 [gkg]

-400 -300 -200 -100 000 100 200

h-values

46L

66L

36L

65L

35L

56L

19L

32L

45L

70L

16L

44L

9L

34L

Labo

rato

ries

Mandels h statistics(Sludge 2 - TOC)

Sludge 2-TOC

Unit gkg

Mandels k statistics(Soil 4 - TOC)Mandels h statistics(Soil 4 - TOC)

Sample Soil 4 Soil 4 - TOC -- Mean PARM = 1641 [gkg]

Element TOC

General calcparmT1= 102171E+03T2= 168700E+04T3= 62T4= 338T5= 94040E+00

n= variabelp= 12

N-table= 5

Mandels statistics End ResultLAB 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

36L 147161 0470 3 -036 068 Fail 147161 04702 3 2 -16965L 155250 0591 4 -032 085 Fail 155250 05909 4 3 -08844L 157900 0115 6 -031 017 Fail 157900 01152 6 5 -06232L 159250 0359 4 -031 052 Fail 159250 03594 4 3 -0489L 160500 0315 6 -030 045 Fail 160500 03146 6 5 -03656L 164927 0113 6 -028 016 Fail 164927 01127 6 5 00835L 165000 0261 6 -028 038 Fail 165000 02608 6 5 00919L 166667 0505 6 -027 073 Fail 166667 05046 6 5 02645L 168850 0763 6 -026 110 Fail 168850 07628 6 5 04816L 173333 0516 6 -024 074 Fail 173333 05164 6 5 09334L 174761 0346 6 -024 050 Fail 174761 03462 6 5 10730L 175333 0473 3 -024 068 Fail 175333 04726 3 2 11366L 189375 2035 4 -017 294 Fail - - 66L - - 25346L 227500 0500 4 000 072 - - 46L - - 63470L 1040400 - 1 360 Fail - - 70L - - 8763

Totgem 22841 0526 gkg 1-level 232 (176) 12 164078 (46L 66L70L) 12 11Totstd= 22541 0469 5-level 186 (152) 3

71RESULTS Mean = 1640777 gkg

Repeatability variance S2r = 018808Repeatability std Sr = 043368 --gt 264 r = 12143Between lab variance S2L = 054747Reproducibility var S2R = 073555Reproducibility std SR = 085764 --gt 523 R = 24014Remarks 3 Labs rejected (46L 66L70L)

000 050 100 150 200 250 300

k-values

36L

65L

44L

32L

9L

56L

35L

19L

45L

16L

34L

30L

66L

46L

70L

Mandels k statistics(Soil 4 - TOC)

-100 00 100 200 300 400 500 600 700 800 900

Deviation from Mean

36L

65L

44L

32L

9L

56L

35L

19L

45L

16L

34L

30L

66L

46L

70L

Labo

rato

ries

Soil 4 - TOC -- Mean PARM = 1641 [gkg]

-100 000 100 200 300 400

h-values

36L

44L

9L

35L

45L

34L

66L

70L

Labo

rato

ries

Mandels h statistics(Soil 4 - TOC)

Soil 4-TOC

Unit gkg

Mandels k statistics(Soil 5 - TOC)Mandels h statistics(Soil 5 - TOC)

Sample Soil 5 Soil 5 - TOC -- Mean PARM = 2102 [gkg]

Element TOC

General calcparmT1= 113661E+03T2= 240201E+04T3= 54T4= 300T5= 51756E+01

n= variabelp= 10

N-table= 5

Mandels statistics End ResultLAB 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

44L 164383 14708 6 -036 325 Fail - - 44L - - -45865L 181250 0830 4 -033 018 Fail 181250 08302 4 3 -29045L 200317 1116 6 -029 025 Fail 200317 11163 6 5 -09935L 201833 1828 6 -029 040 Fail 201833 18280 6 5 -08432L 203250 0585 4 -029 013 Fail 203250 05852 4 3 -07016L 209000 0959 6 -028 021 Fail 209000 09592 6 5 -0129L 211667 0427 6 -027 009 Fail 211667 04274 6 5 01556L 214030 0887 6 -027 020 Fail 214030 08868 6 5 03819L 216000 0795 6 -026 018 Fail 216000 07950 6 5 05834L 226009 1308 6 -024 029 Fail 226009 13076 6 5 15836L 228783 4310 3 -024 095 Fail - - 36L - - 18666L 238750 1234 4 -022 027 Fail 238750 12340 4 3 28570L 2213900 - 1 333 Fail - - 70L - - 20037

Totgem 36224 2416 gkg 1-level 227 (175) 10 210211 (36L44L 70L) 10 9Totstd= 55669 4003 5-level 184 (151) 3

64RESULTS Mean = 2102106 gkg

Repeatability variance S2r = 117627Repeatability std Sr = 108456 --gt 516 r = 30368Between lab variance S2L = 176699Reproducibility var S2R = 294326Reproducibility std SR = 171559 --gt 816 R = 48037Remarks 3 Labs rejected (36L44L 70L)

000 050 100 150 200 250 300 350

k-values

44L

65L

45L

35L

32L

16L

9L

56L

19L

34L

36L

66L

70L

Mandels k statistics(Soil 5 - TOC)

-500 00 500 1000 1500 2000 2500

Deviation from Mean

44L

65L

45L

35L

32L

16L

9L

56L

19L

34L

36L

66L

70L

Labo

rato

ries

Soil 5 - TOC -- Mean PARM = 2102 [gkg]

-100 000 100 200 300 400

h-values

44L

65L

45L

35L

32L

16L

9L

56L

19L

34L

36L

66L

70L

Labo

rato

ries

Mandels h statistics(Soil 5 - TOC)

Soil 5-TOC

17

Annex 4

Raw data submitted

Sample Compost 1 Sample Compost 2 Sample Sewage Sludge 1Element TOC [gkg] Element TOC [gkg] Element TOC [gkg]

LAB PARM LAB PARM LAB PARM30L 2600 19L 1691 19L 286730L 2580 19L 1634 19L 281430L 2560 19L 1619 19L 276934L 2969 19L 1604 19L 272034L 2936 19L 1499 19L 268834L 2958 19L 1414 19L 266234L 2994 34L 1527 34L 315234L 3199 34L 1622 34L 314934L 3024 34L 1519 34L 343035L 2306 34L 1753 34L 336535L 2300 34L 1636 34L 304235L 2298 34L 1874 34L 298335L 2296 35L 1506 35L 270735L 2291 35L 1312 35L 270335L 2259 35L 1294 35L 268836L 2546 35L 1279 35L 267436L 2527 35L 1191 35L 263136L 2470 35L 1177 35L 262644L 2583 36L 1418 36L 271344L 2581 36L 1408 36L 266544L 2578 36L 1320 36L 261444L 2539 44L 1719 44L 292044L 2528 44L 1664 44L 291644L 2525 44L 1654 44L 291245L 2658 44L 1637 44L 290045L 2600 44L 1624 44L 289645L 2546 44L 1620 44L 289345L 2461 45L 1428 45L 297645L 2409 45L 1325 45L 295245L 2350 45L 1323 45L 288546L 2460 45L 1321 45L 286646L 2400 45L 1309 45L 284046L 2370 45L 1253 45L 278746L 2350 46L 1580 46L 233056L 2436 46L 1550 46L 233056L 2435 46L 1170 46L 230056L 2405 46L 1120 46L 229056L 2397 56L 1642 56L 270256L 2375 56L 1626 56L 270156L 2358 56L 1622 56L 269465L 2587 56L 1571 56L 269365L 2542 56L 1561 56L 268465L 2483 56L 1545 56L 268066L 2454 65L 1933 65L 264166L 2429 65L 1838 65L 260966L 2365 65L 1693 65L 260766L 2262 65L 1562 65L 260569L 2730 66L 1561 66L 270169L 2250 66L 1545 66L 267469L 1440 66L 1420 66L 261969L 1420 66L 1417 66L 251470L 2435 69L 2700 69L 2639L 2594 69L 2660 69L 2409L 2570 69L 2170 69L 2199L 2565 69L 2130 69L 2109L 2563 70L 1414 70L 28159L 2562 9L 1644 9L 28579L 2555 9L 1641 9L 2856

32L 2290 9L 1602 9L 285532L 2390 9L 1589 9L 285532L 2510 9L 1526 9L 285332L 2470 9L 1492 9L 284616L 2380 32L 1470 32L 265016L 2530 32L 1520 32L 271016L 2400 32L 1540 32L 271016L 2500 32L 1600 32L 280016L 2420 16L 1400 16L 284016L 2410 16L 1440 16L 2840

16L 1470 16L 286016L 1510 16L 287016L 1360 16L 287016L 1390 16L 2880

Sample Sewage Sludge 2 Sample Soil 4 Sample Soil 5Element TOC [gkg] Element TOC [gkg] Element TOC [gkg]

LAB PARM LAB PARM LAB PARM19L 2308 19L 1720 19L 225019L 2303 19L 1700 19L 223019L 2239 19L 1690 19L 221019L 2204 19L 1670 19L 211019L 2192 19L 1640 19L 210019L 2096 19L 1580 19L 206034L 2631 30L 1790 34L 244334L 2471 30L 1770 34L 233434L 2977 30L 1700 34L 231534L 2785 34L 1740 34L 222134L 2780 34L 1692 34L 217634L 2668 34L 1727 34L 207335L 2179 34L 1767 35L 233035L 2160 34L 1777 35L 208035L 2158 34L 1783 35L 201035L 2132 35L 1700 35L 198035L 2119 35L 1650 35L 193035L 2094 35L 1650 35L 178036L 2096 35L 1640 36L 254036L 2069 35L 1630 36L 253436L 2052 35L 1630 36L 179044L 2325 36L 1500 44L 302144L 2309 36L 1497 44L 298244L 2307 36L 1417 44L 295644L 2305 44L 1594 44L 30744L 2287 44L 1587 44L 30044L 2283 44L 1584 44L 29745L 2331 44L 1574 45L 214945L 2327 44L 1573 45L 209245L 2308 44L 1562 45L 203345L 2287 45L 1827 45L 197145L 2234 45L 1709 45L 193345L 2113 45L 1666 45L 184146L 190 45L 1665 56L 223746L 180 45L 1664 56L 222246L 180 45L 1600 56L 220346L 180 46L 2300 56L 206956L 2204 46L 2300 56L 206856L 2197 46L 2300 56L 204456L 2193 46L 2200 65L 192056L 2185 56L 1668 65L 182056L 2183 56L 1654 65L 179056L 2167 56L 1653 65L 172065L 2136 56L 1643 66L 254365L 2091 56L 1639 66L 242465L 2065 56L 1638 66L 232165L 2047 65L 1630 66L 226266L 2105 65L 1560 70L 2213966L 2022 65L 1530 9L 218066L 2009 65L 1490 9L 214066L 1983 66L 2179 9L 213070L 2272 66L 1900 9L 21109L 2385 66L 1762 9L 20709L 2377 66L 1734 9L 20709L 2375 70L 10404 32L 20509L 2359 9L 1640 32L 21009L 2356 9L 1640 32L 20209L 2354 9L 1610 32L 1960

32L 2240 9L 1590 16L 210032L 2260 9L 1590 16L 220032L 2200 9L 1560 16L 220032L 2270 32L 1640 16L 206016L 2300 32L 1600 16L 197016L 2310 32L 1560 16L 201016L 2350 32L 157016L 2260 16L 170016L 2290 16L 180016L 2240 16L 1700

16L 180016L 170016L 1700

European Commission EUR 23012 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on total organic carbon Author(s) E Sobiecka H van der Sloot K Andersen B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 50 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07412-7 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 total organic carbon (TOC) in soils sludge and treated bio-waste 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

-23012-EN

-C

6

11 Statistical concept underlying the validation According to the requirements of the work package concerning data handling and interpretation of the project HORIZONTAL the respective validation intercomparisons should be evaluated according to ISO 5725-21994 In particular repeatability and reproducibility of the draft standard should be determined 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 work program 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 exercises For each parameter investigated at least 10 laboratories should be nominated to participate The same laboratories should analyse different parameters as far as possible Due to the complexity of analysis and the respective workload of the laboratories it was decided to propose six materials for the validation of the TOC draft standard Each laboratory received two bottles of each material and was requested to perform 6 independent analyses per material1 (3 per bottle) using the draft standard method The 6 analyses 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 was permitted but had to be reported Likewise the different materials could 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 had 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 was set and should 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 The draft standard was made available to the laboratories on the Project Horizontal homepage Each laboratory was requested to provide the signed statements on cooperation as given in Annex 1

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 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

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

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 TOC

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

bull Compost 1 A compost material from Vienna bull Compost 2 A compost material from Germany bull Sewage Sludge 1 A mixed sewage sludge from Essen Germany bull Sewage Sludge 2 A mixed municipal sludge from North Rhine Westphalia

Germany bull Soil 4 A sludge amended soil from Hohenheim Germany bull Soil 5 An agricultural soil from Reading UK

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

122 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 httpwwwecnnldocssocietyhorizontalTOC_standard_for_validationpdf

123 Analytical program Two bottles had to be analysed for each of the six materials and each bottle had to be analysed independently three times 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 dry matter correction was free for each participant

124 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

9

submission of results has been set for TOC to the 31st of January 2007 Alternatively the participants were allowed to submit data electronically as Excel sheet using Email All data were treated in a confidential way Any presentation hereafter refers 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 provided a 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

125 Participants The following table lists the participating organizations and entities in the validation exercise for the horizontal TOC standard

bull Austria o barbara - Engineering Consulting Research amp Service GmbH o Federal Research and Training Centre for Forests Natural Hazards and

Landscape o NUA Umweltanalytik GmbH o Oumlsterreichische Agentur fuumlr Gesundheit und Ernaumlhrungssicherheit o Universitaumlt fuumlr Bodenkultur Wien o Shimadzu Europa GmbH o Umweltbundesamt o University of Natural resources and Applied Life Sciences

bull Belgium o VITO

bull France o INERIS o CEMAGREF - UR QELY o INRA - Laboratoire dAnalyse des Sols

bull Germany o ALBO-tec Technologiezentrum Fuumlr Analytik und Bodenmechanik GmbH

bull Norway o Norwegian Institute for Water Research

bull The Netherlands o ALCONTROL BV o Analytico Milieu B V

11

13 Summary results and derived performance characteristics The result of the various statistical evaluation according to ISO 5725-2 including outlier tests calculation of repeatability and reproducibility standard deviations can be found in Annex 3 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 The calculated average values the repeatability standard deviation (sr) and the reproducibility standard deviation (sR) are given in Table 1 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 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 total organic carbon (TOC) by dry combustion in treated biowaste sludge and soil All concentrations are expressed in gkg dry matter

Matrix Parameter Mean sr sR r R p Outliers Total number of data

No of

LOD

Sludge 1 TOC 272 17 59 13 45 13 2 62 0 Sludge 2 TOC 220 21 50 13 31 12 2 58 0

Compost 1 TOC 246 25 43 17 30 13 2 58 0 Compost 2 TOC 154 59 96 25 41 13 2 64 0

Soil 4 TOC 164 26 52 12 24 12 3 62 0 Soil 5 TOC 210 52 82 30 48 10 3 54 0

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

13

14 Annexes Annex 1 Model questionnaire to be filled by the participating laboratories Annex 2 Report on the validation materials used Annex 3 Statistical calculations Annex 4 Data submitted

14

14

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

15

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

16

Annex 3

Statistical calculations

Unit gkg

Mandels k statistics(Compost 1 - TOC)Mandels h statistics(Compost 1 - TOC)

Sample Compost 1 Compost 1 - TOC -- Mean PARM = 2463 [gkg]

Element TOC

General calcparmT1= 142643E+04T2= 351264E+06T3= 58T4= 292T5= 16501E+03

n= variabelp= 13

N-table= 5

Mandels statistics End ResultLAB 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

69L 1960000 64265 4 -235 352 Fail - - 69L - - -502735L 2291667 1674 6 -081 009 2291667 16741 6 5 -171066L 2377425 8552 4 -041 047 2377425 85518 4 3 -85346L 2395000 4796 4 -033 026 2395000 47958 4 3 -67756L 2401227 3133 6 -030 017 2401227 31330 6 5 -61432L 2415000 9713 4 -024 053 2415000 97125 4 3 -47770L 2435100 - 1 -014 2435100 - 1 -27616L 2440000 6033 6 -012 033 2440000 60332 6 5 -22745L 2503800 11759 6 018 064 2503800 117589 6 5 41136L 2514416 3994 3 023 022 2514416 39937 3 2 51765L 2537333 5216 3 033 029 2537333 52157 3 2 74744L 2555667 2783 6 042 015 2555667 27826 6 5 9309L 2568167 1356 6 048 007 2568167 13556 6 5 105530L 2580000 2000 3 053 011 2580000 20000 3 2 117334L 3013269 9580 6 255 053 Fail - - 34L - - 5506

Totgem 246587 9632 gkg 1-level 232 (176) 13 2462677 (34L 69L) 13 12Totstd= 21507 16070 5-level 186 (152) 2

68RESULTS Mean = 24626770 gkg

Repeatability variance S2r = 3666797Repeatability std Sr = 605541 --gt 246 r = 169551Between lab variance S2L = 7715586Reproducibility var S2R = 11382383Reproducibility std SR = 1066882 --gt 433 R = 298727Remarks 2 Labs rejected (34L 69L)

000 050 100 150 200 250 300 350 400

k-values

69L

35L

66L

46L

56L

32L

70L

16L

45L

36L

65L

44L

9L

30L

34L

Mandels k statistics(Compost 1 - TOC)

-600 -400 -200 00 200 400 600

Deviation from Mean

69L

35L

66L

46L

56L

32L

70L

16L

45L

36L

65L

44L

9L

30L

34L

Labo

rato

ries

Compost 1 - TOC -- Mean PARM = 2463 [gkg]

-300 -200 -100 000 100 200 300

h-values

69L

66L

56L

70L

45L

65L

9L

34L

Labo

rato

ries

Mandels h statistics(Compost 1 - TOC)

Compost 1-TOC

Unit gkg

Mandels k statistics(Compost 2 - TOC)Mandels h statistics(Compost 2 - TOC)

Sample Compost 2 Compost 2 - TOC -- Mean PARM = 1542 [gkg]

Element TOC

General calcparmT1= 994897E+03T2= 155556E+06T3= 64T4= 346T5= 41738E+03

n= variabelp= 13

N-table= 5

Mandels statistics End ResultLAB 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

45L 1326733 5665 6 -100 042 Fail 1326733 56646 6 5 -215046L 1355000 24365 4 -089 181 Fail - - 46L - - -186736L 1381949 5407 3 -078 040 Fail 1381949 54070 3 2 -159870L 1414120 - 1 -066 Fail 1414120 - 1 -127616L 1428333 5565 6 -061 041 1428333 55648 6 5 -113466L 1485550 7805 4 -039 058 1485550 78047 4 3 -56232L 1532500 5377 4 -021 040 1532500 53774 4 3 -09219L 1576833 10138 6 -004 075 1576833 101381 6 5 3519L 1582333 6166 6 -002 046 1582333 61659 6 5 40656L 1594432 4046 6 003 030 1594432 40463 6 5 52744L 1653000 3651 6 025 027 1653000 36508 6 5 111334L 1655127 13717 6 026 102 1655127 137168 6 5 113434L 1655127 13717 6 026 102 1655127 137168 6 5 113465L 1756500 16295 4 065 121 Fail 1756500 162949 4 3 214869L 2415000 30687 4 316 228 Fail - - 69L - - 8733

Totgem 158750 10900 gkg 1-level 232 (176) 13 1541734 (46L 69L) 13 12Totstd= 26187 8164 5-level 186 (152) 2

72RESULTS Mean = 15417337 gkg

Repeatability variance S2r = 8183950Repeatability std Sr = 904652 --gt 587 r = 253303Between lab variance S2L = 13631046Reproducibility var S2R = 21814995Reproducibility std SR = 1476990 --gt 958 R = 413557Remarks 2 Labs rejected (46L 69L)

000 050 100 150 200 250

k-values

45L

46L

36L

70L

16L

66L

32L

19L

9L

56L

44L

34L

34L

65L

69L

Mandels k statistics(Compost 2 - TOC)

-400 -200 00 200 400 600 800 1000

Deviation from Mean

45L

46L

36L

70L

16L

66L

32L

19L

9L

56L

44L

34L

34L

65L

69L

Labo

rato

ries

Compost 2 - TOC -- Mean PARM = 1542 [gkg]

-100 000 100 200 300 400

h-values

45L

36L

16L

32L

9L

44L

34L

69L

Labo

rato

ries

Mandels h statistics(Compost 2 - TOC)

Compost 2-TOC

Unit gkg

Mandels k statistics(Sludge 1 - TOC)Mandels h statistics(Sludge 1 - TOC)

Sample Sludge 1 Sludge 1 - TOC -- Mean PARM = 2721 [gkg]

Element TOC

General calcparmT1= 169626E+04T2= 465445E+06T3= 62T4= 326T5= 10312E+03

n= variabelp= 13

N-table= 5

Mandels statistics End ResultLAB 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

69L 233000 2362 4 -347 037 Fail - - 69L - - -2488046L 2312500 2062 4 -040 032 Fail 2312500 20616 4 3 -408565L 2615500 1708 4 004 026 2615500 17078 4 3 -105566L 2627200 8268 4 006 128 2627200 82678 4 3 -93836L 2664041 4976 3 011 077 2664041 49758 3 2 -56935L 2671500 3533 6 013 055 2671500 35331 6 5 -49556L 2692298 0874 6 016 014 Fail 2692298 08738 6 5 -28732L 2717500 6185 4 019 096 Fail 2717500 61847 4 3 -03519L 2753333 7819 6 025 121 Fail 2753333 78189 6 5 32470L 2814600 - 1 034 Fail 2814600 - 1 9369L 2853667 0398 6 039 006 Fail 2853667 03983 6 5 132716L 2860000 1673 6 040 026 Fail 2860000 16733 6 5 139045L 2884433 7033 6 044 109 Fail 2884433 70331 6 5 163544L 2906167 1129 6 047 017 Fail 2906167 11286 6 5 185234L 3186874 17674 6 089 274 Fail - - 34L - - 4659

Totgem 258617 4692 gkg 1-level 232 (176) 13 2720980 (34L 69L) 13 12Totstd= 67800 4610 5-level 186 (152) 2

72RESULTS Mean = 27209799 gkg

Repeatability variance S2r = 2104538Repeatability std Sr = 458752 --gt 169 r = 128451Between lab variance S2L = 23618387Reproducibility var S2R = 25722925Reproducibility std SR = 1603837 --gt 589 R = 449074Remarks 2 Labs rejected (34L 69L)

000 050 100 150 200 250 300

k-values

69L

46L

65L

66L

36L

35L

56L

32L

19L

70L

9L

16L

45L

44L

34L

Mandels k statistics(Sludge 1 - TOC)

-2500 -2000 -1500 -1000 -500 00 500

Deviation from Mean

69L

46L

65L

66L

36L

35L

56L

32L

19L

70L

9L

16L

45L

44L

34L

Labo

rato

ries

Sludge 1 - TOC -- Mean PARM = 2721 [gkg]

-400 -300 -200 -100 000 100

h-values

69L

65L

36L

56L

19L

9L

45L

34L

Labo

rato

ries

Mandels h statistics(Sludge 1 - TOC)

Sludge 1-TOC

68 Unit gkg

Mandels k statistics(Sludge 2 - TOC)Mandels h statistics(Sludge 2 - TOC)

Sample Sludge 2 Sludge 2 - TOC -- Mean PARM = 2207 [gkg]

Element TOC

General calcparmT1= 128601E+04T2= 285689E+06T3= 58T4= 310T5= 97826E+02

n= variabelp= 12

N-table= 5

Mandels statistics End ResultLAB 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

46L 182500 0500 4 -333 008 Fail - - 46L - - -2024466L 2029475 5267 4 -012 084 2029475 52674 4 3 -177436L 2072609 2222 3 -005 035 2072609 22222 3 2 -134365L 2084750 3865 4 -002 062 2084750 38647 4 3 -122135L 2140333 3119 6 007 050 2140333 31194 6 5 -66556L 2188021 1282 6 015 020 2188021 12822 6 5 -18819L 2223667 7916 6 022 126 Fail 2223667 79157 6 5 16832L 2242500 3096 4 025 049 Fail 2242500 30957 4 3 35645L 2266600 8322 6 029 132 Fail 2266600 83216 6 5 59770L 2272460 - 1 030 Fail 2272460 - 1 65616L 2291667 3869 6 033 062 Fail 2291667 38687 6 5 84844L 2302667 1546 6 035 025 Fail 2302667 15462 6 5 9589L 2367667 1296 6 047 021 Fail 2367667 12956 6 5 160834L 2718591 17124 6 108 273 Fail - - 34L - - 5117

Totgem 209882 4571 gkg 1-level 230 (176) 12 2206868 (34L 46L) 12 11Totstd= 57628 4485 5-level 185 (151) 2

68RESULTS Mean = 22068679 gkg

Repeatability variance S2r = 2126659Repeatability std Sr = 461157 --gt 209 r = 129124Between lab variance S2L = 9960432Reproducibility var S2R = 12087091Reproducibility std SR = 1099413 --gt 498 R = 307836Remarks 2 Labs rejected (34L 46L)

000 050 100 150 200 250 300

k-values

46L

66L

36L

65L

35L

56L

19L

32L

45L

70L

16L

44L

9L

34L

Mandels k statistics(Sludge 2 - TOC)

-2500 -2000 -1500 -1000 -500 00 500 1000

Deviation from Mean

46L

66L

36L

65L

35L

56L

19L

32L

45L

70L

16L

44L

9L

34L

Labo

rato

ries

Sludge 2 - TOC -- Mean PARM = 2207 [gkg]

-400 -300 -200 -100 000 100 200

h-values

46L

66L

36L

65L

35L

56L

19L

32L

45L

70L

16L

44L

9L

34L

Labo

rato

ries

Mandels h statistics(Sludge 2 - TOC)

Sludge 2-TOC

Unit gkg

Mandels k statistics(Soil 4 - TOC)Mandels h statistics(Soil 4 - TOC)

Sample Soil 4 Soil 4 - TOC -- Mean PARM = 1641 [gkg]

Element TOC

General calcparmT1= 102171E+03T2= 168700E+04T3= 62T4= 338T5= 94040E+00

n= variabelp= 12

N-table= 5

Mandels statistics End ResultLAB 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

36L 147161 0470 3 -036 068 Fail 147161 04702 3 2 -16965L 155250 0591 4 -032 085 Fail 155250 05909 4 3 -08844L 157900 0115 6 -031 017 Fail 157900 01152 6 5 -06232L 159250 0359 4 -031 052 Fail 159250 03594 4 3 -0489L 160500 0315 6 -030 045 Fail 160500 03146 6 5 -03656L 164927 0113 6 -028 016 Fail 164927 01127 6 5 00835L 165000 0261 6 -028 038 Fail 165000 02608 6 5 00919L 166667 0505 6 -027 073 Fail 166667 05046 6 5 02645L 168850 0763 6 -026 110 Fail 168850 07628 6 5 04816L 173333 0516 6 -024 074 Fail 173333 05164 6 5 09334L 174761 0346 6 -024 050 Fail 174761 03462 6 5 10730L 175333 0473 3 -024 068 Fail 175333 04726 3 2 11366L 189375 2035 4 -017 294 Fail - - 66L - - 25346L 227500 0500 4 000 072 - - 46L - - 63470L 1040400 - 1 360 Fail - - 70L - - 8763

Totgem 22841 0526 gkg 1-level 232 (176) 12 164078 (46L 66L70L) 12 11Totstd= 22541 0469 5-level 186 (152) 3

71RESULTS Mean = 1640777 gkg

Repeatability variance S2r = 018808Repeatability std Sr = 043368 --gt 264 r = 12143Between lab variance S2L = 054747Reproducibility var S2R = 073555Reproducibility std SR = 085764 --gt 523 R = 24014Remarks 3 Labs rejected (46L 66L70L)

000 050 100 150 200 250 300

k-values

36L

65L

44L

32L

9L

56L

35L

19L

45L

16L

34L

30L

66L

46L

70L

Mandels k statistics(Soil 4 - TOC)

-100 00 100 200 300 400 500 600 700 800 900

Deviation from Mean

36L

65L

44L

32L

9L

56L

35L

19L

45L

16L

34L

30L

66L

46L

70L

Labo

rato

ries

Soil 4 - TOC -- Mean PARM = 1641 [gkg]

-100 000 100 200 300 400

h-values

36L

44L

9L

35L

45L

34L

66L

70L

Labo

rato

ries

Mandels h statistics(Soil 4 - TOC)

Soil 4-TOC

Unit gkg

Mandels k statistics(Soil 5 - TOC)Mandels h statistics(Soil 5 - TOC)

Sample Soil 5 Soil 5 - TOC -- Mean PARM = 2102 [gkg]

Element TOC

General calcparmT1= 113661E+03T2= 240201E+04T3= 54T4= 300T5= 51756E+01

n= variabelp= 10

N-table= 5

Mandels statistics End ResultLAB 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

44L 164383 14708 6 -036 325 Fail - - 44L - - -45865L 181250 0830 4 -033 018 Fail 181250 08302 4 3 -29045L 200317 1116 6 -029 025 Fail 200317 11163 6 5 -09935L 201833 1828 6 -029 040 Fail 201833 18280 6 5 -08432L 203250 0585 4 -029 013 Fail 203250 05852 4 3 -07016L 209000 0959 6 -028 021 Fail 209000 09592 6 5 -0129L 211667 0427 6 -027 009 Fail 211667 04274 6 5 01556L 214030 0887 6 -027 020 Fail 214030 08868 6 5 03819L 216000 0795 6 -026 018 Fail 216000 07950 6 5 05834L 226009 1308 6 -024 029 Fail 226009 13076 6 5 15836L 228783 4310 3 -024 095 Fail - - 36L - - 18666L 238750 1234 4 -022 027 Fail 238750 12340 4 3 28570L 2213900 - 1 333 Fail - - 70L - - 20037

Totgem 36224 2416 gkg 1-level 227 (175) 10 210211 (36L44L 70L) 10 9Totstd= 55669 4003 5-level 184 (151) 3

64RESULTS Mean = 2102106 gkg

Repeatability variance S2r = 117627Repeatability std Sr = 108456 --gt 516 r = 30368Between lab variance S2L = 176699Reproducibility var S2R = 294326Reproducibility std SR = 171559 --gt 816 R = 48037Remarks 3 Labs rejected (36L44L 70L)

000 050 100 150 200 250 300 350

k-values

44L

65L

45L

35L

32L

16L

9L

56L

19L

34L

36L

66L

70L

Mandels k statistics(Soil 5 - TOC)

-500 00 500 1000 1500 2000 2500

Deviation from Mean

44L

65L

45L

35L

32L

16L

9L

56L

19L

34L

36L

66L

70L

Labo

rato

ries

Soil 5 - TOC -- Mean PARM = 2102 [gkg]

-100 000 100 200 300 400

h-values

44L

65L

45L

35L

32L

16L

9L

56L

19L

34L

36L

66L

70L

Labo

rato

ries

Mandels h statistics(Soil 5 - TOC)

Soil 5-TOC

17

Annex 4

Raw data submitted

Sample Compost 1 Sample Compost 2 Sample Sewage Sludge 1Element TOC [gkg] Element TOC [gkg] Element TOC [gkg]

LAB PARM LAB PARM LAB PARM30L 2600 19L 1691 19L 286730L 2580 19L 1634 19L 281430L 2560 19L 1619 19L 276934L 2969 19L 1604 19L 272034L 2936 19L 1499 19L 268834L 2958 19L 1414 19L 266234L 2994 34L 1527 34L 315234L 3199 34L 1622 34L 314934L 3024 34L 1519 34L 343035L 2306 34L 1753 34L 336535L 2300 34L 1636 34L 304235L 2298 34L 1874 34L 298335L 2296 35L 1506 35L 270735L 2291 35L 1312 35L 270335L 2259 35L 1294 35L 268836L 2546 35L 1279 35L 267436L 2527 35L 1191 35L 263136L 2470 35L 1177 35L 262644L 2583 36L 1418 36L 271344L 2581 36L 1408 36L 266544L 2578 36L 1320 36L 261444L 2539 44L 1719 44L 292044L 2528 44L 1664 44L 291644L 2525 44L 1654 44L 291245L 2658 44L 1637 44L 290045L 2600 44L 1624 44L 289645L 2546 44L 1620 44L 289345L 2461 45L 1428 45L 297645L 2409 45L 1325 45L 295245L 2350 45L 1323 45L 288546L 2460 45L 1321 45L 286646L 2400 45L 1309 45L 284046L 2370 45L 1253 45L 278746L 2350 46L 1580 46L 233056L 2436 46L 1550 46L 233056L 2435 46L 1170 46L 230056L 2405 46L 1120 46L 229056L 2397 56L 1642 56L 270256L 2375 56L 1626 56L 270156L 2358 56L 1622 56L 269465L 2587 56L 1571 56L 269365L 2542 56L 1561 56L 268465L 2483 56L 1545 56L 268066L 2454 65L 1933 65L 264166L 2429 65L 1838 65L 260966L 2365 65L 1693 65L 260766L 2262 65L 1562 65L 260569L 2730 66L 1561 66L 270169L 2250 66L 1545 66L 267469L 1440 66L 1420 66L 261969L 1420 66L 1417 66L 251470L 2435 69L 2700 69L 2639L 2594 69L 2660 69L 2409L 2570 69L 2170 69L 2199L 2565 69L 2130 69L 2109L 2563 70L 1414 70L 28159L 2562 9L 1644 9L 28579L 2555 9L 1641 9L 2856

32L 2290 9L 1602 9L 285532L 2390 9L 1589 9L 285532L 2510 9L 1526 9L 285332L 2470 9L 1492 9L 284616L 2380 32L 1470 32L 265016L 2530 32L 1520 32L 271016L 2400 32L 1540 32L 271016L 2500 32L 1600 32L 280016L 2420 16L 1400 16L 284016L 2410 16L 1440 16L 2840

16L 1470 16L 286016L 1510 16L 287016L 1360 16L 287016L 1390 16L 2880

Sample Sewage Sludge 2 Sample Soil 4 Sample Soil 5Element TOC [gkg] Element TOC [gkg] Element TOC [gkg]

LAB PARM LAB PARM LAB PARM19L 2308 19L 1720 19L 225019L 2303 19L 1700 19L 223019L 2239 19L 1690 19L 221019L 2204 19L 1670 19L 211019L 2192 19L 1640 19L 210019L 2096 19L 1580 19L 206034L 2631 30L 1790 34L 244334L 2471 30L 1770 34L 233434L 2977 30L 1700 34L 231534L 2785 34L 1740 34L 222134L 2780 34L 1692 34L 217634L 2668 34L 1727 34L 207335L 2179 34L 1767 35L 233035L 2160 34L 1777 35L 208035L 2158 34L 1783 35L 201035L 2132 35L 1700 35L 198035L 2119 35L 1650 35L 193035L 2094 35L 1650 35L 178036L 2096 35L 1640 36L 254036L 2069 35L 1630 36L 253436L 2052 35L 1630 36L 179044L 2325 36L 1500 44L 302144L 2309 36L 1497 44L 298244L 2307 36L 1417 44L 295644L 2305 44L 1594 44L 30744L 2287 44L 1587 44L 30044L 2283 44L 1584 44L 29745L 2331 44L 1574 45L 214945L 2327 44L 1573 45L 209245L 2308 44L 1562 45L 203345L 2287 45L 1827 45L 197145L 2234 45L 1709 45L 193345L 2113 45L 1666 45L 184146L 190 45L 1665 56L 223746L 180 45L 1664 56L 222246L 180 45L 1600 56L 220346L 180 46L 2300 56L 206956L 2204 46L 2300 56L 206856L 2197 46L 2300 56L 204456L 2193 46L 2200 65L 192056L 2185 56L 1668 65L 182056L 2183 56L 1654 65L 179056L 2167 56L 1653 65L 172065L 2136 56L 1643 66L 254365L 2091 56L 1639 66L 242465L 2065 56L 1638 66L 232165L 2047 65L 1630 66L 226266L 2105 65L 1560 70L 2213966L 2022 65L 1530 9L 218066L 2009 65L 1490 9L 214066L 1983 66L 2179 9L 213070L 2272 66L 1900 9L 21109L 2385 66L 1762 9L 20709L 2377 66L 1734 9L 20709L 2375 70L 10404 32L 20509L 2359 9L 1640 32L 21009L 2356 9L 1640 32L 20209L 2354 9L 1610 32L 1960

32L 2240 9L 1590 16L 210032L 2260 9L 1590 16L 220032L 2200 9L 1560 16L 220032L 2270 32L 1640 16L 206016L 2300 32L 1600 16L 197016L 2310 32L 1560 16L 201016L 2350 32L 157016L 2260 16L 170016L 2290 16L 180016L 2240 16L 1700

16L 180016L 170016L 1700

European Commission EUR 23012 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on total organic carbon Author(s) E Sobiecka H van der Sloot K Andersen B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 50 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07412-7 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 total organic carbon (TOC) in soils sludge and treated bio-waste 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

-23012-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 exercises For each parameter investigated at least 10 laboratories should be nominated to participate The same laboratories should analyse different parameters as far as possible Due to the complexity of analysis and the respective workload of the laboratories it was decided to propose six materials for the validation of the TOC draft standard Each laboratory received two bottles of each material and was requested to perform 6 independent analyses per material1 (3 per bottle) using the draft standard method The 6 analyses 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 was permitted but had to be reported Likewise the different materials could 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 had 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 was set and should 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 The draft standard was made available to the laboratories on the Project Horizontal homepage Each laboratory was requested to provide the signed statements on cooperation as given in Annex 1

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 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

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

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 TOC

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

bull Compost 1 A compost material from Vienna bull Compost 2 A compost material from Germany bull Sewage Sludge 1 A mixed sewage sludge from Essen Germany bull Sewage Sludge 2 A mixed municipal sludge from North Rhine Westphalia

Germany bull Soil 4 A sludge amended soil from Hohenheim Germany bull Soil 5 An agricultural soil from Reading UK

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

122 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 httpwwwecnnldocssocietyhorizontalTOC_standard_for_validationpdf

123 Analytical program Two bottles had to be analysed for each of the six materials and each bottle had to be analysed independently three times 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 dry matter correction was free for each participant

124 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

9

submission of results has been set for TOC to the 31st of January 2007 Alternatively the participants were allowed to submit data electronically as Excel sheet using Email All data were treated in a confidential way Any presentation hereafter refers 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 provided a 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

125 Participants The following table lists the participating organizations and entities in the validation exercise for the horizontal TOC standard

bull Austria o barbara - Engineering Consulting Research amp Service GmbH o Federal Research and Training Centre for Forests Natural Hazards and

Landscape o NUA Umweltanalytik GmbH o Oumlsterreichische Agentur fuumlr Gesundheit und Ernaumlhrungssicherheit o Universitaumlt fuumlr Bodenkultur Wien o Shimadzu Europa GmbH o Umweltbundesamt o University of Natural resources and Applied Life Sciences

bull Belgium o VITO

bull France o INERIS o CEMAGREF - UR QELY o INRA - Laboratoire dAnalyse des Sols

bull Germany o ALBO-tec Technologiezentrum Fuumlr Analytik und Bodenmechanik GmbH

bull Norway o Norwegian Institute for Water Research

bull The Netherlands o ALCONTROL BV o Analytico Milieu B V

11

13 Summary results and derived performance characteristics The result of the various statistical evaluation according to ISO 5725-2 including outlier tests calculation of repeatability and reproducibility standard deviations can be found in Annex 3 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 The calculated average values the repeatability standard deviation (sr) and the reproducibility standard deviation (sR) are given in Table 1 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 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 total organic carbon (TOC) by dry combustion in treated biowaste sludge and soil All concentrations are expressed in gkg dry matter

Matrix Parameter Mean sr sR r R p Outliers Total number of data

No of

LOD

Sludge 1 TOC 272 17 59 13 45 13 2 62 0 Sludge 2 TOC 220 21 50 13 31 12 2 58 0

Compost 1 TOC 246 25 43 17 30 13 2 58 0 Compost 2 TOC 154 59 96 25 41 13 2 64 0

Soil 4 TOC 164 26 52 12 24 12 3 62 0 Soil 5 TOC 210 52 82 30 48 10 3 54 0

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

13

14 Annexes Annex 1 Model questionnaire to be filled by the participating laboratories Annex 2 Report on the validation materials used Annex 3 Statistical calculations Annex 4 Data submitted

14

14

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

15

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

16

Annex 3

Statistical calculations

Unit gkg

Mandels k statistics(Compost 1 - TOC)Mandels h statistics(Compost 1 - TOC)

Sample Compost 1 Compost 1 - TOC -- Mean PARM = 2463 [gkg]

Element TOC

General calcparmT1= 142643E+04T2= 351264E+06T3= 58T4= 292T5= 16501E+03

n= variabelp= 13

N-table= 5

Mandels statistics End ResultLAB 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

69L 1960000 64265 4 -235 352 Fail - - 69L - - -502735L 2291667 1674 6 -081 009 2291667 16741 6 5 -171066L 2377425 8552 4 -041 047 2377425 85518 4 3 -85346L 2395000 4796 4 -033 026 2395000 47958 4 3 -67756L 2401227 3133 6 -030 017 2401227 31330 6 5 -61432L 2415000 9713 4 -024 053 2415000 97125 4 3 -47770L 2435100 - 1 -014 2435100 - 1 -27616L 2440000 6033 6 -012 033 2440000 60332 6 5 -22745L 2503800 11759 6 018 064 2503800 117589 6 5 41136L 2514416 3994 3 023 022 2514416 39937 3 2 51765L 2537333 5216 3 033 029 2537333 52157 3 2 74744L 2555667 2783 6 042 015 2555667 27826 6 5 9309L 2568167 1356 6 048 007 2568167 13556 6 5 105530L 2580000 2000 3 053 011 2580000 20000 3 2 117334L 3013269 9580 6 255 053 Fail - - 34L - - 5506

Totgem 246587 9632 gkg 1-level 232 (176) 13 2462677 (34L 69L) 13 12Totstd= 21507 16070 5-level 186 (152) 2

68RESULTS Mean = 24626770 gkg

Repeatability variance S2r = 3666797Repeatability std Sr = 605541 --gt 246 r = 169551Between lab variance S2L = 7715586Reproducibility var S2R = 11382383Reproducibility std SR = 1066882 --gt 433 R = 298727Remarks 2 Labs rejected (34L 69L)

000 050 100 150 200 250 300 350 400

k-values

69L

35L

66L

46L

56L

32L

70L

16L

45L

36L

65L

44L

9L

30L

34L

Mandels k statistics(Compost 1 - TOC)

-600 -400 -200 00 200 400 600

Deviation from Mean

69L

35L

66L

46L

56L

32L

70L

16L

45L

36L

65L

44L

9L

30L

34L

Labo

rato

ries

Compost 1 - TOC -- Mean PARM = 2463 [gkg]

-300 -200 -100 000 100 200 300

h-values

69L

66L

56L

70L

45L

65L

9L

34L

Labo

rato

ries

Mandels h statistics(Compost 1 - TOC)

Compost 1-TOC

Unit gkg

Mandels k statistics(Compost 2 - TOC)Mandels h statistics(Compost 2 - TOC)

Sample Compost 2 Compost 2 - TOC -- Mean PARM = 1542 [gkg]

Element TOC

General calcparmT1= 994897E+03T2= 155556E+06T3= 64T4= 346T5= 41738E+03

n= variabelp= 13

N-table= 5

Mandels statistics End ResultLAB 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

45L 1326733 5665 6 -100 042 Fail 1326733 56646 6 5 -215046L 1355000 24365 4 -089 181 Fail - - 46L - - -186736L 1381949 5407 3 -078 040 Fail 1381949 54070 3 2 -159870L 1414120 - 1 -066 Fail 1414120 - 1 -127616L 1428333 5565 6 -061 041 1428333 55648 6 5 -113466L 1485550 7805 4 -039 058 1485550 78047 4 3 -56232L 1532500 5377 4 -021 040 1532500 53774 4 3 -09219L 1576833 10138 6 -004 075 1576833 101381 6 5 3519L 1582333 6166 6 -002 046 1582333 61659 6 5 40656L 1594432 4046 6 003 030 1594432 40463 6 5 52744L 1653000 3651 6 025 027 1653000 36508 6 5 111334L 1655127 13717 6 026 102 1655127 137168 6 5 113434L 1655127 13717 6 026 102 1655127 137168 6 5 113465L 1756500 16295 4 065 121 Fail 1756500 162949 4 3 214869L 2415000 30687 4 316 228 Fail - - 69L - - 8733

Totgem 158750 10900 gkg 1-level 232 (176) 13 1541734 (46L 69L) 13 12Totstd= 26187 8164 5-level 186 (152) 2

72RESULTS Mean = 15417337 gkg

Repeatability variance S2r = 8183950Repeatability std Sr = 904652 --gt 587 r = 253303Between lab variance S2L = 13631046Reproducibility var S2R = 21814995Reproducibility std SR = 1476990 --gt 958 R = 413557Remarks 2 Labs rejected (46L 69L)

000 050 100 150 200 250

k-values

45L

46L

36L

70L

16L

66L

32L

19L

9L

56L

44L

34L

34L

65L

69L

Mandels k statistics(Compost 2 - TOC)

-400 -200 00 200 400 600 800 1000

Deviation from Mean

45L

46L

36L

70L

16L

66L

32L

19L

9L

56L

44L

34L

34L

65L

69L

Labo

rato

ries

Compost 2 - TOC -- Mean PARM = 1542 [gkg]

-100 000 100 200 300 400

h-values

45L

36L

16L

32L

9L

44L

34L

69L

Labo

rato

ries

Mandels h statistics(Compost 2 - TOC)

Compost 2-TOC

Unit gkg

Mandels k statistics(Sludge 1 - TOC)Mandels h statistics(Sludge 1 - TOC)

Sample Sludge 1 Sludge 1 - TOC -- Mean PARM = 2721 [gkg]

Element TOC

General calcparmT1= 169626E+04T2= 465445E+06T3= 62T4= 326T5= 10312E+03

n= variabelp= 13

N-table= 5

Mandels statistics End ResultLAB 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

69L 233000 2362 4 -347 037 Fail - - 69L - - -2488046L 2312500 2062 4 -040 032 Fail 2312500 20616 4 3 -408565L 2615500 1708 4 004 026 2615500 17078 4 3 -105566L 2627200 8268 4 006 128 2627200 82678 4 3 -93836L 2664041 4976 3 011 077 2664041 49758 3 2 -56935L 2671500 3533 6 013 055 2671500 35331 6 5 -49556L 2692298 0874 6 016 014 Fail 2692298 08738 6 5 -28732L 2717500 6185 4 019 096 Fail 2717500 61847 4 3 -03519L 2753333 7819 6 025 121 Fail 2753333 78189 6 5 32470L 2814600 - 1 034 Fail 2814600 - 1 9369L 2853667 0398 6 039 006 Fail 2853667 03983 6 5 132716L 2860000 1673 6 040 026 Fail 2860000 16733 6 5 139045L 2884433 7033 6 044 109 Fail 2884433 70331 6 5 163544L 2906167 1129 6 047 017 Fail 2906167 11286 6 5 185234L 3186874 17674 6 089 274 Fail - - 34L - - 4659

Totgem 258617 4692 gkg 1-level 232 (176) 13 2720980 (34L 69L) 13 12Totstd= 67800 4610 5-level 186 (152) 2

72RESULTS Mean = 27209799 gkg

Repeatability variance S2r = 2104538Repeatability std Sr = 458752 --gt 169 r = 128451Between lab variance S2L = 23618387Reproducibility var S2R = 25722925Reproducibility std SR = 1603837 --gt 589 R = 449074Remarks 2 Labs rejected (34L 69L)

000 050 100 150 200 250 300

k-values

69L

46L

65L

66L

36L

35L

56L

32L

19L

70L

9L

16L

45L

44L

34L

Mandels k statistics(Sludge 1 - TOC)

-2500 -2000 -1500 -1000 -500 00 500

Deviation from Mean

69L

46L

65L

66L

36L

35L

56L

32L

19L

70L

9L

16L

45L

44L

34L

Labo

rato

ries

Sludge 1 - TOC -- Mean PARM = 2721 [gkg]

-400 -300 -200 -100 000 100

h-values

69L

65L

36L

56L

19L

9L

45L

34L

Labo

rato

ries

Mandels h statistics(Sludge 1 - TOC)

Sludge 1-TOC

68 Unit gkg

Mandels k statistics(Sludge 2 - TOC)Mandels h statistics(Sludge 2 - TOC)

Sample Sludge 2 Sludge 2 - TOC -- Mean PARM = 2207 [gkg]

Element TOC

General calcparmT1= 128601E+04T2= 285689E+06T3= 58T4= 310T5= 97826E+02

n= variabelp= 12

N-table= 5

Mandels statistics End ResultLAB 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

46L 182500 0500 4 -333 008 Fail - - 46L - - -2024466L 2029475 5267 4 -012 084 2029475 52674 4 3 -177436L 2072609 2222 3 -005 035 2072609 22222 3 2 -134365L 2084750 3865 4 -002 062 2084750 38647 4 3 -122135L 2140333 3119 6 007 050 2140333 31194 6 5 -66556L 2188021 1282 6 015 020 2188021 12822 6 5 -18819L 2223667 7916 6 022 126 Fail 2223667 79157 6 5 16832L 2242500 3096 4 025 049 Fail 2242500 30957 4 3 35645L 2266600 8322 6 029 132 Fail 2266600 83216 6 5 59770L 2272460 - 1 030 Fail 2272460 - 1 65616L 2291667 3869 6 033 062 Fail 2291667 38687 6 5 84844L 2302667 1546 6 035 025 Fail 2302667 15462 6 5 9589L 2367667 1296 6 047 021 Fail 2367667 12956 6 5 160834L 2718591 17124 6 108 273 Fail - - 34L - - 5117

Totgem 209882 4571 gkg 1-level 230 (176) 12 2206868 (34L 46L) 12 11Totstd= 57628 4485 5-level 185 (151) 2

68RESULTS Mean = 22068679 gkg

Repeatability variance S2r = 2126659Repeatability std Sr = 461157 --gt 209 r = 129124Between lab variance S2L = 9960432Reproducibility var S2R = 12087091Reproducibility std SR = 1099413 --gt 498 R = 307836Remarks 2 Labs rejected (34L 46L)

000 050 100 150 200 250 300

k-values

46L

66L

36L

65L

35L

56L

19L

32L

45L

70L

16L

44L

9L

34L

Mandels k statistics(Sludge 2 - TOC)

-2500 -2000 -1500 -1000 -500 00 500 1000

Deviation from Mean

46L

66L

36L

65L

35L

56L

19L

32L

45L

70L

16L

44L

9L

34L

Labo

rato

ries

Sludge 2 - TOC -- Mean PARM = 2207 [gkg]

-400 -300 -200 -100 000 100 200

h-values

46L

66L

36L

65L

35L

56L

19L

32L

45L

70L

16L

44L

9L

34L

Labo

rato

ries

Mandels h statistics(Sludge 2 - TOC)

Sludge 2-TOC

Unit gkg

Mandels k statistics(Soil 4 - TOC)Mandels h statistics(Soil 4 - TOC)

Sample Soil 4 Soil 4 - TOC -- Mean PARM = 1641 [gkg]

Element TOC

General calcparmT1= 102171E+03T2= 168700E+04T3= 62T4= 338T5= 94040E+00

n= variabelp= 12

N-table= 5

Mandels statistics End ResultLAB 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

36L 147161 0470 3 -036 068 Fail 147161 04702 3 2 -16965L 155250 0591 4 -032 085 Fail 155250 05909 4 3 -08844L 157900 0115 6 -031 017 Fail 157900 01152 6 5 -06232L 159250 0359 4 -031 052 Fail 159250 03594 4 3 -0489L 160500 0315 6 -030 045 Fail 160500 03146 6 5 -03656L 164927 0113 6 -028 016 Fail 164927 01127 6 5 00835L 165000 0261 6 -028 038 Fail 165000 02608 6 5 00919L 166667 0505 6 -027 073 Fail 166667 05046 6 5 02645L 168850 0763 6 -026 110 Fail 168850 07628 6 5 04816L 173333 0516 6 -024 074 Fail 173333 05164 6 5 09334L 174761 0346 6 -024 050 Fail 174761 03462 6 5 10730L 175333 0473 3 -024 068 Fail 175333 04726 3 2 11366L 189375 2035 4 -017 294 Fail - - 66L - - 25346L 227500 0500 4 000 072 - - 46L - - 63470L 1040400 - 1 360 Fail - - 70L - - 8763

Totgem 22841 0526 gkg 1-level 232 (176) 12 164078 (46L 66L70L) 12 11Totstd= 22541 0469 5-level 186 (152) 3

71RESULTS Mean = 1640777 gkg

Repeatability variance S2r = 018808Repeatability std Sr = 043368 --gt 264 r = 12143Between lab variance S2L = 054747Reproducibility var S2R = 073555Reproducibility std SR = 085764 --gt 523 R = 24014Remarks 3 Labs rejected (46L 66L70L)

000 050 100 150 200 250 300

k-values

36L

65L

44L

32L

9L

56L

35L

19L

45L

16L

34L

30L

66L

46L

70L

Mandels k statistics(Soil 4 - TOC)

-100 00 100 200 300 400 500 600 700 800 900

Deviation from Mean

36L

65L

44L

32L

9L

56L

35L

19L

45L

16L

34L

30L

66L

46L

70L

Labo

rato

ries

Soil 4 - TOC -- Mean PARM = 1641 [gkg]

-100 000 100 200 300 400

h-values

36L

44L

9L

35L

45L

34L

66L

70L

Labo

rato

ries

Mandels h statistics(Soil 4 - TOC)

Soil 4-TOC

Unit gkg

Mandels k statistics(Soil 5 - TOC)Mandels h statistics(Soil 5 - TOC)

Sample Soil 5 Soil 5 - TOC -- Mean PARM = 2102 [gkg]

Element TOC

General calcparmT1= 113661E+03T2= 240201E+04T3= 54T4= 300T5= 51756E+01

n= variabelp= 10

N-table= 5

Mandels statistics End ResultLAB 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

44L 164383 14708 6 -036 325 Fail - - 44L - - -45865L 181250 0830 4 -033 018 Fail 181250 08302 4 3 -29045L 200317 1116 6 -029 025 Fail 200317 11163 6 5 -09935L 201833 1828 6 -029 040 Fail 201833 18280 6 5 -08432L 203250 0585 4 -029 013 Fail 203250 05852 4 3 -07016L 209000 0959 6 -028 021 Fail 209000 09592 6 5 -0129L 211667 0427 6 -027 009 Fail 211667 04274 6 5 01556L 214030 0887 6 -027 020 Fail 214030 08868 6 5 03819L 216000 0795 6 -026 018 Fail 216000 07950 6 5 05834L 226009 1308 6 -024 029 Fail 226009 13076 6 5 15836L 228783 4310 3 -024 095 Fail - - 36L - - 18666L 238750 1234 4 -022 027 Fail 238750 12340 4 3 28570L 2213900 - 1 333 Fail - - 70L - - 20037

Totgem 36224 2416 gkg 1-level 227 (175) 10 210211 (36L44L 70L) 10 9Totstd= 55669 4003 5-level 184 (151) 3

64RESULTS Mean = 2102106 gkg

Repeatability variance S2r = 117627Repeatability std Sr = 108456 --gt 516 r = 30368Between lab variance S2L = 176699Reproducibility var S2R = 294326Reproducibility std SR = 171559 --gt 816 R = 48037Remarks 3 Labs rejected (36L44L 70L)

000 050 100 150 200 250 300 350

k-values

44L

65L

45L

35L

32L

16L

9L

56L

19L

34L

36L

66L

70L

Mandels k statistics(Soil 5 - TOC)

-500 00 500 1000 1500 2000 2500

Deviation from Mean

44L

65L

45L

35L

32L

16L

9L

56L

19L

34L

36L

66L

70L

Labo

rato

ries

Soil 5 - TOC -- Mean PARM = 2102 [gkg]

-100 000 100 200 300 400

h-values

44L

65L

45L

35L

32L

16L

9L

56L

19L

34L

36L

66L

70L

Labo

rato

ries

Mandels h statistics(Soil 5 - TOC)

Soil 5-TOC

17

Annex 4

Raw data submitted

Sample Compost 1 Sample Compost 2 Sample Sewage Sludge 1Element TOC [gkg] Element TOC [gkg] Element TOC [gkg]

LAB PARM LAB PARM LAB PARM30L 2600 19L 1691 19L 286730L 2580 19L 1634 19L 281430L 2560 19L 1619 19L 276934L 2969 19L 1604 19L 272034L 2936 19L 1499 19L 268834L 2958 19L 1414 19L 266234L 2994 34L 1527 34L 315234L 3199 34L 1622 34L 314934L 3024 34L 1519 34L 343035L 2306 34L 1753 34L 336535L 2300 34L 1636 34L 304235L 2298 34L 1874 34L 298335L 2296 35L 1506 35L 270735L 2291 35L 1312 35L 270335L 2259 35L 1294 35L 268836L 2546 35L 1279 35L 267436L 2527 35L 1191 35L 263136L 2470 35L 1177 35L 262644L 2583 36L 1418 36L 271344L 2581 36L 1408 36L 266544L 2578 36L 1320 36L 261444L 2539 44L 1719 44L 292044L 2528 44L 1664 44L 291644L 2525 44L 1654 44L 291245L 2658 44L 1637 44L 290045L 2600 44L 1624 44L 289645L 2546 44L 1620 44L 289345L 2461 45L 1428 45L 297645L 2409 45L 1325 45L 295245L 2350 45L 1323 45L 288546L 2460 45L 1321 45L 286646L 2400 45L 1309 45L 284046L 2370 45L 1253 45L 278746L 2350 46L 1580 46L 233056L 2436 46L 1550 46L 233056L 2435 46L 1170 46L 230056L 2405 46L 1120 46L 229056L 2397 56L 1642 56L 270256L 2375 56L 1626 56L 270156L 2358 56L 1622 56L 269465L 2587 56L 1571 56L 269365L 2542 56L 1561 56L 268465L 2483 56L 1545 56L 268066L 2454 65L 1933 65L 264166L 2429 65L 1838 65L 260966L 2365 65L 1693 65L 260766L 2262 65L 1562 65L 260569L 2730 66L 1561 66L 270169L 2250 66L 1545 66L 267469L 1440 66L 1420 66L 261969L 1420 66L 1417 66L 251470L 2435 69L 2700 69L 2639L 2594 69L 2660 69L 2409L 2570 69L 2170 69L 2199L 2565 69L 2130 69L 2109L 2563 70L 1414 70L 28159L 2562 9L 1644 9L 28579L 2555 9L 1641 9L 2856

32L 2290 9L 1602 9L 285532L 2390 9L 1589 9L 285532L 2510 9L 1526 9L 285332L 2470 9L 1492 9L 284616L 2380 32L 1470 32L 265016L 2530 32L 1520 32L 271016L 2400 32L 1540 32L 271016L 2500 32L 1600 32L 280016L 2420 16L 1400 16L 284016L 2410 16L 1440 16L 2840

16L 1470 16L 286016L 1510 16L 287016L 1360 16L 287016L 1390 16L 2880

Sample Sewage Sludge 2 Sample Soil 4 Sample Soil 5Element TOC [gkg] Element TOC [gkg] Element TOC [gkg]

LAB PARM LAB PARM LAB PARM19L 2308 19L 1720 19L 225019L 2303 19L 1700 19L 223019L 2239 19L 1690 19L 221019L 2204 19L 1670 19L 211019L 2192 19L 1640 19L 210019L 2096 19L 1580 19L 206034L 2631 30L 1790 34L 244334L 2471 30L 1770 34L 233434L 2977 30L 1700 34L 231534L 2785 34L 1740 34L 222134L 2780 34L 1692 34L 217634L 2668 34L 1727 34L 207335L 2179 34L 1767 35L 233035L 2160 34L 1777 35L 208035L 2158 34L 1783 35L 201035L 2132 35L 1700 35L 198035L 2119 35L 1650 35L 193035L 2094 35L 1650 35L 178036L 2096 35L 1640 36L 254036L 2069 35L 1630 36L 253436L 2052 35L 1630 36L 179044L 2325 36L 1500 44L 302144L 2309 36L 1497 44L 298244L 2307 36L 1417 44L 295644L 2305 44L 1594 44L 30744L 2287 44L 1587 44L 30044L 2283 44L 1584 44L 29745L 2331 44L 1574 45L 214945L 2327 44L 1573 45L 209245L 2308 44L 1562 45L 203345L 2287 45L 1827 45L 197145L 2234 45L 1709 45L 193345L 2113 45L 1666 45L 184146L 190 45L 1665 56L 223746L 180 45L 1664 56L 222246L 180 45L 1600 56L 220346L 180 46L 2300 56L 206956L 2204 46L 2300 56L 206856L 2197 46L 2300 56L 204456L 2193 46L 2200 65L 192056L 2185 56L 1668 65L 182056L 2183 56L 1654 65L 179056L 2167 56L 1653 65L 172065L 2136 56L 1643 66L 254365L 2091 56L 1639 66L 242465L 2065 56L 1638 66L 232165L 2047 65L 1630 66L 226266L 2105 65L 1560 70L 2213966L 2022 65L 1530 9L 218066L 2009 65L 1490 9L 214066L 1983 66L 2179 9L 213070L 2272 66L 1900 9L 21109L 2385 66L 1762 9L 20709L 2377 66L 1734 9L 20709L 2375 70L 10404 32L 20509L 2359 9L 1640 32L 21009L 2356 9L 1640 32L 20209L 2354 9L 1610 32L 1960

32L 2240 9L 1590 16L 210032L 2260 9L 1590 16L 220032L 2200 9L 1560 16L 220032L 2270 32L 1640 16L 206016L 2300 32L 1600 16L 197016L 2310 32L 1560 16L 201016L 2350 32L 157016L 2260 16L 170016L 2290 16L 180016L 2240 16L 1700

16L 180016L 170016L 1700

European Commission EUR 23012 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on total organic carbon Author(s) E Sobiecka H van der Sloot K Andersen B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 50 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07412-7 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 total organic carbon (TOC) in soils sludge and treated bio-waste 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

-23012-EN

-C

8

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 TOC

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

bull Compost 1 A compost material from Vienna bull Compost 2 A compost material from Germany bull Sewage Sludge 1 A mixed sewage sludge from Essen Germany bull Sewage Sludge 2 A mixed municipal sludge from North Rhine Westphalia

Germany bull Soil 4 A sludge amended soil from Hohenheim Germany bull Soil 5 An agricultural soil from Reading UK

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

122 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 httpwwwecnnldocssocietyhorizontalTOC_standard_for_validationpdf

123 Analytical program Two bottles had to be analysed for each of the six materials and each bottle had to be analysed independently three times 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 dry matter correction was free for each participant

124 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

9

submission of results has been set for TOC to the 31st of January 2007 Alternatively the participants were allowed to submit data electronically as Excel sheet using Email All data were treated in a confidential way Any presentation hereafter refers 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 provided a 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

125 Participants The following table lists the participating organizations and entities in the validation exercise for the horizontal TOC standard

bull Austria o barbara - Engineering Consulting Research amp Service GmbH o Federal Research and Training Centre for Forests Natural Hazards and

Landscape o NUA Umweltanalytik GmbH o Oumlsterreichische Agentur fuumlr Gesundheit und Ernaumlhrungssicherheit o Universitaumlt fuumlr Bodenkultur Wien o Shimadzu Europa GmbH o Umweltbundesamt o University of Natural resources and Applied Life Sciences

bull Belgium o VITO

bull France o INERIS o CEMAGREF - UR QELY o INRA - Laboratoire dAnalyse des Sols

bull Germany o ALBO-tec Technologiezentrum Fuumlr Analytik und Bodenmechanik GmbH

bull Norway o Norwegian Institute for Water Research

bull The Netherlands o ALCONTROL BV o Analytico Milieu B V

11

13 Summary results and derived performance characteristics The result of the various statistical evaluation according to ISO 5725-2 including outlier tests calculation of repeatability and reproducibility standard deviations can be found in Annex 3 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 The calculated average values the repeatability standard deviation (sr) and the reproducibility standard deviation (sR) are given in Table 1 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 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 total organic carbon (TOC) by dry combustion in treated biowaste sludge and soil All concentrations are expressed in gkg dry matter

Matrix Parameter Mean sr sR r R p Outliers Total number of data

No of

LOD

Sludge 1 TOC 272 17 59 13 45 13 2 62 0 Sludge 2 TOC 220 21 50 13 31 12 2 58 0

Compost 1 TOC 246 25 43 17 30 13 2 58 0 Compost 2 TOC 154 59 96 25 41 13 2 64 0

Soil 4 TOC 164 26 52 12 24 12 3 62 0 Soil 5 TOC 210 52 82 30 48 10 3 54 0

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

13

14 Annexes Annex 1 Model questionnaire to be filled by the participating laboratories Annex 2 Report on the validation materials used Annex 3 Statistical calculations Annex 4 Data submitted

14

14

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

15

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

16

Annex 3

Statistical calculations

Unit gkg

Mandels k statistics(Compost 1 - TOC)Mandels h statistics(Compost 1 - TOC)

Sample Compost 1 Compost 1 - TOC -- Mean PARM = 2463 [gkg]

Element TOC

General calcparmT1= 142643E+04T2= 351264E+06T3= 58T4= 292T5= 16501E+03

n= variabelp= 13

N-table= 5

Mandels statistics End ResultLAB 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

69L 1960000 64265 4 -235 352 Fail - - 69L - - -502735L 2291667 1674 6 -081 009 2291667 16741 6 5 -171066L 2377425 8552 4 -041 047 2377425 85518 4 3 -85346L 2395000 4796 4 -033 026 2395000 47958 4 3 -67756L 2401227 3133 6 -030 017 2401227 31330 6 5 -61432L 2415000 9713 4 -024 053 2415000 97125 4 3 -47770L 2435100 - 1 -014 2435100 - 1 -27616L 2440000 6033 6 -012 033 2440000 60332 6 5 -22745L 2503800 11759 6 018 064 2503800 117589 6 5 41136L 2514416 3994 3 023 022 2514416 39937 3 2 51765L 2537333 5216 3 033 029 2537333 52157 3 2 74744L 2555667 2783 6 042 015 2555667 27826 6 5 9309L 2568167 1356 6 048 007 2568167 13556 6 5 105530L 2580000 2000 3 053 011 2580000 20000 3 2 117334L 3013269 9580 6 255 053 Fail - - 34L - - 5506

Totgem 246587 9632 gkg 1-level 232 (176) 13 2462677 (34L 69L) 13 12Totstd= 21507 16070 5-level 186 (152) 2

68RESULTS Mean = 24626770 gkg

Repeatability variance S2r = 3666797Repeatability std Sr = 605541 --gt 246 r = 169551Between lab variance S2L = 7715586Reproducibility var S2R = 11382383Reproducibility std SR = 1066882 --gt 433 R = 298727Remarks 2 Labs rejected (34L 69L)

000 050 100 150 200 250 300 350 400

k-values

69L

35L

66L

46L

56L

32L

70L

16L

45L

36L

65L

44L

9L

30L

34L

Mandels k statistics(Compost 1 - TOC)

-600 -400 -200 00 200 400 600

Deviation from Mean

69L

35L

66L

46L

56L

32L

70L

16L

45L

36L

65L

44L

9L

30L

34L

Labo

rato

ries

Compost 1 - TOC -- Mean PARM = 2463 [gkg]

-300 -200 -100 000 100 200 300

h-values

69L

66L

56L

70L

45L

65L

9L

34L

Labo

rato

ries

Mandels h statistics(Compost 1 - TOC)

Compost 1-TOC

Unit gkg

Mandels k statistics(Compost 2 - TOC)Mandels h statistics(Compost 2 - TOC)

Sample Compost 2 Compost 2 - TOC -- Mean PARM = 1542 [gkg]

Element TOC

General calcparmT1= 994897E+03T2= 155556E+06T3= 64T4= 346T5= 41738E+03

n= variabelp= 13

N-table= 5

Mandels statistics End ResultLAB 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

45L 1326733 5665 6 -100 042 Fail 1326733 56646 6 5 -215046L 1355000 24365 4 -089 181 Fail - - 46L - - -186736L 1381949 5407 3 -078 040 Fail 1381949 54070 3 2 -159870L 1414120 - 1 -066 Fail 1414120 - 1 -127616L 1428333 5565 6 -061 041 1428333 55648 6 5 -113466L 1485550 7805 4 -039 058 1485550 78047 4 3 -56232L 1532500 5377 4 -021 040 1532500 53774 4 3 -09219L 1576833 10138 6 -004 075 1576833 101381 6 5 3519L 1582333 6166 6 -002 046 1582333 61659 6 5 40656L 1594432 4046 6 003 030 1594432 40463 6 5 52744L 1653000 3651 6 025 027 1653000 36508 6 5 111334L 1655127 13717 6 026 102 1655127 137168 6 5 113434L 1655127 13717 6 026 102 1655127 137168 6 5 113465L 1756500 16295 4 065 121 Fail 1756500 162949 4 3 214869L 2415000 30687 4 316 228 Fail - - 69L - - 8733

Totgem 158750 10900 gkg 1-level 232 (176) 13 1541734 (46L 69L) 13 12Totstd= 26187 8164 5-level 186 (152) 2

72RESULTS Mean = 15417337 gkg

Repeatability variance S2r = 8183950Repeatability std Sr = 904652 --gt 587 r = 253303Between lab variance S2L = 13631046Reproducibility var S2R = 21814995Reproducibility std SR = 1476990 --gt 958 R = 413557Remarks 2 Labs rejected (46L 69L)

000 050 100 150 200 250

k-values

45L

46L

36L

70L

16L

66L

32L

19L

9L

56L

44L

34L

34L

65L

69L

Mandels k statistics(Compost 2 - TOC)

-400 -200 00 200 400 600 800 1000

Deviation from Mean

45L

46L

36L

70L

16L

66L

32L

19L

9L

56L

44L

34L

34L

65L

69L

Labo

rato

ries

Compost 2 - TOC -- Mean PARM = 1542 [gkg]

-100 000 100 200 300 400

h-values

45L

36L

16L

32L

9L

44L

34L

69L

Labo

rato

ries

Mandels h statistics(Compost 2 - TOC)

Compost 2-TOC

Unit gkg

Mandels k statistics(Sludge 1 - TOC)Mandels h statistics(Sludge 1 - TOC)

Sample Sludge 1 Sludge 1 - TOC -- Mean PARM = 2721 [gkg]

Element TOC

General calcparmT1= 169626E+04T2= 465445E+06T3= 62T4= 326T5= 10312E+03

n= variabelp= 13

N-table= 5

Mandels statistics End ResultLAB 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

69L 233000 2362 4 -347 037 Fail - - 69L - - -2488046L 2312500 2062 4 -040 032 Fail 2312500 20616 4 3 -408565L 2615500 1708 4 004 026 2615500 17078 4 3 -105566L 2627200 8268 4 006 128 2627200 82678 4 3 -93836L 2664041 4976 3 011 077 2664041 49758 3 2 -56935L 2671500 3533 6 013 055 2671500 35331 6 5 -49556L 2692298 0874 6 016 014 Fail 2692298 08738 6 5 -28732L 2717500 6185 4 019 096 Fail 2717500 61847 4 3 -03519L 2753333 7819 6 025 121 Fail 2753333 78189 6 5 32470L 2814600 - 1 034 Fail 2814600 - 1 9369L 2853667 0398 6 039 006 Fail 2853667 03983 6 5 132716L 2860000 1673 6 040 026 Fail 2860000 16733 6 5 139045L 2884433 7033 6 044 109 Fail 2884433 70331 6 5 163544L 2906167 1129 6 047 017 Fail 2906167 11286 6 5 185234L 3186874 17674 6 089 274 Fail - - 34L - - 4659

Totgem 258617 4692 gkg 1-level 232 (176) 13 2720980 (34L 69L) 13 12Totstd= 67800 4610 5-level 186 (152) 2

72RESULTS Mean = 27209799 gkg

Repeatability variance S2r = 2104538Repeatability std Sr = 458752 --gt 169 r = 128451Between lab variance S2L = 23618387Reproducibility var S2R = 25722925Reproducibility std SR = 1603837 --gt 589 R = 449074Remarks 2 Labs rejected (34L 69L)

000 050 100 150 200 250 300

k-values

69L

46L

65L

66L

36L

35L

56L

32L

19L

70L

9L

16L

45L

44L

34L

Mandels k statistics(Sludge 1 - TOC)

-2500 -2000 -1500 -1000 -500 00 500

Deviation from Mean

69L

46L

65L

66L

36L

35L

56L

32L

19L

70L

9L

16L

45L

44L

34L

Labo

rato

ries

Sludge 1 - TOC -- Mean PARM = 2721 [gkg]

-400 -300 -200 -100 000 100

h-values

69L

65L

36L

56L

19L

9L

45L

34L

Labo

rato

ries

Mandels h statistics(Sludge 1 - TOC)

Sludge 1-TOC

68 Unit gkg

Mandels k statistics(Sludge 2 - TOC)Mandels h statistics(Sludge 2 - TOC)

Sample Sludge 2 Sludge 2 - TOC -- Mean PARM = 2207 [gkg]

Element TOC

General calcparmT1= 128601E+04T2= 285689E+06T3= 58T4= 310T5= 97826E+02

n= variabelp= 12

N-table= 5

Mandels statistics End ResultLAB 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

46L 182500 0500 4 -333 008 Fail - - 46L - - -2024466L 2029475 5267 4 -012 084 2029475 52674 4 3 -177436L 2072609 2222 3 -005 035 2072609 22222 3 2 -134365L 2084750 3865 4 -002 062 2084750 38647 4 3 -122135L 2140333 3119 6 007 050 2140333 31194 6 5 -66556L 2188021 1282 6 015 020 2188021 12822 6 5 -18819L 2223667 7916 6 022 126 Fail 2223667 79157 6 5 16832L 2242500 3096 4 025 049 Fail 2242500 30957 4 3 35645L 2266600 8322 6 029 132 Fail 2266600 83216 6 5 59770L 2272460 - 1 030 Fail 2272460 - 1 65616L 2291667 3869 6 033 062 Fail 2291667 38687 6 5 84844L 2302667 1546 6 035 025 Fail 2302667 15462 6 5 9589L 2367667 1296 6 047 021 Fail 2367667 12956 6 5 160834L 2718591 17124 6 108 273 Fail - - 34L - - 5117

Totgem 209882 4571 gkg 1-level 230 (176) 12 2206868 (34L 46L) 12 11Totstd= 57628 4485 5-level 185 (151) 2

68RESULTS Mean = 22068679 gkg

Repeatability variance S2r = 2126659Repeatability std Sr = 461157 --gt 209 r = 129124Between lab variance S2L = 9960432Reproducibility var S2R = 12087091Reproducibility std SR = 1099413 --gt 498 R = 307836Remarks 2 Labs rejected (34L 46L)

000 050 100 150 200 250 300

k-values

46L

66L

36L

65L

35L

56L

19L

32L

45L

70L

16L

44L

9L

34L

Mandels k statistics(Sludge 2 - TOC)

-2500 -2000 -1500 -1000 -500 00 500 1000

Deviation from Mean

46L

66L

36L

65L

35L

56L

19L

32L

45L

70L

16L

44L

9L

34L

Labo

rato

ries

Sludge 2 - TOC -- Mean PARM = 2207 [gkg]

-400 -300 -200 -100 000 100 200

h-values

46L

66L

36L

65L

35L

56L

19L

32L

45L

70L

16L

44L

9L

34L

Labo

rato

ries

Mandels h statistics(Sludge 2 - TOC)

Sludge 2-TOC

Unit gkg

Mandels k statistics(Soil 4 - TOC)Mandels h statistics(Soil 4 - TOC)

Sample Soil 4 Soil 4 - TOC -- Mean PARM = 1641 [gkg]

Element TOC

General calcparmT1= 102171E+03T2= 168700E+04T3= 62T4= 338T5= 94040E+00

n= variabelp= 12

N-table= 5

Mandels statistics End ResultLAB 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

36L 147161 0470 3 -036 068 Fail 147161 04702 3 2 -16965L 155250 0591 4 -032 085 Fail 155250 05909 4 3 -08844L 157900 0115 6 -031 017 Fail 157900 01152 6 5 -06232L 159250 0359 4 -031 052 Fail 159250 03594 4 3 -0489L 160500 0315 6 -030 045 Fail 160500 03146 6 5 -03656L 164927 0113 6 -028 016 Fail 164927 01127 6 5 00835L 165000 0261 6 -028 038 Fail 165000 02608 6 5 00919L 166667 0505 6 -027 073 Fail 166667 05046 6 5 02645L 168850 0763 6 -026 110 Fail 168850 07628 6 5 04816L 173333 0516 6 -024 074 Fail 173333 05164 6 5 09334L 174761 0346 6 -024 050 Fail 174761 03462 6 5 10730L 175333 0473 3 -024 068 Fail 175333 04726 3 2 11366L 189375 2035 4 -017 294 Fail - - 66L - - 25346L 227500 0500 4 000 072 - - 46L - - 63470L 1040400 - 1 360 Fail - - 70L - - 8763

Totgem 22841 0526 gkg 1-level 232 (176) 12 164078 (46L 66L70L) 12 11Totstd= 22541 0469 5-level 186 (152) 3

71RESULTS Mean = 1640777 gkg

Repeatability variance S2r = 018808Repeatability std Sr = 043368 --gt 264 r = 12143Between lab variance S2L = 054747Reproducibility var S2R = 073555Reproducibility std SR = 085764 --gt 523 R = 24014Remarks 3 Labs rejected (46L 66L70L)

000 050 100 150 200 250 300

k-values

36L

65L

44L

32L

9L

56L

35L

19L

45L

16L

34L

30L

66L

46L

70L

Mandels k statistics(Soil 4 - TOC)

-100 00 100 200 300 400 500 600 700 800 900

Deviation from Mean

36L

65L

44L

32L

9L

56L

35L

19L

45L

16L

34L

30L

66L

46L

70L

Labo

rato

ries

Soil 4 - TOC -- Mean PARM = 1641 [gkg]

-100 000 100 200 300 400

h-values

36L

44L

9L

35L

45L

34L

66L

70L

Labo

rato

ries

Mandels h statistics(Soil 4 - TOC)

Soil 4-TOC

Unit gkg

Mandels k statistics(Soil 5 - TOC)Mandels h statistics(Soil 5 - TOC)

Sample Soil 5 Soil 5 - TOC -- Mean PARM = 2102 [gkg]

Element TOC

General calcparmT1= 113661E+03T2= 240201E+04T3= 54T4= 300T5= 51756E+01

n= variabelp= 10

N-table= 5

Mandels statistics End ResultLAB 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

44L 164383 14708 6 -036 325 Fail - - 44L - - -45865L 181250 0830 4 -033 018 Fail 181250 08302 4 3 -29045L 200317 1116 6 -029 025 Fail 200317 11163 6 5 -09935L 201833 1828 6 -029 040 Fail 201833 18280 6 5 -08432L 203250 0585 4 -029 013 Fail 203250 05852 4 3 -07016L 209000 0959 6 -028 021 Fail 209000 09592 6 5 -0129L 211667 0427 6 -027 009 Fail 211667 04274 6 5 01556L 214030 0887 6 -027 020 Fail 214030 08868 6 5 03819L 216000 0795 6 -026 018 Fail 216000 07950 6 5 05834L 226009 1308 6 -024 029 Fail 226009 13076 6 5 15836L 228783 4310 3 -024 095 Fail - - 36L - - 18666L 238750 1234 4 -022 027 Fail 238750 12340 4 3 28570L 2213900 - 1 333 Fail - - 70L - - 20037

Totgem 36224 2416 gkg 1-level 227 (175) 10 210211 (36L44L 70L) 10 9Totstd= 55669 4003 5-level 184 (151) 3

64RESULTS Mean = 2102106 gkg

Repeatability variance S2r = 117627Repeatability std Sr = 108456 --gt 516 r = 30368Between lab variance S2L = 176699Reproducibility var S2R = 294326Reproducibility std SR = 171559 --gt 816 R = 48037Remarks 3 Labs rejected (36L44L 70L)

000 050 100 150 200 250 300 350

k-values

44L

65L

45L

35L

32L

16L

9L

56L

19L

34L

36L

66L

70L

Mandels k statistics(Soil 5 - TOC)

-500 00 500 1000 1500 2000 2500

Deviation from Mean

44L

65L

45L

35L

32L

16L

9L

56L

19L

34L

36L

66L

70L

Labo

rato

ries

Soil 5 - TOC -- Mean PARM = 2102 [gkg]

-100 000 100 200 300 400

h-values

44L

65L

45L

35L

32L

16L

9L

56L

19L

34L

36L

66L

70L

Labo

rato

ries

Mandels h statistics(Soil 5 - TOC)

Soil 5-TOC

17

Annex 4

Raw data submitted

Sample Compost 1 Sample Compost 2 Sample Sewage Sludge 1Element TOC [gkg] Element TOC [gkg] Element TOC [gkg]

LAB PARM LAB PARM LAB PARM30L 2600 19L 1691 19L 286730L 2580 19L 1634 19L 281430L 2560 19L 1619 19L 276934L 2969 19L 1604 19L 272034L 2936 19L 1499 19L 268834L 2958 19L 1414 19L 266234L 2994 34L 1527 34L 315234L 3199 34L 1622 34L 314934L 3024 34L 1519 34L 343035L 2306 34L 1753 34L 336535L 2300 34L 1636 34L 304235L 2298 34L 1874 34L 298335L 2296 35L 1506 35L 270735L 2291 35L 1312 35L 270335L 2259 35L 1294 35L 268836L 2546 35L 1279 35L 267436L 2527 35L 1191 35L 263136L 2470 35L 1177 35L 262644L 2583 36L 1418 36L 271344L 2581 36L 1408 36L 266544L 2578 36L 1320 36L 261444L 2539 44L 1719 44L 292044L 2528 44L 1664 44L 291644L 2525 44L 1654 44L 291245L 2658 44L 1637 44L 290045L 2600 44L 1624 44L 289645L 2546 44L 1620 44L 289345L 2461 45L 1428 45L 297645L 2409 45L 1325 45L 295245L 2350 45L 1323 45L 288546L 2460 45L 1321 45L 286646L 2400 45L 1309 45L 284046L 2370 45L 1253 45L 278746L 2350 46L 1580 46L 233056L 2436 46L 1550 46L 233056L 2435 46L 1170 46L 230056L 2405 46L 1120 46L 229056L 2397 56L 1642 56L 270256L 2375 56L 1626 56L 270156L 2358 56L 1622 56L 269465L 2587 56L 1571 56L 269365L 2542 56L 1561 56L 268465L 2483 56L 1545 56L 268066L 2454 65L 1933 65L 264166L 2429 65L 1838 65L 260966L 2365 65L 1693 65L 260766L 2262 65L 1562 65L 260569L 2730 66L 1561 66L 270169L 2250 66L 1545 66L 267469L 1440 66L 1420 66L 261969L 1420 66L 1417 66L 251470L 2435 69L 2700 69L 2639L 2594 69L 2660 69L 2409L 2570 69L 2170 69L 2199L 2565 69L 2130 69L 2109L 2563 70L 1414 70L 28159L 2562 9L 1644 9L 28579L 2555 9L 1641 9L 2856

32L 2290 9L 1602 9L 285532L 2390 9L 1589 9L 285532L 2510 9L 1526 9L 285332L 2470 9L 1492 9L 284616L 2380 32L 1470 32L 265016L 2530 32L 1520 32L 271016L 2400 32L 1540 32L 271016L 2500 32L 1600 32L 280016L 2420 16L 1400 16L 284016L 2410 16L 1440 16L 2840

16L 1470 16L 286016L 1510 16L 287016L 1360 16L 287016L 1390 16L 2880

Sample Sewage Sludge 2 Sample Soil 4 Sample Soil 5Element TOC [gkg] Element TOC [gkg] Element TOC [gkg]

LAB PARM LAB PARM LAB PARM19L 2308 19L 1720 19L 225019L 2303 19L 1700 19L 223019L 2239 19L 1690 19L 221019L 2204 19L 1670 19L 211019L 2192 19L 1640 19L 210019L 2096 19L 1580 19L 206034L 2631 30L 1790 34L 244334L 2471 30L 1770 34L 233434L 2977 30L 1700 34L 231534L 2785 34L 1740 34L 222134L 2780 34L 1692 34L 217634L 2668 34L 1727 34L 207335L 2179 34L 1767 35L 233035L 2160 34L 1777 35L 208035L 2158 34L 1783 35L 201035L 2132 35L 1700 35L 198035L 2119 35L 1650 35L 193035L 2094 35L 1650 35L 178036L 2096 35L 1640 36L 254036L 2069 35L 1630 36L 253436L 2052 35L 1630 36L 179044L 2325 36L 1500 44L 302144L 2309 36L 1497 44L 298244L 2307 36L 1417 44L 295644L 2305 44L 1594 44L 30744L 2287 44L 1587 44L 30044L 2283 44L 1584 44L 29745L 2331 44L 1574 45L 214945L 2327 44L 1573 45L 209245L 2308 44L 1562 45L 203345L 2287 45L 1827 45L 197145L 2234 45L 1709 45L 193345L 2113 45L 1666 45L 184146L 190 45L 1665 56L 223746L 180 45L 1664 56L 222246L 180 45L 1600 56L 220346L 180 46L 2300 56L 206956L 2204 46L 2300 56L 206856L 2197 46L 2300 56L 204456L 2193 46L 2200 65L 192056L 2185 56L 1668 65L 182056L 2183 56L 1654 65L 179056L 2167 56L 1653 65L 172065L 2136 56L 1643 66L 254365L 2091 56L 1639 66L 242465L 2065 56L 1638 66L 232165L 2047 65L 1630 66L 226266L 2105 65L 1560 70L 2213966L 2022 65L 1530 9L 218066L 2009 65L 1490 9L 214066L 1983 66L 2179 9L 213070L 2272 66L 1900 9L 21109L 2385 66L 1762 9L 20709L 2377 66L 1734 9L 20709L 2375 70L 10404 32L 20509L 2359 9L 1640 32L 21009L 2356 9L 1640 32L 20209L 2354 9L 1610 32L 1960

32L 2240 9L 1590 16L 210032L 2260 9L 1590 16L 220032L 2200 9L 1560 16L 220032L 2270 32L 1640 16L 206016L 2300 32L 1600 16L 197016L 2310 32L 1560 16L 201016L 2350 32L 157016L 2260 16L 170016L 2290 16L 180016L 2240 16L 1700

16L 180016L 170016L 1700

European Commission EUR 23012 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on total organic carbon Author(s) E Sobiecka H van der Sloot K Andersen B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 50 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07412-7 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 total organic carbon (TOC) in soils sludge and treated bio-waste 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

-23012-EN

-C

9

submission of results has been set for TOC to the 31st of January 2007 Alternatively the participants were allowed to submit data electronically as Excel sheet using Email All data were treated in a confidential way Any presentation hereafter refers 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 provided a 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

125 Participants The following table lists the participating organizations and entities in the validation exercise for the horizontal TOC standard

bull Austria o barbara - Engineering Consulting Research amp Service GmbH o Federal Research and Training Centre for Forests Natural Hazards and

Landscape o NUA Umweltanalytik GmbH o Oumlsterreichische Agentur fuumlr Gesundheit und Ernaumlhrungssicherheit o Universitaumlt fuumlr Bodenkultur Wien o Shimadzu Europa GmbH o Umweltbundesamt o University of Natural resources and Applied Life Sciences

bull Belgium o VITO

bull France o INERIS o CEMAGREF - UR QELY o INRA - Laboratoire dAnalyse des Sols

bull Germany o ALBO-tec Technologiezentrum Fuumlr Analytik und Bodenmechanik GmbH

bull Norway o Norwegian Institute for Water Research

bull The Netherlands o ALCONTROL BV o Analytico Milieu B V

11

13 Summary results and derived performance characteristics The result of the various statistical evaluation according to ISO 5725-2 including outlier tests calculation of repeatability and reproducibility standard deviations can be found in Annex 3 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 The calculated average values the repeatability standard deviation (sr) and the reproducibility standard deviation (sR) are given in Table 1 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 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 total organic carbon (TOC) by dry combustion in treated biowaste sludge and soil All concentrations are expressed in gkg dry matter

Matrix Parameter Mean sr sR r R p Outliers Total number of data

No of

LOD

Sludge 1 TOC 272 17 59 13 45 13 2 62 0 Sludge 2 TOC 220 21 50 13 31 12 2 58 0

Compost 1 TOC 246 25 43 17 30 13 2 58 0 Compost 2 TOC 154 59 96 25 41 13 2 64 0

Soil 4 TOC 164 26 52 12 24 12 3 62 0 Soil 5 TOC 210 52 82 30 48 10 3 54 0

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

13

14 Annexes Annex 1 Model questionnaire to be filled by the participating laboratories Annex 2 Report on the validation materials used Annex 3 Statistical calculations Annex 4 Data submitted

14

14

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

15

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

16

Annex 3

Statistical calculations

Unit gkg

Mandels k statistics(Compost 1 - TOC)Mandels h statistics(Compost 1 - TOC)

Sample Compost 1 Compost 1 - TOC -- Mean PARM = 2463 [gkg]

Element TOC

General calcparmT1= 142643E+04T2= 351264E+06T3= 58T4= 292T5= 16501E+03

n= variabelp= 13

N-table= 5

Mandels statistics End ResultLAB 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

69L 1960000 64265 4 -235 352 Fail - - 69L - - -502735L 2291667 1674 6 -081 009 2291667 16741 6 5 -171066L 2377425 8552 4 -041 047 2377425 85518 4 3 -85346L 2395000 4796 4 -033 026 2395000 47958 4 3 -67756L 2401227 3133 6 -030 017 2401227 31330 6 5 -61432L 2415000 9713 4 -024 053 2415000 97125 4 3 -47770L 2435100 - 1 -014 2435100 - 1 -27616L 2440000 6033 6 -012 033 2440000 60332 6 5 -22745L 2503800 11759 6 018 064 2503800 117589 6 5 41136L 2514416 3994 3 023 022 2514416 39937 3 2 51765L 2537333 5216 3 033 029 2537333 52157 3 2 74744L 2555667 2783 6 042 015 2555667 27826 6 5 9309L 2568167 1356 6 048 007 2568167 13556 6 5 105530L 2580000 2000 3 053 011 2580000 20000 3 2 117334L 3013269 9580 6 255 053 Fail - - 34L - - 5506

Totgem 246587 9632 gkg 1-level 232 (176) 13 2462677 (34L 69L) 13 12Totstd= 21507 16070 5-level 186 (152) 2

68RESULTS Mean = 24626770 gkg

Repeatability variance S2r = 3666797Repeatability std Sr = 605541 --gt 246 r = 169551Between lab variance S2L = 7715586Reproducibility var S2R = 11382383Reproducibility std SR = 1066882 --gt 433 R = 298727Remarks 2 Labs rejected (34L 69L)

000 050 100 150 200 250 300 350 400

k-values

69L

35L

66L

46L

56L

32L

70L

16L

45L

36L

65L

44L

9L

30L

34L

Mandels k statistics(Compost 1 - TOC)

-600 -400 -200 00 200 400 600

Deviation from Mean

69L

35L

66L

46L

56L

32L

70L

16L

45L

36L

65L

44L

9L

30L

34L

Labo

rato

ries

Compost 1 - TOC -- Mean PARM = 2463 [gkg]

-300 -200 -100 000 100 200 300

h-values

69L

66L

56L

70L

45L

65L

9L

34L

Labo

rato

ries

Mandels h statistics(Compost 1 - TOC)

Compost 1-TOC

Unit gkg

Mandels k statistics(Compost 2 - TOC)Mandels h statistics(Compost 2 - TOC)

Sample Compost 2 Compost 2 - TOC -- Mean PARM = 1542 [gkg]

Element TOC

General calcparmT1= 994897E+03T2= 155556E+06T3= 64T4= 346T5= 41738E+03

n= variabelp= 13

N-table= 5

Mandels statistics End ResultLAB 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

45L 1326733 5665 6 -100 042 Fail 1326733 56646 6 5 -215046L 1355000 24365 4 -089 181 Fail - - 46L - - -186736L 1381949 5407 3 -078 040 Fail 1381949 54070 3 2 -159870L 1414120 - 1 -066 Fail 1414120 - 1 -127616L 1428333 5565 6 -061 041 1428333 55648 6 5 -113466L 1485550 7805 4 -039 058 1485550 78047 4 3 -56232L 1532500 5377 4 -021 040 1532500 53774 4 3 -09219L 1576833 10138 6 -004 075 1576833 101381 6 5 3519L 1582333 6166 6 -002 046 1582333 61659 6 5 40656L 1594432 4046 6 003 030 1594432 40463 6 5 52744L 1653000 3651 6 025 027 1653000 36508 6 5 111334L 1655127 13717 6 026 102 1655127 137168 6 5 113434L 1655127 13717 6 026 102 1655127 137168 6 5 113465L 1756500 16295 4 065 121 Fail 1756500 162949 4 3 214869L 2415000 30687 4 316 228 Fail - - 69L - - 8733

Totgem 158750 10900 gkg 1-level 232 (176) 13 1541734 (46L 69L) 13 12Totstd= 26187 8164 5-level 186 (152) 2

72RESULTS Mean = 15417337 gkg

Repeatability variance S2r = 8183950Repeatability std Sr = 904652 --gt 587 r = 253303Between lab variance S2L = 13631046Reproducibility var S2R = 21814995Reproducibility std SR = 1476990 --gt 958 R = 413557Remarks 2 Labs rejected (46L 69L)

000 050 100 150 200 250

k-values

45L

46L

36L

70L

16L

66L

32L

19L

9L

56L

44L

34L

34L

65L

69L

Mandels k statistics(Compost 2 - TOC)

-400 -200 00 200 400 600 800 1000

Deviation from Mean

45L

46L

36L

70L

16L

66L

32L

19L

9L

56L

44L

34L

34L

65L

69L

Labo

rato

ries

Compost 2 - TOC -- Mean PARM = 1542 [gkg]

-100 000 100 200 300 400

h-values

45L

36L

16L

32L

9L

44L

34L

69L

Labo

rato

ries

Mandels h statistics(Compost 2 - TOC)

Compost 2-TOC

Unit gkg

Mandels k statistics(Sludge 1 - TOC)Mandels h statistics(Sludge 1 - TOC)

Sample Sludge 1 Sludge 1 - TOC -- Mean PARM = 2721 [gkg]

Element TOC

General calcparmT1= 169626E+04T2= 465445E+06T3= 62T4= 326T5= 10312E+03

n= variabelp= 13

N-table= 5

Mandels statistics End ResultLAB 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

69L 233000 2362 4 -347 037 Fail - - 69L - - -2488046L 2312500 2062 4 -040 032 Fail 2312500 20616 4 3 -408565L 2615500 1708 4 004 026 2615500 17078 4 3 -105566L 2627200 8268 4 006 128 2627200 82678 4 3 -93836L 2664041 4976 3 011 077 2664041 49758 3 2 -56935L 2671500 3533 6 013 055 2671500 35331 6 5 -49556L 2692298 0874 6 016 014 Fail 2692298 08738 6 5 -28732L 2717500 6185 4 019 096 Fail 2717500 61847 4 3 -03519L 2753333 7819 6 025 121 Fail 2753333 78189 6 5 32470L 2814600 - 1 034 Fail 2814600 - 1 9369L 2853667 0398 6 039 006 Fail 2853667 03983 6 5 132716L 2860000 1673 6 040 026 Fail 2860000 16733 6 5 139045L 2884433 7033 6 044 109 Fail 2884433 70331 6 5 163544L 2906167 1129 6 047 017 Fail 2906167 11286 6 5 185234L 3186874 17674 6 089 274 Fail - - 34L - - 4659

Totgem 258617 4692 gkg 1-level 232 (176) 13 2720980 (34L 69L) 13 12Totstd= 67800 4610 5-level 186 (152) 2

72RESULTS Mean = 27209799 gkg

Repeatability variance S2r = 2104538Repeatability std Sr = 458752 --gt 169 r = 128451Between lab variance S2L = 23618387Reproducibility var S2R = 25722925Reproducibility std SR = 1603837 --gt 589 R = 449074Remarks 2 Labs rejected (34L 69L)

000 050 100 150 200 250 300

k-values

69L

46L

65L

66L

36L

35L

56L

32L

19L

70L

9L

16L

45L

44L

34L

Mandels k statistics(Sludge 1 - TOC)

-2500 -2000 -1500 -1000 -500 00 500

Deviation from Mean

69L

46L

65L

66L

36L

35L

56L

32L

19L

70L

9L

16L

45L

44L

34L

Labo

rato

ries

Sludge 1 - TOC -- Mean PARM = 2721 [gkg]

-400 -300 -200 -100 000 100

h-values

69L

65L

36L

56L

19L

9L

45L

34L

Labo

rato

ries

Mandels h statistics(Sludge 1 - TOC)

Sludge 1-TOC

68 Unit gkg

Mandels k statistics(Sludge 2 - TOC)Mandels h statistics(Sludge 2 - TOC)

Sample Sludge 2 Sludge 2 - TOC -- Mean PARM = 2207 [gkg]

Element TOC

General calcparmT1= 128601E+04T2= 285689E+06T3= 58T4= 310T5= 97826E+02

n= variabelp= 12

N-table= 5

Mandels statistics End ResultLAB 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

46L 182500 0500 4 -333 008 Fail - - 46L - - -2024466L 2029475 5267 4 -012 084 2029475 52674 4 3 -177436L 2072609 2222 3 -005 035 2072609 22222 3 2 -134365L 2084750 3865 4 -002 062 2084750 38647 4 3 -122135L 2140333 3119 6 007 050 2140333 31194 6 5 -66556L 2188021 1282 6 015 020 2188021 12822 6 5 -18819L 2223667 7916 6 022 126 Fail 2223667 79157 6 5 16832L 2242500 3096 4 025 049 Fail 2242500 30957 4 3 35645L 2266600 8322 6 029 132 Fail 2266600 83216 6 5 59770L 2272460 - 1 030 Fail 2272460 - 1 65616L 2291667 3869 6 033 062 Fail 2291667 38687 6 5 84844L 2302667 1546 6 035 025 Fail 2302667 15462 6 5 9589L 2367667 1296 6 047 021 Fail 2367667 12956 6 5 160834L 2718591 17124 6 108 273 Fail - - 34L - - 5117

Totgem 209882 4571 gkg 1-level 230 (176) 12 2206868 (34L 46L) 12 11Totstd= 57628 4485 5-level 185 (151) 2

68RESULTS Mean = 22068679 gkg

Repeatability variance S2r = 2126659Repeatability std Sr = 461157 --gt 209 r = 129124Between lab variance S2L = 9960432Reproducibility var S2R = 12087091Reproducibility std SR = 1099413 --gt 498 R = 307836Remarks 2 Labs rejected (34L 46L)

000 050 100 150 200 250 300

k-values

46L

66L

36L

65L

35L

56L

19L

32L

45L

70L

16L

44L

9L

34L

Mandels k statistics(Sludge 2 - TOC)

-2500 -2000 -1500 -1000 -500 00 500 1000

Deviation from Mean

46L

66L

36L

65L

35L

56L

19L

32L

45L

70L

16L

44L

9L

34L

Labo

rato

ries

Sludge 2 - TOC -- Mean PARM = 2207 [gkg]

-400 -300 -200 -100 000 100 200

h-values

46L

66L

36L

65L

35L

56L

19L

32L

45L

70L

16L

44L

9L

34L

Labo

rato

ries

Mandels h statistics(Sludge 2 - TOC)

Sludge 2-TOC

Unit gkg

Mandels k statistics(Soil 4 - TOC)Mandels h statistics(Soil 4 - TOC)

Sample Soil 4 Soil 4 - TOC -- Mean PARM = 1641 [gkg]

Element TOC

General calcparmT1= 102171E+03T2= 168700E+04T3= 62T4= 338T5= 94040E+00

n= variabelp= 12

N-table= 5

Mandels statistics End ResultLAB 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

36L 147161 0470 3 -036 068 Fail 147161 04702 3 2 -16965L 155250 0591 4 -032 085 Fail 155250 05909 4 3 -08844L 157900 0115 6 -031 017 Fail 157900 01152 6 5 -06232L 159250 0359 4 -031 052 Fail 159250 03594 4 3 -0489L 160500 0315 6 -030 045 Fail 160500 03146 6 5 -03656L 164927 0113 6 -028 016 Fail 164927 01127 6 5 00835L 165000 0261 6 -028 038 Fail 165000 02608 6 5 00919L 166667 0505 6 -027 073 Fail 166667 05046 6 5 02645L 168850 0763 6 -026 110 Fail 168850 07628 6 5 04816L 173333 0516 6 -024 074 Fail 173333 05164 6 5 09334L 174761 0346 6 -024 050 Fail 174761 03462 6 5 10730L 175333 0473 3 -024 068 Fail 175333 04726 3 2 11366L 189375 2035 4 -017 294 Fail - - 66L - - 25346L 227500 0500 4 000 072 - - 46L - - 63470L 1040400 - 1 360 Fail - - 70L - - 8763

Totgem 22841 0526 gkg 1-level 232 (176) 12 164078 (46L 66L70L) 12 11Totstd= 22541 0469 5-level 186 (152) 3

71RESULTS Mean = 1640777 gkg

Repeatability variance S2r = 018808Repeatability std Sr = 043368 --gt 264 r = 12143Between lab variance S2L = 054747Reproducibility var S2R = 073555Reproducibility std SR = 085764 --gt 523 R = 24014Remarks 3 Labs rejected (46L 66L70L)

000 050 100 150 200 250 300

k-values

36L

65L

44L

32L

9L

56L

35L

19L

45L

16L

34L

30L

66L

46L

70L

Mandels k statistics(Soil 4 - TOC)

-100 00 100 200 300 400 500 600 700 800 900

Deviation from Mean

36L

65L

44L

32L

9L

56L

35L

19L

45L

16L

34L

30L

66L

46L

70L

Labo

rato

ries

Soil 4 - TOC -- Mean PARM = 1641 [gkg]

-100 000 100 200 300 400

h-values

36L

44L

9L

35L

45L

34L

66L

70L

Labo

rato

ries

Mandels h statistics(Soil 4 - TOC)

Soil 4-TOC

Unit gkg

Mandels k statistics(Soil 5 - TOC)Mandels h statistics(Soil 5 - TOC)

Sample Soil 5 Soil 5 - TOC -- Mean PARM = 2102 [gkg]

Element TOC

General calcparmT1= 113661E+03T2= 240201E+04T3= 54T4= 300T5= 51756E+01

n= variabelp= 10

N-table= 5

Mandels statistics End ResultLAB 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

44L 164383 14708 6 -036 325 Fail - - 44L - - -45865L 181250 0830 4 -033 018 Fail 181250 08302 4 3 -29045L 200317 1116 6 -029 025 Fail 200317 11163 6 5 -09935L 201833 1828 6 -029 040 Fail 201833 18280 6 5 -08432L 203250 0585 4 -029 013 Fail 203250 05852 4 3 -07016L 209000 0959 6 -028 021 Fail 209000 09592 6 5 -0129L 211667 0427 6 -027 009 Fail 211667 04274 6 5 01556L 214030 0887 6 -027 020 Fail 214030 08868 6 5 03819L 216000 0795 6 -026 018 Fail 216000 07950 6 5 05834L 226009 1308 6 -024 029 Fail 226009 13076 6 5 15836L 228783 4310 3 -024 095 Fail - - 36L - - 18666L 238750 1234 4 -022 027 Fail 238750 12340 4 3 28570L 2213900 - 1 333 Fail - - 70L - - 20037

Totgem 36224 2416 gkg 1-level 227 (175) 10 210211 (36L44L 70L) 10 9Totstd= 55669 4003 5-level 184 (151) 3

64RESULTS Mean = 2102106 gkg

Repeatability variance S2r = 117627Repeatability std Sr = 108456 --gt 516 r = 30368Between lab variance S2L = 176699Reproducibility var S2R = 294326Reproducibility std SR = 171559 --gt 816 R = 48037Remarks 3 Labs rejected (36L44L 70L)

000 050 100 150 200 250 300 350

k-values

44L

65L

45L

35L

32L

16L

9L

56L

19L

34L

36L

66L

70L

Mandels k statistics(Soil 5 - TOC)

-500 00 500 1000 1500 2000 2500

Deviation from Mean

44L

65L

45L

35L

32L

16L

9L

56L

19L

34L

36L

66L

70L

Labo

rato

ries

Soil 5 - TOC -- Mean PARM = 2102 [gkg]

-100 000 100 200 300 400

h-values

44L

65L

45L

35L

32L

16L

9L

56L

19L

34L

36L

66L

70L

Labo

rato

ries

Mandels h statistics(Soil 5 - TOC)

Soil 5-TOC

17

Annex 4

Raw data submitted

Sample Compost 1 Sample Compost 2 Sample Sewage Sludge 1Element TOC [gkg] Element TOC [gkg] Element TOC [gkg]

LAB PARM LAB PARM LAB PARM30L 2600 19L 1691 19L 286730L 2580 19L 1634 19L 281430L 2560 19L 1619 19L 276934L 2969 19L 1604 19L 272034L 2936 19L 1499 19L 268834L 2958 19L 1414 19L 266234L 2994 34L 1527 34L 315234L 3199 34L 1622 34L 314934L 3024 34L 1519 34L 343035L 2306 34L 1753 34L 336535L 2300 34L 1636 34L 304235L 2298 34L 1874 34L 298335L 2296 35L 1506 35L 270735L 2291 35L 1312 35L 270335L 2259 35L 1294 35L 268836L 2546 35L 1279 35L 267436L 2527 35L 1191 35L 263136L 2470 35L 1177 35L 262644L 2583 36L 1418 36L 271344L 2581 36L 1408 36L 266544L 2578 36L 1320 36L 261444L 2539 44L 1719 44L 292044L 2528 44L 1664 44L 291644L 2525 44L 1654 44L 291245L 2658 44L 1637 44L 290045L 2600 44L 1624 44L 289645L 2546 44L 1620 44L 289345L 2461 45L 1428 45L 297645L 2409 45L 1325 45L 295245L 2350 45L 1323 45L 288546L 2460 45L 1321 45L 286646L 2400 45L 1309 45L 284046L 2370 45L 1253 45L 278746L 2350 46L 1580 46L 233056L 2436 46L 1550 46L 233056L 2435 46L 1170 46L 230056L 2405 46L 1120 46L 229056L 2397 56L 1642 56L 270256L 2375 56L 1626 56L 270156L 2358 56L 1622 56L 269465L 2587 56L 1571 56L 269365L 2542 56L 1561 56L 268465L 2483 56L 1545 56L 268066L 2454 65L 1933 65L 264166L 2429 65L 1838 65L 260966L 2365 65L 1693 65L 260766L 2262 65L 1562 65L 260569L 2730 66L 1561 66L 270169L 2250 66L 1545 66L 267469L 1440 66L 1420 66L 261969L 1420 66L 1417 66L 251470L 2435 69L 2700 69L 2639L 2594 69L 2660 69L 2409L 2570 69L 2170 69L 2199L 2565 69L 2130 69L 2109L 2563 70L 1414 70L 28159L 2562 9L 1644 9L 28579L 2555 9L 1641 9L 2856

32L 2290 9L 1602 9L 285532L 2390 9L 1589 9L 285532L 2510 9L 1526 9L 285332L 2470 9L 1492 9L 284616L 2380 32L 1470 32L 265016L 2530 32L 1520 32L 271016L 2400 32L 1540 32L 271016L 2500 32L 1600 32L 280016L 2420 16L 1400 16L 284016L 2410 16L 1440 16L 2840

16L 1470 16L 286016L 1510 16L 287016L 1360 16L 287016L 1390 16L 2880

Sample Sewage Sludge 2 Sample Soil 4 Sample Soil 5Element TOC [gkg] Element TOC [gkg] Element TOC [gkg]

LAB PARM LAB PARM LAB PARM19L 2308 19L 1720 19L 225019L 2303 19L 1700 19L 223019L 2239 19L 1690 19L 221019L 2204 19L 1670 19L 211019L 2192 19L 1640 19L 210019L 2096 19L 1580 19L 206034L 2631 30L 1790 34L 244334L 2471 30L 1770 34L 233434L 2977 30L 1700 34L 231534L 2785 34L 1740 34L 222134L 2780 34L 1692 34L 217634L 2668 34L 1727 34L 207335L 2179 34L 1767 35L 233035L 2160 34L 1777 35L 208035L 2158 34L 1783 35L 201035L 2132 35L 1700 35L 198035L 2119 35L 1650 35L 193035L 2094 35L 1650 35L 178036L 2096 35L 1640 36L 254036L 2069 35L 1630 36L 253436L 2052 35L 1630 36L 179044L 2325 36L 1500 44L 302144L 2309 36L 1497 44L 298244L 2307 36L 1417 44L 295644L 2305 44L 1594 44L 30744L 2287 44L 1587 44L 30044L 2283 44L 1584 44L 29745L 2331 44L 1574 45L 214945L 2327 44L 1573 45L 209245L 2308 44L 1562 45L 203345L 2287 45L 1827 45L 197145L 2234 45L 1709 45L 193345L 2113 45L 1666 45L 184146L 190 45L 1665 56L 223746L 180 45L 1664 56L 222246L 180 45L 1600 56L 220346L 180 46L 2300 56L 206956L 2204 46L 2300 56L 206856L 2197 46L 2300 56L 204456L 2193 46L 2200 65L 192056L 2185 56L 1668 65L 182056L 2183 56L 1654 65L 179056L 2167 56L 1653 65L 172065L 2136 56L 1643 66L 254365L 2091 56L 1639 66L 242465L 2065 56L 1638 66L 232165L 2047 65L 1630 66L 226266L 2105 65L 1560 70L 2213966L 2022 65L 1530 9L 218066L 2009 65L 1490 9L 214066L 1983 66L 2179 9L 213070L 2272 66L 1900 9L 21109L 2385 66L 1762 9L 20709L 2377 66L 1734 9L 20709L 2375 70L 10404 32L 20509L 2359 9L 1640 32L 21009L 2356 9L 1640 32L 20209L 2354 9L 1610 32L 1960

32L 2240 9L 1590 16L 210032L 2260 9L 1590 16L 220032L 2200 9L 1560 16L 220032L 2270 32L 1640 16L 206016L 2300 32L 1600 16L 197016L 2310 32L 1560 16L 201016L 2350 32L 157016L 2260 16L 170016L 2290 16L 180016L 2240 16L 1700

16L 180016L 170016L 1700

European Commission EUR 23012 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on total organic carbon Author(s) E Sobiecka H van der Sloot K Andersen B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 50 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07412-7 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 total organic carbon (TOC) in soils sludge and treated bio-waste 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

-23012-EN

-C

10

125 Participants The following table lists the participating organizations and entities in the validation exercise for the horizontal TOC standard

bull Austria o barbara - Engineering Consulting Research amp Service GmbH o Federal Research and Training Centre for Forests Natural Hazards and

Landscape o NUA Umweltanalytik GmbH o Oumlsterreichische Agentur fuumlr Gesundheit und Ernaumlhrungssicherheit o Universitaumlt fuumlr Bodenkultur Wien o Shimadzu Europa GmbH o Umweltbundesamt o University of Natural resources and Applied Life Sciences

bull Belgium o VITO

bull France o INERIS o CEMAGREF - UR QELY o INRA - Laboratoire dAnalyse des Sols

bull Germany o ALBO-tec Technologiezentrum Fuumlr Analytik und Bodenmechanik GmbH

bull Norway o Norwegian Institute for Water Research

bull The Netherlands o ALCONTROL BV o Analytico Milieu B V

11

13 Summary results and derived performance characteristics The result of the various statistical evaluation according to ISO 5725-2 including outlier tests calculation of repeatability and reproducibility standard deviations can be found in Annex 3 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 The calculated average values the repeatability standard deviation (sr) and the reproducibility standard deviation (sR) are given in Table 1 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 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 total organic carbon (TOC) by dry combustion in treated biowaste sludge and soil All concentrations are expressed in gkg dry matter

Matrix Parameter Mean sr sR r R p Outliers Total number of data

No of

LOD

Sludge 1 TOC 272 17 59 13 45 13 2 62 0 Sludge 2 TOC 220 21 50 13 31 12 2 58 0

Compost 1 TOC 246 25 43 17 30 13 2 58 0 Compost 2 TOC 154 59 96 25 41 13 2 64 0

Soil 4 TOC 164 26 52 12 24 12 3 62 0 Soil 5 TOC 210 52 82 30 48 10 3 54 0

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

13

14 Annexes Annex 1 Model questionnaire to be filled by the participating laboratories Annex 2 Report on the validation materials used Annex 3 Statistical calculations Annex 4 Data submitted

14

14

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

15

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

16

Annex 3

Statistical calculations

Unit gkg

Mandels k statistics(Compost 1 - TOC)Mandels h statistics(Compost 1 - TOC)

Sample Compost 1 Compost 1 - TOC -- Mean PARM = 2463 [gkg]

Element TOC

General calcparmT1= 142643E+04T2= 351264E+06T3= 58T4= 292T5= 16501E+03

n= variabelp= 13

N-table= 5

Mandels statistics End ResultLAB 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

69L 1960000 64265 4 -235 352 Fail - - 69L - - -502735L 2291667 1674 6 -081 009 2291667 16741 6 5 -171066L 2377425 8552 4 -041 047 2377425 85518 4 3 -85346L 2395000 4796 4 -033 026 2395000 47958 4 3 -67756L 2401227 3133 6 -030 017 2401227 31330 6 5 -61432L 2415000 9713 4 -024 053 2415000 97125 4 3 -47770L 2435100 - 1 -014 2435100 - 1 -27616L 2440000 6033 6 -012 033 2440000 60332 6 5 -22745L 2503800 11759 6 018 064 2503800 117589 6 5 41136L 2514416 3994 3 023 022 2514416 39937 3 2 51765L 2537333 5216 3 033 029 2537333 52157 3 2 74744L 2555667 2783 6 042 015 2555667 27826 6 5 9309L 2568167 1356 6 048 007 2568167 13556 6 5 105530L 2580000 2000 3 053 011 2580000 20000 3 2 117334L 3013269 9580 6 255 053 Fail - - 34L - - 5506

Totgem 246587 9632 gkg 1-level 232 (176) 13 2462677 (34L 69L) 13 12Totstd= 21507 16070 5-level 186 (152) 2

68RESULTS Mean = 24626770 gkg

Repeatability variance S2r = 3666797Repeatability std Sr = 605541 --gt 246 r = 169551Between lab variance S2L = 7715586Reproducibility var S2R = 11382383Reproducibility std SR = 1066882 --gt 433 R = 298727Remarks 2 Labs rejected (34L 69L)

000 050 100 150 200 250 300 350 400

k-values

69L

35L

66L

46L

56L

32L

70L

16L

45L

36L

65L

44L

9L

30L

34L

Mandels k statistics(Compost 1 - TOC)

-600 -400 -200 00 200 400 600

Deviation from Mean

69L

35L

66L

46L

56L

32L

70L

16L

45L

36L

65L

44L

9L

30L

34L

Labo

rato

ries

Compost 1 - TOC -- Mean PARM = 2463 [gkg]

-300 -200 -100 000 100 200 300

h-values

69L

66L

56L

70L

45L

65L

9L

34L

Labo

rato

ries

Mandels h statistics(Compost 1 - TOC)

Compost 1-TOC

Unit gkg

Mandels k statistics(Compost 2 - TOC)Mandels h statistics(Compost 2 - TOC)

Sample Compost 2 Compost 2 - TOC -- Mean PARM = 1542 [gkg]

Element TOC

General calcparmT1= 994897E+03T2= 155556E+06T3= 64T4= 346T5= 41738E+03

n= variabelp= 13

N-table= 5

Mandels statistics End ResultLAB 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

45L 1326733 5665 6 -100 042 Fail 1326733 56646 6 5 -215046L 1355000 24365 4 -089 181 Fail - - 46L - - -186736L 1381949 5407 3 -078 040 Fail 1381949 54070 3 2 -159870L 1414120 - 1 -066 Fail 1414120 - 1 -127616L 1428333 5565 6 -061 041 1428333 55648 6 5 -113466L 1485550 7805 4 -039 058 1485550 78047 4 3 -56232L 1532500 5377 4 -021 040 1532500 53774 4 3 -09219L 1576833 10138 6 -004 075 1576833 101381 6 5 3519L 1582333 6166 6 -002 046 1582333 61659 6 5 40656L 1594432 4046 6 003 030 1594432 40463 6 5 52744L 1653000 3651 6 025 027 1653000 36508 6 5 111334L 1655127 13717 6 026 102 1655127 137168 6 5 113434L 1655127 13717 6 026 102 1655127 137168 6 5 113465L 1756500 16295 4 065 121 Fail 1756500 162949 4 3 214869L 2415000 30687 4 316 228 Fail - - 69L - - 8733

Totgem 158750 10900 gkg 1-level 232 (176) 13 1541734 (46L 69L) 13 12Totstd= 26187 8164 5-level 186 (152) 2

72RESULTS Mean = 15417337 gkg

Repeatability variance S2r = 8183950Repeatability std Sr = 904652 --gt 587 r = 253303Between lab variance S2L = 13631046Reproducibility var S2R = 21814995Reproducibility std SR = 1476990 --gt 958 R = 413557Remarks 2 Labs rejected (46L 69L)

000 050 100 150 200 250

k-values

45L

46L

36L

70L

16L

66L

32L

19L

9L

56L

44L

34L

34L

65L

69L

Mandels k statistics(Compost 2 - TOC)

-400 -200 00 200 400 600 800 1000

Deviation from Mean

45L

46L

36L

70L

16L

66L

32L

19L

9L

56L

44L

34L

34L

65L

69L

Labo

rato

ries

Compost 2 - TOC -- Mean PARM = 1542 [gkg]

-100 000 100 200 300 400

h-values

45L

36L

16L

32L

9L

44L

34L

69L

Labo

rato

ries

Mandels h statistics(Compost 2 - TOC)

Compost 2-TOC

Unit gkg

Mandels k statistics(Sludge 1 - TOC)Mandels h statistics(Sludge 1 - TOC)

Sample Sludge 1 Sludge 1 - TOC -- Mean PARM = 2721 [gkg]

Element TOC

General calcparmT1= 169626E+04T2= 465445E+06T3= 62T4= 326T5= 10312E+03

n= variabelp= 13

N-table= 5

Mandels statistics End ResultLAB 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

69L 233000 2362 4 -347 037 Fail - - 69L - - -2488046L 2312500 2062 4 -040 032 Fail 2312500 20616 4 3 -408565L 2615500 1708 4 004 026 2615500 17078 4 3 -105566L 2627200 8268 4 006 128 2627200 82678 4 3 -93836L 2664041 4976 3 011 077 2664041 49758 3 2 -56935L 2671500 3533 6 013 055 2671500 35331 6 5 -49556L 2692298 0874 6 016 014 Fail 2692298 08738 6 5 -28732L 2717500 6185 4 019 096 Fail 2717500 61847 4 3 -03519L 2753333 7819 6 025 121 Fail 2753333 78189 6 5 32470L 2814600 - 1 034 Fail 2814600 - 1 9369L 2853667 0398 6 039 006 Fail 2853667 03983 6 5 132716L 2860000 1673 6 040 026 Fail 2860000 16733 6 5 139045L 2884433 7033 6 044 109 Fail 2884433 70331 6 5 163544L 2906167 1129 6 047 017 Fail 2906167 11286 6 5 185234L 3186874 17674 6 089 274 Fail - - 34L - - 4659

Totgem 258617 4692 gkg 1-level 232 (176) 13 2720980 (34L 69L) 13 12Totstd= 67800 4610 5-level 186 (152) 2

72RESULTS Mean = 27209799 gkg

Repeatability variance S2r = 2104538Repeatability std Sr = 458752 --gt 169 r = 128451Between lab variance S2L = 23618387Reproducibility var S2R = 25722925Reproducibility std SR = 1603837 --gt 589 R = 449074Remarks 2 Labs rejected (34L 69L)

000 050 100 150 200 250 300

k-values

69L

46L

65L

66L

36L

35L

56L

32L

19L

70L

9L

16L

45L

44L

34L

Mandels k statistics(Sludge 1 - TOC)

-2500 -2000 -1500 -1000 -500 00 500

Deviation from Mean

69L

46L

65L

66L

36L

35L

56L

32L

19L

70L

9L

16L

45L

44L

34L

Labo

rato

ries

Sludge 1 - TOC -- Mean PARM = 2721 [gkg]

-400 -300 -200 -100 000 100

h-values

69L

65L

36L

56L

19L

9L

45L

34L

Labo

rato

ries

Mandels h statistics(Sludge 1 - TOC)

Sludge 1-TOC

68 Unit gkg

Mandels k statistics(Sludge 2 - TOC)Mandels h statistics(Sludge 2 - TOC)

Sample Sludge 2 Sludge 2 - TOC -- Mean PARM = 2207 [gkg]

Element TOC

General calcparmT1= 128601E+04T2= 285689E+06T3= 58T4= 310T5= 97826E+02

n= variabelp= 12

N-table= 5

Mandels statistics End ResultLAB 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

46L 182500 0500 4 -333 008 Fail - - 46L - - -2024466L 2029475 5267 4 -012 084 2029475 52674 4 3 -177436L 2072609 2222 3 -005 035 2072609 22222 3 2 -134365L 2084750 3865 4 -002 062 2084750 38647 4 3 -122135L 2140333 3119 6 007 050 2140333 31194 6 5 -66556L 2188021 1282 6 015 020 2188021 12822 6 5 -18819L 2223667 7916 6 022 126 Fail 2223667 79157 6 5 16832L 2242500 3096 4 025 049 Fail 2242500 30957 4 3 35645L 2266600 8322 6 029 132 Fail 2266600 83216 6 5 59770L 2272460 - 1 030 Fail 2272460 - 1 65616L 2291667 3869 6 033 062 Fail 2291667 38687 6 5 84844L 2302667 1546 6 035 025 Fail 2302667 15462 6 5 9589L 2367667 1296 6 047 021 Fail 2367667 12956 6 5 160834L 2718591 17124 6 108 273 Fail - - 34L - - 5117

Totgem 209882 4571 gkg 1-level 230 (176) 12 2206868 (34L 46L) 12 11Totstd= 57628 4485 5-level 185 (151) 2

68RESULTS Mean = 22068679 gkg

Repeatability variance S2r = 2126659Repeatability std Sr = 461157 --gt 209 r = 129124Between lab variance S2L = 9960432Reproducibility var S2R = 12087091Reproducibility std SR = 1099413 --gt 498 R = 307836Remarks 2 Labs rejected (34L 46L)

000 050 100 150 200 250 300

k-values

46L

66L

36L

65L

35L

56L

19L

32L

45L

70L

16L

44L

9L

34L

Mandels k statistics(Sludge 2 - TOC)

-2500 -2000 -1500 -1000 -500 00 500 1000

Deviation from Mean

46L

66L

36L

65L

35L

56L

19L

32L

45L

70L

16L

44L

9L

34L

Labo

rato

ries

Sludge 2 - TOC -- Mean PARM = 2207 [gkg]

-400 -300 -200 -100 000 100 200

h-values

46L

66L

36L

65L

35L

56L

19L

32L

45L

70L

16L

44L

9L

34L

Labo

rato

ries

Mandels h statistics(Sludge 2 - TOC)

Sludge 2-TOC

Unit gkg

Mandels k statistics(Soil 4 - TOC)Mandels h statistics(Soil 4 - TOC)

Sample Soil 4 Soil 4 - TOC -- Mean PARM = 1641 [gkg]

Element TOC

General calcparmT1= 102171E+03T2= 168700E+04T3= 62T4= 338T5= 94040E+00

n= variabelp= 12

N-table= 5

Mandels statistics End ResultLAB 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

36L 147161 0470 3 -036 068 Fail 147161 04702 3 2 -16965L 155250 0591 4 -032 085 Fail 155250 05909 4 3 -08844L 157900 0115 6 -031 017 Fail 157900 01152 6 5 -06232L 159250 0359 4 -031 052 Fail 159250 03594 4 3 -0489L 160500 0315 6 -030 045 Fail 160500 03146 6 5 -03656L 164927 0113 6 -028 016 Fail 164927 01127 6 5 00835L 165000 0261 6 -028 038 Fail 165000 02608 6 5 00919L 166667 0505 6 -027 073 Fail 166667 05046 6 5 02645L 168850 0763 6 -026 110 Fail 168850 07628 6 5 04816L 173333 0516 6 -024 074 Fail 173333 05164 6 5 09334L 174761 0346 6 -024 050 Fail 174761 03462 6 5 10730L 175333 0473 3 -024 068 Fail 175333 04726 3 2 11366L 189375 2035 4 -017 294 Fail - - 66L - - 25346L 227500 0500 4 000 072 - - 46L - - 63470L 1040400 - 1 360 Fail - - 70L - - 8763

Totgem 22841 0526 gkg 1-level 232 (176) 12 164078 (46L 66L70L) 12 11Totstd= 22541 0469 5-level 186 (152) 3

71RESULTS Mean = 1640777 gkg

Repeatability variance S2r = 018808Repeatability std Sr = 043368 --gt 264 r = 12143Between lab variance S2L = 054747Reproducibility var S2R = 073555Reproducibility std SR = 085764 --gt 523 R = 24014Remarks 3 Labs rejected (46L 66L70L)

000 050 100 150 200 250 300

k-values

36L

65L

44L

32L

9L

56L

35L

19L

45L

16L

34L

30L

66L

46L

70L

Mandels k statistics(Soil 4 - TOC)

-100 00 100 200 300 400 500 600 700 800 900

Deviation from Mean

36L

65L

44L

32L

9L

56L

35L

19L

45L

16L

34L

30L

66L

46L

70L

Labo

rato

ries

Soil 4 - TOC -- Mean PARM = 1641 [gkg]

-100 000 100 200 300 400

h-values

36L

44L

9L

35L

45L

34L

66L

70L

Labo

rato

ries

Mandels h statistics(Soil 4 - TOC)

Soil 4-TOC

Unit gkg

Mandels k statistics(Soil 5 - TOC)Mandels h statistics(Soil 5 - TOC)

Sample Soil 5 Soil 5 - TOC -- Mean PARM = 2102 [gkg]

Element TOC

General calcparmT1= 113661E+03T2= 240201E+04T3= 54T4= 300T5= 51756E+01

n= variabelp= 10

N-table= 5

Mandels statistics End ResultLAB 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

44L 164383 14708 6 -036 325 Fail - - 44L - - -45865L 181250 0830 4 -033 018 Fail 181250 08302 4 3 -29045L 200317 1116 6 -029 025 Fail 200317 11163 6 5 -09935L 201833 1828 6 -029 040 Fail 201833 18280 6 5 -08432L 203250 0585 4 -029 013 Fail 203250 05852 4 3 -07016L 209000 0959 6 -028 021 Fail 209000 09592 6 5 -0129L 211667 0427 6 -027 009 Fail 211667 04274 6 5 01556L 214030 0887 6 -027 020 Fail 214030 08868 6 5 03819L 216000 0795 6 -026 018 Fail 216000 07950 6 5 05834L 226009 1308 6 -024 029 Fail 226009 13076 6 5 15836L 228783 4310 3 -024 095 Fail - - 36L - - 18666L 238750 1234 4 -022 027 Fail 238750 12340 4 3 28570L 2213900 - 1 333 Fail - - 70L - - 20037

Totgem 36224 2416 gkg 1-level 227 (175) 10 210211 (36L44L 70L) 10 9Totstd= 55669 4003 5-level 184 (151) 3

64RESULTS Mean = 2102106 gkg

Repeatability variance S2r = 117627Repeatability std Sr = 108456 --gt 516 r = 30368Between lab variance S2L = 176699Reproducibility var S2R = 294326Reproducibility std SR = 171559 --gt 816 R = 48037Remarks 3 Labs rejected (36L44L 70L)

000 050 100 150 200 250 300 350

k-values

44L

65L

45L

35L

32L

16L

9L

56L

19L

34L

36L

66L

70L

Mandels k statistics(Soil 5 - TOC)

-500 00 500 1000 1500 2000 2500

Deviation from Mean

44L

65L

45L

35L

32L

16L

9L

56L

19L

34L

36L

66L

70L

Labo

rato

ries

Soil 5 - TOC -- Mean PARM = 2102 [gkg]

-100 000 100 200 300 400

h-values

44L

65L

45L

35L

32L

16L

9L

56L

19L

34L

36L

66L

70L

Labo

rato

ries

Mandels h statistics(Soil 5 - TOC)

Soil 5-TOC

17

Annex 4

Raw data submitted

Sample Compost 1 Sample Compost 2 Sample Sewage Sludge 1Element TOC [gkg] Element TOC [gkg] Element TOC [gkg]

LAB PARM LAB PARM LAB PARM30L 2600 19L 1691 19L 286730L 2580 19L 1634 19L 281430L 2560 19L 1619 19L 276934L 2969 19L 1604 19L 272034L 2936 19L 1499 19L 268834L 2958 19L 1414 19L 266234L 2994 34L 1527 34L 315234L 3199 34L 1622 34L 314934L 3024 34L 1519 34L 343035L 2306 34L 1753 34L 336535L 2300 34L 1636 34L 304235L 2298 34L 1874 34L 298335L 2296 35L 1506 35L 270735L 2291 35L 1312 35L 270335L 2259 35L 1294 35L 268836L 2546 35L 1279 35L 267436L 2527 35L 1191 35L 263136L 2470 35L 1177 35L 262644L 2583 36L 1418 36L 271344L 2581 36L 1408 36L 266544L 2578 36L 1320 36L 261444L 2539 44L 1719 44L 292044L 2528 44L 1664 44L 291644L 2525 44L 1654 44L 291245L 2658 44L 1637 44L 290045L 2600 44L 1624 44L 289645L 2546 44L 1620 44L 289345L 2461 45L 1428 45L 297645L 2409 45L 1325 45L 295245L 2350 45L 1323 45L 288546L 2460 45L 1321 45L 286646L 2400 45L 1309 45L 284046L 2370 45L 1253 45L 278746L 2350 46L 1580 46L 233056L 2436 46L 1550 46L 233056L 2435 46L 1170 46L 230056L 2405 46L 1120 46L 229056L 2397 56L 1642 56L 270256L 2375 56L 1626 56L 270156L 2358 56L 1622 56L 269465L 2587 56L 1571 56L 269365L 2542 56L 1561 56L 268465L 2483 56L 1545 56L 268066L 2454 65L 1933 65L 264166L 2429 65L 1838 65L 260966L 2365 65L 1693 65L 260766L 2262 65L 1562 65L 260569L 2730 66L 1561 66L 270169L 2250 66L 1545 66L 267469L 1440 66L 1420 66L 261969L 1420 66L 1417 66L 251470L 2435 69L 2700 69L 2639L 2594 69L 2660 69L 2409L 2570 69L 2170 69L 2199L 2565 69L 2130 69L 2109L 2563 70L 1414 70L 28159L 2562 9L 1644 9L 28579L 2555 9L 1641 9L 2856

32L 2290 9L 1602 9L 285532L 2390 9L 1589 9L 285532L 2510 9L 1526 9L 285332L 2470 9L 1492 9L 284616L 2380 32L 1470 32L 265016L 2530 32L 1520 32L 271016L 2400 32L 1540 32L 271016L 2500 32L 1600 32L 280016L 2420 16L 1400 16L 284016L 2410 16L 1440 16L 2840

16L 1470 16L 286016L 1510 16L 287016L 1360 16L 287016L 1390 16L 2880

Sample Sewage Sludge 2 Sample Soil 4 Sample Soil 5Element TOC [gkg] Element TOC [gkg] Element TOC [gkg]

LAB PARM LAB PARM LAB PARM19L 2308 19L 1720 19L 225019L 2303 19L 1700 19L 223019L 2239 19L 1690 19L 221019L 2204 19L 1670 19L 211019L 2192 19L 1640 19L 210019L 2096 19L 1580 19L 206034L 2631 30L 1790 34L 244334L 2471 30L 1770 34L 233434L 2977 30L 1700 34L 231534L 2785 34L 1740 34L 222134L 2780 34L 1692 34L 217634L 2668 34L 1727 34L 207335L 2179 34L 1767 35L 233035L 2160 34L 1777 35L 208035L 2158 34L 1783 35L 201035L 2132 35L 1700 35L 198035L 2119 35L 1650 35L 193035L 2094 35L 1650 35L 178036L 2096 35L 1640 36L 254036L 2069 35L 1630 36L 253436L 2052 35L 1630 36L 179044L 2325 36L 1500 44L 302144L 2309 36L 1497 44L 298244L 2307 36L 1417 44L 295644L 2305 44L 1594 44L 30744L 2287 44L 1587 44L 30044L 2283 44L 1584 44L 29745L 2331 44L 1574 45L 214945L 2327 44L 1573 45L 209245L 2308 44L 1562 45L 203345L 2287 45L 1827 45L 197145L 2234 45L 1709 45L 193345L 2113 45L 1666 45L 184146L 190 45L 1665 56L 223746L 180 45L 1664 56L 222246L 180 45L 1600 56L 220346L 180 46L 2300 56L 206956L 2204 46L 2300 56L 206856L 2197 46L 2300 56L 204456L 2193 46L 2200 65L 192056L 2185 56L 1668 65L 182056L 2183 56L 1654 65L 179056L 2167 56L 1653 65L 172065L 2136 56L 1643 66L 254365L 2091 56L 1639 66L 242465L 2065 56L 1638 66L 232165L 2047 65L 1630 66L 226266L 2105 65L 1560 70L 2213966L 2022 65L 1530 9L 218066L 2009 65L 1490 9L 214066L 1983 66L 2179 9L 213070L 2272 66L 1900 9L 21109L 2385 66L 1762 9L 20709L 2377 66L 1734 9L 20709L 2375 70L 10404 32L 20509L 2359 9L 1640 32L 21009L 2356 9L 1640 32L 20209L 2354 9L 1610 32L 1960

32L 2240 9L 1590 16L 210032L 2260 9L 1590 16L 220032L 2200 9L 1560 16L 220032L 2270 32L 1640 16L 206016L 2300 32L 1600 16L 197016L 2310 32L 1560 16L 201016L 2350 32L 157016L 2260 16L 170016L 2290 16L 180016L 2240 16L 1700

16L 180016L 170016L 1700

European Commission EUR 23012 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on total organic carbon Author(s) E Sobiecka H van der Sloot K Andersen B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 50 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07412-7 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 total organic carbon (TOC) in soils sludge and treated bio-waste 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

-23012-EN

-C

11

13 Summary results and derived performance characteristics The result of the various statistical evaluation according to ISO 5725-2 including outlier tests calculation of repeatability and reproducibility standard deviations can be found in Annex 3 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 The calculated average values the repeatability standard deviation (sr) and the reproducibility standard deviation (sR) are given in Table 1 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 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 total organic carbon (TOC) by dry combustion in treated biowaste sludge and soil All concentrations are expressed in gkg dry matter

Matrix Parameter Mean sr sR r R p Outliers Total number of data

No of

LOD

Sludge 1 TOC 272 17 59 13 45 13 2 62 0 Sludge 2 TOC 220 21 50 13 31 12 2 58 0

Compost 1 TOC 246 25 43 17 30 13 2 58 0 Compost 2 TOC 154 59 96 25 41 13 2 64 0

Soil 4 TOC 164 26 52 12 24 12 3 62 0 Soil 5 TOC 210 52 82 30 48 10 3 54 0

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

13

14 Annexes Annex 1 Model questionnaire to be filled by the participating laboratories Annex 2 Report on the validation materials used Annex 3 Statistical calculations Annex 4 Data submitted

14

14

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

15

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

16

Annex 3

Statistical calculations

Unit gkg

Mandels k statistics(Compost 1 - TOC)Mandels h statistics(Compost 1 - TOC)

Sample Compost 1 Compost 1 - TOC -- Mean PARM = 2463 [gkg]

Element TOC

General calcparmT1= 142643E+04T2= 351264E+06T3= 58T4= 292T5= 16501E+03

n= variabelp= 13

N-table= 5

Mandels statistics End ResultLAB 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

69L 1960000 64265 4 -235 352 Fail - - 69L - - -502735L 2291667 1674 6 -081 009 2291667 16741 6 5 -171066L 2377425 8552 4 -041 047 2377425 85518 4 3 -85346L 2395000 4796 4 -033 026 2395000 47958 4 3 -67756L 2401227 3133 6 -030 017 2401227 31330 6 5 -61432L 2415000 9713 4 -024 053 2415000 97125 4 3 -47770L 2435100 - 1 -014 2435100 - 1 -27616L 2440000 6033 6 -012 033 2440000 60332 6 5 -22745L 2503800 11759 6 018 064 2503800 117589 6 5 41136L 2514416 3994 3 023 022 2514416 39937 3 2 51765L 2537333 5216 3 033 029 2537333 52157 3 2 74744L 2555667 2783 6 042 015 2555667 27826 6 5 9309L 2568167 1356 6 048 007 2568167 13556 6 5 105530L 2580000 2000 3 053 011 2580000 20000 3 2 117334L 3013269 9580 6 255 053 Fail - - 34L - - 5506

Totgem 246587 9632 gkg 1-level 232 (176) 13 2462677 (34L 69L) 13 12Totstd= 21507 16070 5-level 186 (152) 2

68RESULTS Mean = 24626770 gkg

Repeatability variance S2r = 3666797Repeatability std Sr = 605541 --gt 246 r = 169551Between lab variance S2L = 7715586Reproducibility var S2R = 11382383Reproducibility std SR = 1066882 --gt 433 R = 298727Remarks 2 Labs rejected (34L 69L)

000 050 100 150 200 250 300 350 400

k-values

69L

35L

66L

46L

56L

32L

70L

16L

45L

36L

65L

44L

9L

30L

34L

Mandels k statistics(Compost 1 - TOC)

-600 -400 -200 00 200 400 600

Deviation from Mean

69L

35L

66L

46L

56L

32L

70L

16L

45L

36L

65L

44L

9L

30L

34L

Labo

rato

ries

Compost 1 - TOC -- Mean PARM = 2463 [gkg]

-300 -200 -100 000 100 200 300

h-values

69L

66L

56L

70L

45L

65L

9L

34L

Labo

rato

ries

Mandels h statistics(Compost 1 - TOC)

Compost 1-TOC

Unit gkg

Mandels k statistics(Compost 2 - TOC)Mandels h statistics(Compost 2 - TOC)

Sample Compost 2 Compost 2 - TOC -- Mean PARM = 1542 [gkg]

Element TOC

General calcparmT1= 994897E+03T2= 155556E+06T3= 64T4= 346T5= 41738E+03

n= variabelp= 13

N-table= 5

Mandels statistics End ResultLAB 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

45L 1326733 5665 6 -100 042 Fail 1326733 56646 6 5 -215046L 1355000 24365 4 -089 181 Fail - - 46L - - -186736L 1381949 5407 3 -078 040 Fail 1381949 54070 3 2 -159870L 1414120 - 1 -066 Fail 1414120 - 1 -127616L 1428333 5565 6 -061 041 1428333 55648 6 5 -113466L 1485550 7805 4 -039 058 1485550 78047 4 3 -56232L 1532500 5377 4 -021 040 1532500 53774 4 3 -09219L 1576833 10138 6 -004 075 1576833 101381 6 5 3519L 1582333 6166 6 -002 046 1582333 61659 6 5 40656L 1594432 4046 6 003 030 1594432 40463 6 5 52744L 1653000 3651 6 025 027 1653000 36508 6 5 111334L 1655127 13717 6 026 102 1655127 137168 6 5 113434L 1655127 13717 6 026 102 1655127 137168 6 5 113465L 1756500 16295 4 065 121 Fail 1756500 162949 4 3 214869L 2415000 30687 4 316 228 Fail - - 69L - - 8733

Totgem 158750 10900 gkg 1-level 232 (176) 13 1541734 (46L 69L) 13 12Totstd= 26187 8164 5-level 186 (152) 2

72RESULTS Mean = 15417337 gkg

Repeatability variance S2r = 8183950Repeatability std Sr = 904652 --gt 587 r = 253303Between lab variance S2L = 13631046Reproducibility var S2R = 21814995Reproducibility std SR = 1476990 --gt 958 R = 413557Remarks 2 Labs rejected (46L 69L)

000 050 100 150 200 250

k-values

45L

46L

36L

70L

16L

66L

32L

19L

9L

56L

44L

34L

34L

65L

69L

Mandels k statistics(Compost 2 - TOC)

-400 -200 00 200 400 600 800 1000

Deviation from Mean

45L

46L

36L

70L

16L

66L

32L

19L

9L

56L

44L

34L

34L

65L

69L

Labo

rato

ries

Compost 2 - TOC -- Mean PARM = 1542 [gkg]

-100 000 100 200 300 400

h-values

45L

36L

16L

32L

9L

44L

34L

69L

Labo

rato

ries

Mandels h statistics(Compost 2 - TOC)

Compost 2-TOC

Unit gkg

Mandels k statistics(Sludge 1 - TOC)Mandels h statistics(Sludge 1 - TOC)

Sample Sludge 1 Sludge 1 - TOC -- Mean PARM = 2721 [gkg]

Element TOC

General calcparmT1= 169626E+04T2= 465445E+06T3= 62T4= 326T5= 10312E+03

n= variabelp= 13

N-table= 5

Mandels statistics End ResultLAB 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

69L 233000 2362 4 -347 037 Fail - - 69L - - -2488046L 2312500 2062 4 -040 032 Fail 2312500 20616 4 3 -408565L 2615500 1708 4 004 026 2615500 17078 4 3 -105566L 2627200 8268 4 006 128 2627200 82678 4 3 -93836L 2664041 4976 3 011 077 2664041 49758 3 2 -56935L 2671500 3533 6 013 055 2671500 35331 6 5 -49556L 2692298 0874 6 016 014 Fail 2692298 08738 6 5 -28732L 2717500 6185 4 019 096 Fail 2717500 61847 4 3 -03519L 2753333 7819 6 025 121 Fail 2753333 78189 6 5 32470L 2814600 - 1 034 Fail 2814600 - 1 9369L 2853667 0398 6 039 006 Fail 2853667 03983 6 5 132716L 2860000 1673 6 040 026 Fail 2860000 16733 6 5 139045L 2884433 7033 6 044 109 Fail 2884433 70331 6 5 163544L 2906167 1129 6 047 017 Fail 2906167 11286 6 5 185234L 3186874 17674 6 089 274 Fail - - 34L - - 4659

Totgem 258617 4692 gkg 1-level 232 (176) 13 2720980 (34L 69L) 13 12Totstd= 67800 4610 5-level 186 (152) 2

72RESULTS Mean = 27209799 gkg

Repeatability variance S2r = 2104538Repeatability std Sr = 458752 --gt 169 r = 128451Between lab variance S2L = 23618387Reproducibility var S2R = 25722925Reproducibility std SR = 1603837 --gt 589 R = 449074Remarks 2 Labs rejected (34L 69L)

000 050 100 150 200 250 300

k-values

69L

46L

65L

66L

36L

35L

56L

32L

19L

70L

9L

16L

45L

44L

34L

Mandels k statistics(Sludge 1 - TOC)

-2500 -2000 -1500 -1000 -500 00 500

Deviation from Mean

69L

46L

65L

66L

36L

35L

56L

32L

19L

70L

9L

16L

45L

44L

34L

Labo

rato

ries

Sludge 1 - TOC -- Mean PARM = 2721 [gkg]

-400 -300 -200 -100 000 100

h-values

69L

65L

36L

56L

19L

9L

45L

34L

Labo

rato

ries

Mandels h statistics(Sludge 1 - TOC)

Sludge 1-TOC

68 Unit gkg

Mandels k statistics(Sludge 2 - TOC)Mandels h statistics(Sludge 2 - TOC)

Sample Sludge 2 Sludge 2 - TOC -- Mean PARM = 2207 [gkg]

Element TOC

General calcparmT1= 128601E+04T2= 285689E+06T3= 58T4= 310T5= 97826E+02

n= variabelp= 12

N-table= 5

Mandels statistics End ResultLAB 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

46L 182500 0500 4 -333 008 Fail - - 46L - - -2024466L 2029475 5267 4 -012 084 2029475 52674 4 3 -177436L 2072609 2222 3 -005 035 2072609 22222 3 2 -134365L 2084750 3865 4 -002 062 2084750 38647 4 3 -122135L 2140333 3119 6 007 050 2140333 31194 6 5 -66556L 2188021 1282 6 015 020 2188021 12822 6 5 -18819L 2223667 7916 6 022 126 Fail 2223667 79157 6 5 16832L 2242500 3096 4 025 049 Fail 2242500 30957 4 3 35645L 2266600 8322 6 029 132 Fail 2266600 83216 6 5 59770L 2272460 - 1 030 Fail 2272460 - 1 65616L 2291667 3869 6 033 062 Fail 2291667 38687 6 5 84844L 2302667 1546 6 035 025 Fail 2302667 15462 6 5 9589L 2367667 1296 6 047 021 Fail 2367667 12956 6 5 160834L 2718591 17124 6 108 273 Fail - - 34L - - 5117

Totgem 209882 4571 gkg 1-level 230 (176) 12 2206868 (34L 46L) 12 11Totstd= 57628 4485 5-level 185 (151) 2

68RESULTS Mean = 22068679 gkg

Repeatability variance S2r = 2126659Repeatability std Sr = 461157 --gt 209 r = 129124Between lab variance S2L = 9960432Reproducibility var S2R = 12087091Reproducibility std SR = 1099413 --gt 498 R = 307836Remarks 2 Labs rejected (34L 46L)

000 050 100 150 200 250 300

k-values

46L

66L

36L

65L

35L

56L

19L

32L

45L

70L

16L

44L

9L

34L

Mandels k statistics(Sludge 2 - TOC)

-2500 -2000 -1500 -1000 -500 00 500 1000

Deviation from Mean

46L

66L

36L

65L

35L

56L

19L

32L

45L

70L

16L

44L

9L

34L

Labo

rato

ries

Sludge 2 - TOC -- Mean PARM = 2207 [gkg]

-400 -300 -200 -100 000 100 200

h-values

46L

66L

36L

65L

35L

56L

19L

32L

45L

70L

16L

44L

9L

34L

Labo

rato

ries

Mandels h statistics(Sludge 2 - TOC)

Sludge 2-TOC

Unit gkg

Mandels k statistics(Soil 4 - TOC)Mandels h statistics(Soil 4 - TOC)

Sample Soil 4 Soil 4 - TOC -- Mean PARM = 1641 [gkg]

Element TOC

General calcparmT1= 102171E+03T2= 168700E+04T3= 62T4= 338T5= 94040E+00

n= variabelp= 12

N-table= 5

Mandels statistics End ResultLAB 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

36L 147161 0470 3 -036 068 Fail 147161 04702 3 2 -16965L 155250 0591 4 -032 085 Fail 155250 05909 4 3 -08844L 157900 0115 6 -031 017 Fail 157900 01152 6 5 -06232L 159250 0359 4 -031 052 Fail 159250 03594 4 3 -0489L 160500 0315 6 -030 045 Fail 160500 03146 6 5 -03656L 164927 0113 6 -028 016 Fail 164927 01127 6 5 00835L 165000 0261 6 -028 038 Fail 165000 02608 6 5 00919L 166667 0505 6 -027 073 Fail 166667 05046 6 5 02645L 168850 0763 6 -026 110 Fail 168850 07628 6 5 04816L 173333 0516 6 -024 074 Fail 173333 05164 6 5 09334L 174761 0346 6 -024 050 Fail 174761 03462 6 5 10730L 175333 0473 3 -024 068 Fail 175333 04726 3 2 11366L 189375 2035 4 -017 294 Fail - - 66L - - 25346L 227500 0500 4 000 072 - - 46L - - 63470L 1040400 - 1 360 Fail - - 70L - - 8763

Totgem 22841 0526 gkg 1-level 232 (176) 12 164078 (46L 66L70L) 12 11Totstd= 22541 0469 5-level 186 (152) 3

71RESULTS Mean = 1640777 gkg

Repeatability variance S2r = 018808Repeatability std Sr = 043368 --gt 264 r = 12143Between lab variance S2L = 054747Reproducibility var S2R = 073555Reproducibility std SR = 085764 --gt 523 R = 24014Remarks 3 Labs rejected (46L 66L70L)

000 050 100 150 200 250 300

k-values

36L

65L

44L

32L

9L

56L

35L

19L

45L

16L

34L

30L

66L

46L

70L

Mandels k statistics(Soil 4 - TOC)

-100 00 100 200 300 400 500 600 700 800 900

Deviation from Mean

36L

65L

44L

32L

9L

56L

35L

19L

45L

16L

34L

30L

66L

46L

70L

Labo

rato

ries

Soil 4 - TOC -- Mean PARM = 1641 [gkg]

-100 000 100 200 300 400

h-values

36L

44L

9L

35L

45L

34L

66L

70L

Labo

rato

ries

Mandels h statistics(Soil 4 - TOC)

Soil 4-TOC

Unit gkg

Mandels k statistics(Soil 5 - TOC)Mandels h statistics(Soil 5 - TOC)

Sample Soil 5 Soil 5 - TOC -- Mean PARM = 2102 [gkg]

Element TOC

General calcparmT1= 113661E+03T2= 240201E+04T3= 54T4= 300T5= 51756E+01

n= variabelp= 10

N-table= 5

Mandels statistics End ResultLAB 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

44L 164383 14708 6 -036 325 Fail - - 44L - - -45865L 181250 0830 4 -033 018 Fail 181250 08302 4 3 -29045L 200317 1116 6 -029 025 Fail 200317 11163 6 5 -09935L 201833 1828 6 -029 040 Fail 201833 18280 6 5 -08432L 203250 0585 4 -029 013 Fail 203250 05852 4 3 -07016L 209000 0959 6 -028 021 Fail 209000 09592 6 5 -0129L 211667 0427 6 -027 009 Fail 211667 04274 6 5 01556L 214030 0887 6 -027 020 Fail 214030 08868 6 5 03819L 216000 0795 6 -026 018 Fail 216000 07950 6 5 05834L 226009 1308 6 -024 029 Fail 226009 13076 6 5 15836L 228783 4310 3 -024 095 Fail - - 36L - - 18666L 238750 1234 4 -022 027 Fail 238750 12340 4 3 28570L 2213900 - 1 333 Fail - - 70L - - 20037

Totgem 36224 2416 gkg 1-level 227 (175) 10 210211 (36L44L 70L) 10 9Totstd= 55669 4003 5-level 184 (151) 3

64RESULTS Mean = 2102106 gkg

Repeatability variance S2r = 117627Repeatability std Sr = 108456 --gt 516 r = 30368Between lab variance S2L = 176699Reproducibility var S2R = 294326Reproducibility std SR = 171559 --gt 816 R = 48037Remarks 3 Labs rejected (36L44L 70L)

000 050 100 150 200 250 300 350

k-values

44L

65L

45L

35L

32L

16L

9L

56L

19L

34L

36L

66L

70L

Mandels k statistics(Soil 5 - TOC)

-500 00 500 1000 1500 2000 2500

Deviation from Mean

44L

65L

45L

35L

32L

16L

9L

56L

19L

34L

36L

66L

70L

Labo

rato

ries

Soil 5 - TOC -- Mean PARM = 2102 [gkg]

-100 000 100 200 300 400

h-values

44L

65L

45L

35L

32L

16L

9L

56L

19L

34L

36L

66L

70L

Labo

rato

ries

Mandels h statistics(Soil 5 - TOC)

Soil 5-TOC

17

Annex 4

Raw data submitted

Sample Compost 1 Sample Compost 2 Sample Sewage Sludge 1Element TOC [gkg] Element TOC [gkg] Element TOC [gkg]

LAB PARM LAB PARM LAB PARM30L 2600 19L 1691 19L 286730L 2580 19L 1634 19L 281430L 2560 19L 1619 19L 276934L 2969 19L 1604 19L 272034L 2936 19L 1499 19L 268834L 2958 19L 1414 19L 266234L 2994 34L 1527 34L 315234L 3199 34L 1622 34L 314934L 3024 34L 1519 34L 343035L 2306 34L 1753 34L 336535L 2300 34L 1636 34L 304235L 2298 34L 1874 34L 298335L 2296 35L 1506 35L 270735L 2291 35L 1312 35L 270335L 2259 35L 1294 35L 268836L 2546 35L 1279 35L 267436L 2527 35L 1191 35L 263136L 2470 35L 1177 35L 262644L 2583 36L 1418 36L 271344L 2581 36L 1408 36L 266544L 2578 36L 1320 36L 261444L 2539 44L 1719 44L 292044L 2528 44L 1664 44L 291644L 2525 44L 1654 44L 291245L 2658 44L 1637 44L 290045L 2600 44L 1624 44L 289645L 2546 44L 1620 44L 289345L 2461 45L 1428 45L 297645L 2409 45L 1325 45L 295245L 2350 45L 1323 45L 288546L 2460 45L 1321 45L 286646L 2400 45L 1309 45L 284046L 2370 45L 1253 45L 278746L 2350 46L 1580 46L 233056L 2436 46L 1550 46L 233056L 2435 46L 1170 46L 230056L 2405 46L 1120 46L 229056L 2397 56L 1642 56L 270256L 2375 56L 1626 56L 270156L 2358 56L 1622 56L 269465L 2587 56L 1571 56L 269365L 2542 56L 1561 56L 268465L 2483 56L 1545 56L 268066L 2454 65L 1933 65L 264166L 2429 65L 1838 65L 260966L 2365 65L 1693 65L 260766L 2262 65L 1562 65L 260569L 2730 66L 1561 66L 270169L 2250 66L 1545 66L 267469L 1440 66L 1420 66L 261969L 1420 66L 1417 66L 251470L 2435 69L 2700 69L 2639L 2594 69L 2660 69L 2409L 2570 69L 2170 69L 2199L 2565 69L 2130 69L 2109L 2563 70L 1414 70L 28159L 2562 9L 1644 9L 28579L 2555 9L 1641 9L 2856

32L 2290 9L 1602 9L 285532L 2390 9L 1589 9L 285532L 2510 9L 1526 9L 285332L 2470 9L 1492 9L 284616L 2380 32L 1470 32L 265016L 2530 32L 1520 32L 271016L 2400 32L 1540 32L 271016L 2500 32L 1600 32L 280016L 2420 16L 1400 16L 284016L 2410 16L 1440 16L 2840

16L 1470 16L 286016L 1510 16L 287016L 1360 16L 287016L 1390 16L 2880

Sample Sewage Sludge 2 Sample Soil 4 Sample Soil 5Element TOC [gkg] Element TOC [gkg] Element TOC [gkg]

LAB PARM LAB PARM LAB PARM19L 2308 19L 1720 19L 225019L 2303 19L 1700 19L 223019L 2239 19L 1690 19L 221019L 2204 19L 1670 19L 211019L 2192 19L 1640 19L 210019L 2096 19L 1580 19L 206034L 2631 30L 1790 34L 244334L 2471 30L 1770 34L 233434L 2977 30L 1700 34L 231534L 2785 34L 1740 34L 222134L 2780 34L 1692 34L 217634L 2668 34L 1727 34L 207335L 2179 34L 1767 35L 233035L 2160 34L 1777 35L 208035L 2158 34L 1783 35L 201035L 2132 35L 1700 35L 198035L 2119 35L 1650 35L 193035L 2094 35L 1650 35L 178036L 2096 35L 1640 36L 254036L 2069 35L 1630 36L 253436L 2052 35L 1630 36L 179044L 2325 36L 1500 44L 302144L 2309 36L 1497 44L 298244L 2307 36L 1417 44L 295644L 2305 44L 1594 44L 30744L 2287 44L 1587 44L 30044L 2283 44L 1584 44L 29745L 2331 44L 1574 45L 214945L 2327 44L 1573 45L 209245L 2308 44L 1562 45L 203345L 2287 45L 1827 45L 197145L 2234 45L 1709 45L 193345L 2113 45L 1666 45L 184146L 190 45L 1665 56L 223746L 180 45L 1664 56L 222246L 180 45L 1600 56L 220346L 180 46L 2300 56L 206956L 2204 46L 2300 56L 206856L 2197 46L 2300 56L 204456L 2193 46L 2200 65L 192056L 2185 56L 1668 65L 182056L 2183 56L 1654 65L 179056L 2167 56L 1653 65L 172065L 2136 56L 1643 66L 254365L 2091 56L 1639 66L 242465L 2065 56L 1638 66L 232165L 2047 65L 1630 66L 226266L 2105 65L 1560 70L 2213966L 2022 65L 1530 9L 218066L 2009 65L 1490 9L 214066L 1983 66L 2179 9L 213070L 2272 66L 1900 9L 21109L 2385 66L 1762 9L 20709L 2377 66L 1734 9L 20709L 2375 70L 10404 32L 20509L 2359 9L 1640 32L 21009L 2356 9L 1640 32L 20209L 2354 9L 1610 32L 1960

32L 2240 9L 1590 16L 210032L 2260 9L 1590 16L 220032L 2200 9L 1560 16L 220032L 2270 32L 1640 16L 206016L 2300 32L 1600 16L 197016L 2310 32L 1560 16L 201016L 2350 32L 157016L 2260 16L 170016L 2290 16L 180016L 2240 16L 1700

16L 180016L 170016L 1700

European Commission EUR 23012 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on total organic carbon Author(s) E Sobiecka H van der Sloot K Andersen B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 50 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07412-7 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 total organic carbon (TOC) in soils sludge and treated bio-waste 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

-23012-EN

-C

12

Table 1 - Results of the interlaboratory comparison studies of the determination of total organic carbon (TOC) by dry combustion in treated biowaste sludge and soil All concentrations are expressed in gkg dry matter

Matrix Parameter Mean sr sR r R p Outliers Total number of data

No of

LOD

Sludge 1 TOC 272 17 59 13 45 13 2 62 0 Sludge 2 TOC 220 21 50 13 31 12 2 58 0

Compost 1 TOC 246 25 43 17 30 13 2 58 0 Compost 2 TOC 154 59 96 25 41 13 2 64 0

Soil 4 TOC 164 26 52 12 24 12 3 62 0 Soil 5 TOC 210 52 82 30 48 10 3 54 0

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

13

14 Annexes Annex 1 Model questionnaire to be filled by the participating laboratories Annex 2 Report on the validation materials used Annex 3 Statistical calculations Annex 4 Data submitted

14

14

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

15

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

16

Annex 3

Statistical calculations

Unit gkg

Mandels k statistics(Compost 1 - TOC)Mandels h statistics(Compost 1 - TOC)

Sample Compost 1 Compost 1 - TOC -- Mean PARM = 2463 [gkg]

Element TOC

General calcparmT1= 142643E+04T2= 351264E+06T3= 58T4= 292T5= 16501E+03

n= variabelp= 13

N-table= 5

Mandels statistics End ResultLAB 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

69L 1960000 64265 4 -235 352 Fail - - 69L - - -502735L 2291667 1674 6 -081 009 2291667 16741 6 5 -171066L 2377425 8552 4 -041 047 2377425 85518 4 3 -85346L 2395000 4796 4 -033 026 2395000 47958 4 3 -67756L 2401227 3133 6 -030 017 2401227 31330 6 5 -61432L 2415000 9713 4 -024 053 2415000 97125 4 3 -47770L 2435100 - 1 -014 2435100 - 1 -27616L 2440000 6033 6 -012 033 2440000 60332 6 5 -22745L 2503800 11759 6 018 064 2503800 117589 6 5 41136L 2514416 3994 3 023 022 2514416 39937 3 2 51765L 2537333 5216 3 033 029 2537333 52157 3 2 74744L 2555667 2783 6 042 015 2555667 27826 6 5 9309L 2568167 1356 6 048 007 2568167 13556 6 5 105530L 2580000 2000 3 053 011 2580000 20000 3 2 117334L 3013269 9580 6 255 053 Fail - - 34L - - 5506

Totgem 246587 9632 gkg 1-level 232 (176) 13 2462677 (34L 69L) 13 12Totstd= 21507 16070 5-level 186 (152) 2

68RESULTS Mean = 24626770 gkg

Repeatability variance S2r = 3666797Repeatability std Sr = 605541 --gt 246 r = 169551Between lab variance S2L = 7715586Reproducibility var S2R = 11382383Reproducibility std SR = 1066882 --gt 433 R = 298727Remarks 2 Labs rejected (34L 69L)

000 050 100 150 200 250 300 350 400

k-values

69L

35L

66L

46L

56L

32L

70L

16L

45L

36L

65L

44L

9L

30L

34L

Mandels k statistics(Compost 1 - TOC)

-600 -400 -200 00 200 400 600

Deviation from Mean

69L

35L

66L

46L

56L

32L

70L

16L

45L

36L

65L

44L

9L

30L

34L

Labo

rato

ries

Compost 1 - TOC -- Mean PARM = 2463 [gkg]

-300 -200 -100 000 100 200 300

h-values

69L

66L

56L

70L

45L

65L

9L

34L

Labo

rato

ries

Mandels h statistics(Compost 1 - TOC)

Compost 1-TOC

Unit gkg

Mandels k statistics(Compost 2 - TOC)Mandels h statistics(Compost 2 - TOC)

Sample Compost 2 Compost 2 - TOC -- Mean PARM = 1542 [gkg]

Element TOC

General calcparmT1= 994897E+03T2= 155556E+06T3= 64T4= 346T5= 41738E+03

n= variabelp= 13

N-table= 5

Mandels statistics End ResultLAB 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

45L 1326733 5665 6 -100 042 Fail 1326733 56646 6 5 -215046L 1355000 24365 4 -089 181 Fail - - 46L - - -186736L 1381949 5407 3 -078 040 Fail 1381949 54070 3 2 -159870L 1414120 - 1 -066 Fail 1414120 - 1 -127616L 1428333 5565 6 -061 041 1428333 55648 6 5 -113466L 1485550 7805 4 -039 058 1485550 78047 4 3 -56232L 1532500 5377 4 -021 040 1532500 53774 4 3 -09219L 1576833 10138 6 -004 075 1576833 101381 6 5 3519L 1582333 6166 6 -002 046 1582333 61659 6 5 40656L 1594432 4046 6 003 030 1594432 40463 6 5 52744L 1653000 3651 6 025 027 1653000 36508 6 5 111334L 1655127 13717 6 026 102 1655127 137168 6 5 113434L 1655127 13717 6 026 102 1655127 137168 6 5 113465L 1756500 16295 4 065 121 Fail 1756500 162949 4 3 214869L 2415000 30687 4 316 228 Fail - - 69L - - 8733

Totgem 158750 10900 gkg 1-level 232 (176) 13 1541734 (46L 69L) 13 12Totstd= 26187 8164 5-level 186 (152) 2

72RESULTS Mean = 15417337 gkg

Repeatability variance S2r = 8183950Repeatability std Sr = 904652 --gt 587 r = 253303Between lab variance S2L = 13631046Reproducibility var S2R = 21814995Reproducibility std SR = 1476990 --gt 958 R = 413557Remarks 2 Labs rejected (46L 69L)

000 050 100 150 200 250

k-values

45L

46L

36L

70L

16L

66L

32L

19L

9L

56L

44L

34L

34L

65L

69L

Mandels k statistics(Compost 2 - TOC)

-400 -200 00 200 400 600 800 1000

Deviation from Mean

45L

46L

36L

70L

16L

66L

32L

19L

9L

56L

44L

34L

34L

65L

69L

Labo

rato

ries

Compost 2 - TOC -- Mean PARM = 1542 [gkg]

-100 000 100 200 300 400

h-values

45L

36L

16L

32L

9L

44L

34L

69L

Labo

rato

ries

Mandels h statistics(Compost 2 - TOC)

Compost 2-TOC

Unit gkg

Mandels k statistics(Sludge 1 - TOC)Mandels h statistics(Sludge 1 - TOC)

Sample Sludge 1 Sludge 1 - TOC -- Mean PARM = 2721 [gkg]

Element TOC

General calcparmT1= 169626E+04T2= 465445E+06T3= 62T4= 326T5= 10312E+03

n= variabelp= 13

N-table= 5

Mandels statistics End ResultLAB 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

69L 233000 2362 4 -347 037 Fail - - 69L - - -2488046L 2312500 2062 4 -040 032 Fail 2312500 20616 4 3 -408565L 2615500 1708 4 004 026 2615500 17078 4 3 -105566L 2627200 8268 4 006 128 2627200 82678 4 3 -93836L 2664041 4976 3 011 077 2664041 49758 3 2 -56935L 2671500 3533 6 013 055 2671500 35331 6 5 -49556L 2692298 0874 6 016 014 Fail 2692298 08738 6 5 -28732L 2717500 6185 4 019 096 Fail 2717500 61847 4 3 -03519L 2753333 7819 6 025 121 Fail 2753333 78189 6 5 32470L 2814600 - 1 034 Fail 2814600 - 1 9369L 2853667 0398 6 039 006 Fail 2853667 03983 6 5 132716L 2860000 1673 6 040 026 Fail 2860000 16733 6 5 139045L 2884433 7033 6 044 109 Fail 2884433 70331 6 5 163544L 2906167 1129 6 047 017 Fail 2906167 11286 6 5 185234L 3186874 17674 6 089 274 Fail - - 34L - - 4659

Totgem 258617 4692 gkg 1-level 232 (176) 13 2720980 (34L 69L) 13 12Totstd= 67800 4610 5-level 186 (152) 2

72RESULTS Mean = 27209799 gkg

Repeatability variance S2r = 2104538Repeatability std Sr = 458752 --gt 169 r = 128451Between lab variance S2L = 23618387Reproducibility var S2R = 25722925Reproducibility std SR = 1603837 --gt 589 R = 449074Remarks 2 Labs rejected (34L 69L)

000 050 100 150 200 250 300

k-values

69L

46L

65L

66L

36L

35L

56L

32L

19L

70L

9L

16L

45L

44L

34L

Mandels k statistics(Sludge 1 - TOC)

-2500 -2000 -1500 -1000 -500 00 500

Deviation from Mean

69L

46L

65L

66L

36L

35L

56L

32L

19L

70L

9L

16L

45L

44L

34L

Labo

rato

ries

Sludge 1 - TOC -- Mean PARM = 2721 [gkg]

-400 -300 -200 -100 000 100

h-values

69L

65L

36L

56L

19L

9L

45L

34L

Labo

rato

ries

Mandels h statistics(Sludge 1 - TOC)

Sludge 1-TOC

68 Unit gkg

Mandels k statistics(Sludge 2 - TOC)Mandels h statistics(Sludge 2 - TOC)

Sample Sludge 2 Sludge 2 - TOC -- Mean PARM = 2207 [gkg]

Element TOC

General calcparmT1= 128601E+04T2= 285689E+06T3= 58T4= 310T5= 97826E+02

n= variabelp= 12

N-table= 5

Mandels statistics End ResultLAB 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

46L 182500 0500 4 -333 008 Fail - - 46L - - -2024466L 2029475 5267 4 -012 084 2029475 52674 4 3 -177436L 2072609 2222 3 -005 035 2072609 22222 3 2 -134365L 2084750 3865 4 -002 062 2084750 38647 4 3 -122135L 2140333 3119 6 007 050 2140333 31194 6 5 -66556L 2188021 1282 6 015 020 2188021 12822 6 5 -18819L 2223667 7916 6 022 126 Fail 2223667 79157 6 5 16832L 2242500 3096 4 025 049 Fail 2242500 30957 4 3 35645L 2266600 8322 6 029 132 Fail 2266600 83216 6 5 59770L 2272460 - 1 030 Fail 2272460 - 1 65616L 2291667 3869 6 033 062 Fail 2291667 38687 6 5 84844L 2302667 1546 6 035 025 Fail 2302667 15462 6 5 9589L 2367667 1296 6 047 021 Fail 2367667 12956 6 5 160834L 2718591 17124 6 108 273 Fail - - 34L - - 5117

Totgem 209882 4571 gkg 1-level 230 (176) 12 2206868 (34L 46L) 12 11Totstd= 57628 4485 5-level 185 (151) 2

68RESULTS Mean = 22068679 gkg

Repeatability variance S2r = 2126659Repeatability std Sr = 461157 --gt 209 r = 129124Between lab variance S2L = 9960432Reproducibility var S2R = 12087091Reproducibility std SR = 1099413 --gt 498 R = 307836Remarks 2 Labs rejected (34L 46L)

000 050 100 150 200 250 300

k-values

46L

66L

36L

65L

35L

56L

19L

32L

45L

70L

16L

44L

9L

34L

Mandels k statistics(Sludge 2 - TOC)

-2500 -2000 -1500 -1000 -500 00 500 1000

Deviation from Mean

46L

66L

36L

65L

35L

56L

19L

32L

45L

70L

16L

44L

9L

34L

Labo

rato

ries

Sludge 2 - TOC -- Mean PARM = 2207 [gkg]

-400 -300 -200 -100 000 100 200

h-values

46L

66L

36L

65L

35L

56L

19L

32L

45L

70L

16L

44L

9L

34L

Labo

rato

ries

Mandels h statistics(Sludge 2 - TOC)

Sludge 2-TOC

Unit gkg

Mandels k statistics(Soil 4 - TOC)Mandels h statistics(Soil 4 - TOC)

Sample Soil 4 Soil 4 - TOC -- Mean PARM = 1641 [gkg]

Element TOC

General calcparmT1= 102171E+03T2= 168700E+04T3= 62T4= 338T5= 94040E+00

n= variabelp= 12

N-table= 5

Mandels statistics End ResultLAB 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

36L 147161 0470 3 -036 068 Fail 147161 04702 3 2 -16965L 155250 0591 4 -032 085 Fail 155250 05909 4 3 -08844L 157900 0115 6 -031 017 Fail 157900 01152 6 5 -06232L 159250 0359 4 -031 052 Fail 159250 03594 4 3 -0489L 160500 0315 6 -030 045 Fail 160500 03146 6 5 -03656L 164927 0113 6 -028 016 Fail 164927 01127 6 5 00835L 165000 0261 6 -028 038 Fail 165000 02608 6 5 00919L 166667 0505 6 -027 073 Fail 166667 05046 6 5 02645L 168850 0763 6 -026 110 Fail 168850 07628 6 5 04816L 173333 0516 6 -024 074 Fail 173333 05164 6 5 09334L 174761 0346 6 -024 050 Fail 174761 03462 6 5 10730L 175333 0473 3 -024 068 Fail 175333 04726 3 2 11366L 189375 2035 4 -017 294 Fail - - 66L - - 25346L 227500 0500 4 000 072 - - 46L - - 63470L 1040400 - 1 360 Fail - - 70L - - 8763

Totgem 22841 0526 gkg 1-level 232 (176) 12 164078 (46L 66L70L) 12 11Totstd= 22541 0469 5-level 186 (152) 3

71RESULTS Mean = 1640777 gkg

Repeatability variance S2r = 018808Repeatability std Sr = 043368 --gt 264 r = 12143Between lab variance S2L = 054747Reproducibility var S2R = 073555Reproducibility std SR = 085764 --gt 523 R = 24014Remarks 3 Labs rejected (46L 66L70L)

000 050 100 150 200 250 300

k-values

36L

65L

44L

32L

9L

56L

35L

19L

45L

16L

34L

30L

66L

46L

70L

Mandels k statistics(Soil 4 - TOC)

-100 00 100 200 300 400 500 600 700 800 900

Deviation from Mean

36L

65L

44L

32L

9L

56L

35L

19L

45L

16L

34L

30L

66L

46L

70L

Labo

rato

ries

Soil 4 - TOC -- Mean PARM = 1641 [gkg]

-100 000 100 200 300 400

h-values

36L

44L

9L

35L

45L

34L

66L

70L

Labo

rato

ries

Mandels h statistics(Soil 4 - TOC)

Soil 4-TOC

Unit gkg

Mandels k statistics(Soil 5 - TOC)Mandels h statistics(Soil 5 - TOC)

Sample Soil 5 Soil 5 - TOC -- Mean PARM = 2102 [gkg]

Element TOC

General calcparmT1= 113661E+03T2= 240201E+04T3= 54T4= 300T5= 51756E+01

n= variabelp= 10

N-table= 5

Mandels statistics End ResultLAB 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

44L 164383 14708 6 -036 325 Fail - - 44L - - -45865L 181250 0830 4 -033 018 Fail 181250 08302 4 3 -29045L 200317 1116 6 -029 025 Fail 200317 11163 6 5 -09935L 201833 1828 6 -029 040 Fail 201833 18280 6 5 -08432L 203250 0585 4 -029 013 Fail 203250 05852 4 3 -07016L 209000 0959 6 -028 021 Fail 209000 09592 6 5 -0129L 211667 0427 6 -027 009 Fail 211667 04274 6 5 01556L 214030 0887 6 -027 020 Fail 214030 08868 6 5 03819L 216000 0795 6 -026 018 Fail 216000 07950 6 5 05834L 226009 1308 6 -024 029 Fail 226009 13076 6 5 15836L 228783 4310 3 -024 095 Fail - - 36L - - 18666L 238750 1234 4 -022 027 Fail 238750 12340 4 3 28570L 2213900 - 1 333 Fail - - 70L - - 20037

Totgem 36224 2416 gkg 1-level 227 (175) 10 210211 (36L44L 70L) 10 9Totstd= 55669 4003 5-level 184 (151) 3

64RESULTS Mean = 2102106 gkg

Repeatability variance S2r = 117627Repeatability std Sr = 108456 --gt 516 r = 30368Between lab variance S2L = 176699Reproducibility var S2R = 294326Reproducibility std SR = 171559 --gt 816 R = 48037Remarks 3 Labs rejected (36L44L 70L)

000 050 100 150 200 250 300 350

k-values

44L

65L

45L

35L

32L

16L

9L

56L

19L

34L

36L

66L

70L

Mandels k statistics(Soil 5 - TOC)

-500 00 500 1000 1500 2000 2500

Deviation from Mean

44L

65L

45L

35L

32L

16L

9L

56L

19L

34L

36L

66L

70L

Labo

rato

ries

Soil 5 - TOC -- Mean PARM = 2102 [gkg]

-100 000 100 200 300 400

h-values

44L

65L

45L

35L

32L

16L

9L

56L

19L

34L

36L

66L

70L

Labo

rato

ries

Mandels h statistics(Soil 5 - TOC)

Soil 5-TOC

17

Annex 4

Raw data submitted

Sample Compost 1 Sample Compost 2 Sample Sewage Sludge 1Element TOC [gkg] Element TOC [gkg] Element TOC [gkg]

LAB PARM LAB PARM LAB PARM30L 2600 19L 1691 19L 286730L 2580 19L 1634 19L 281430L 2560 19L 1619 19L 276934L 2969 19L 1604 19L 272034L 2936 19L 1499 19L 268834L 2958 19L 1414 19L 266234L 2994 34L 1527 34L 315234L 3199 34L 1622 34L 314934L 3024 34L 1519 34L 343035L 2306 34L 1753 34L 336535L 2300 34L 1636 34L 304235L 2298 34L 1874 34L 298335L 2296 35L 1506 35L 270735L 2291 35L 1312 35L 270335L 2259 35L 1294 35L 268836L 2546 35L 1279 35L 267436L 2527 35L 1191 35L 263136L 2470 35L 1177 35L 262644L 2583 36L 1418 36L 271344L 2581 36L 1408 36L 266544L 2578 36L 1320 36L 261444L 2539 44L 1719 44L 292044L 2528 44L 1664 44L 291644L 2525 44L 1654 44L 291245L 2658 44L 1637 44L 290045L 2600 44L 1624 44L 289645L 2546 44L 1620 44L 289345L 2461 45L 1428 45L 297645L 2409 45L 1325 45L 295245L 2350 45L 1323 45L 288546L 2460 45L 1321 45L 286646L 2400 45L 1309 45L 284046L 2370 45L 1253 45L 278746L 2350 46L 1580 46L 233056L 2436 46L 1550 46L 233056L 2435 46L 1170 46L 230056L 2405 46L 1120 46L 229056L 2397 56L 1642 56L 270256L 2375 56L 1626 56L 270156L 2358 56L 1622 56L 269465L 2587 56L 1571 56L 269365L 2542 56L 1561 56L 268465L 2483 56L 1545 56L 268066L 2454 65L 1933 65L 264166L 2429 65L 1838 65L 260966L 2365 65L 1693 65L 260766L 2262 65L 1562 65L 260569L 2730 66L 1561 66L 270169L 2250 66L 1545 66L 267469L 1440 66L 1420 66L 261969L 1420 66L 1417 66L 251470L 2435 69L 2700 69L 2639L 2594 69L 2660 69L 2409L 2570 69L 2170 69L 2199L 2565 69L 2130 69L 2109L 2563 70L 1414 70L 28159L 2562 9L 1644 9L 28579L 2555 9L 1641 9L 2856

32L 2290 9L 1602 9L 285532L 2390 9L 1589 9L 285532L 2510 9L 1526 9L 285332L 2470 9L 1492 9L 284616L 2380 32L 1470 32L 265016L 2530 32L 1520 32L 271016L 2400 32L 1540 32L 271016L 2500 32L 1600 32L 280016L 2420 16L 1400 16L 284016L 2410 16L 1440 16L 2840

16L 1470 16L 286016L 1510 16L 287016L 1360 16L 287016L 1390 16L 2880

Sample Sewage Sludge 2 Sample Soil 4 Sample Soil 5Element TOC [gkg] Element TOC [gkg] Element TOC [gkg]

LAB PARM LAB PARM LAB PARM19L 2308 19L 1720 19L 225019L 2303 19L 1700 19L 223019L 2239 19L 1690 19L 221019L 2204 19L 1670 19L 211019L 2192 19L 1640 19L 210019L 2096 19L 1580 19L 206034L 2631 30L 1790 34L 244334L 2471 30L 1770 34L 233434L 2977 30L 1700 34L 231534L 2785 34L 1740 34L 222134L 2780 34L 1692 34L 217634L 2668 34L 1727 34L 207335L 2179 34L 1767 35L 233035L 2160 34L 1777 35L 208035L 2158 34L 1783 35L 201035L 2132 35L 1700 35L 198035L 2119 35L 1650 35L 193035L 2094 35L 1650 35L 178036L 2096 35L 1640 36L 254036L 2069 35L 1630 36L 253436L 2052 35L 1630 36L 179044L 2325 36L 1500 44L 302144L 2309 36L 1497 44L 298244L 2307 36L 1417 44L 295644L 2305 44L 1594 44L 30744L 2287 44L 1587 44L 30044L 2283 44L 1584 44L 29745L 2331 44L 1574 45L 214945L 2327 44L 1573 45L 209245L 2308 44L 1562 45L 203345L 2287 45L 1827 45L 197145L 2234 45L 1709 45L 193345L 2113 45L 1666 45L 184146L 190 45L 1665 56L 223746L 180 45L 1664 56L 222246L 180 45L 1600 56L 220346L 180 46L 2300 56L 206956L 2204 46L 2300 56L 206856L 2197 46L 2300 56L 204456L 2193 46L 2200 65L 192056L 2185 56L 1668 65L 182056L 2183 56L 1654 65L 179056L 2167 56L 1653 65L 172065L 2136 56L 1643 66L 254365L 2091 56L 1639 66L 242465L 2065 56L 1638 66L 232165L 2047 65L 1630 66L 226266L 2105 65L 1560 70L 2213966L 2022 65L 1530 9L 218066L 2009 65L 1490 9L 214066L 1983 66L 2179 9L 213070L 2272 66L 1900 9L 21109L 2385 66L 1762 9L 20709L 2377 66L 1734 9L 20709L 2375 70L 10404 32L 20509L 2359 9L 1640 32L 21009L 2356 9L 1640 32L 20209L 2354 9L 1610 32L 1960

32L 2240 9L 1590 16L 210032L 2260 9L 1590 16L 220032L 2200 9L 1560 16L 220032L 2270 32L 1640 16L 206016L 2300 32L 1600 16L 197016L 2310 32L 1560 16L 201016L 2350 32L 157016L 2260 16L 170016L 2290 16L 180016L 2240 16L 1700

16L 180016L 170016L 1700

European Commission EUR 23012 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on total organic carbon Author(s) E Sobiecka H van der Sloot K Andersen B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 50 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07412-7 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 total organic carbon (TOC) in soils sludge and treated bio-waste 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

-23012-EN

-C

13

14 Annexes Annex 1 Model questionnaire to be filled by the participating laboratories Annex 2 Report on the validation materials used Annex 3 Statistical calculations Annex 4 Data submitted

14

14

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

15

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

16

Annex 3

Statistical calculations

Unit gkg

Mandels k statistics(Compost 1 - TOC)Mandels h statistics(Compost 1 - TOC)

Sample Compost 1 Compost 1 - TOC -- Mean PARM = 2463 [gkg]

Element TOC

General calcparmT1= 142643E+04T2= 351264E+06T3= 58T4= 292T5= 16501E+03

n= variabelp= 13

N-table= 5

Mandels statistics End ResultLAB 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

69L 1960000 64265 4 -235 352 Fail - - 69L - - -502735L 2291667 1674 6 -081 009 2291667 16741 6 5 -171066L 2377425 8552 4 -041 047 2377425 85518 4 3 -85346L 2395000 4796 4 -033 026 2395000 47958 4 3 -67756L 2401227 3133 6 -030 017 2401227 31330 6 5 -61432L 2415000 9713 4 -024 053 2415000 97125 4 3 -47770L 2435100 - 1 -014 2435100 - 1 -27616L 2440000 6033 6 -012 033 2440000 60332 6 5 -22745L 2503800 11759 6 018 064 2503800 117589 6 5 41136L 2514416 3994 3 023 022 2514416 39937 3 2 51765L 2537333 5216 3 033 029 2537333 52157 3 2 74744L 2555667 2783 6 042 015 2555667 27826 6 5 9309L 2568167 1356 6 048 007 2568167 13556 6 5 105530L 2580000 2000 3 053 011 2580000 20000 3 2 117334L 3013269 9580 6 255 053 Fail - - 34L - - 5506

Totgem 246587 9632 gkg 1-level 232 (176) 13 2462677 (34L 69L) 13 12Totstd= 21507 16070 5-level 186 (152) 2

68RESULTS Mean = 24626770 gkg

Repeatability variance S2r = 3666797Repeatability std Sr = 605541 --gt 246 r = 169551Between lab variance S2L = 7715586Reproducibility var S2R = 11382383Reproducibility std SR = 1066882 --gt 433 R = 298727Remarks 2 Labs rejected (34L 69L)

000 050 100 150 200 250 300 350 400

k-values

69L

35L

66L

46L

56L

32L

70L

16L

45L

36L

65L

44L

9L

30L

34L

Mandels k statistics(Compost 1 - TOC)

-600 -400 -200 00 200 400 600

Deviation from Mean

69L

35L

66L

46L

56L

32L

70L

16L

45L

36L

65L

44L

9L

30L

34L

Labo

rato

ries

Compost 1 - TOC -- Mean PARM = 2463 [gkg]

-300 -200 -100 000 100 200 300

h-values

69L

66L

56L

70L

45L

65L

9L

34L

Labo

rato

ries

Mandels h statistics(Compost 1 - TOC)

Compost 1-TOC

Unit gkg

Mandels k statistics(Compost 2 - TOC)Mandels h statistics(Compost 2 - TOC)

Sample Compost 2 Compost 2 - TOC -- Mean PARM = 1542 [gkg]

Element TOC

General calcparmT1= 994897E+03T2= 155556E+06T3= 64T4= 346T5= 41738E+03

n= variabelp= 13

N-table= 5

Mandels statistics End ResultLAB 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

45L 1326733 5665 6 -100 042 Fail 1326733 56646 6 5 -215046L 1355000 24365 4 -089 181 Fail - - 46L - - -186736L 1381949 5407 3 -078 040 Fail 1381949 54070 3 2 -159870L 1414120 - 1 -066 Fail 1414120 - 1 -127616L 1428333 5565 6 -061 041 1428333 55648 6 5 -113466L 1485550 7805 4 -039 058 1485550 78047 4 3 -56232L 1532500 5377 4 -021 040 1532500 53774 4 3 -09219L 1576833 10138 6 -004 075 1576833 101381 6 5 3519L 1582333 6166 6 -002 046 1582333 61659 6 5 40656L 1594432 4046 6 003 030 1594432 40463 6 5 52744L 1653000 3651 6 025 027 1653000 36508 6 5 111334L 1655127 13717 6 026 102 1655127 137168 6 5 113434L 1655127 13717 6 026 102 1655127 137168 6 5 113465L 1756500 16295 4 065 121 Fail 1756500 162949 4 3 214869L 2415000 30687 4 316 228 Fail - - 69L - - 8733

Totgem 158750 10900 gkg 1-level 232 (176) 13 1541734 (46L 69L) 13 12Totstd= 26187 8164 5-level 186 (152) 2

72RESULTS Mean = 15417337 gkg

Repeatability variance S2r = 8183950Repeatability std Sr = 904652 --gt 587 r = 253303Between lab variance S2L = 13631046Reproducibility var S2R = 21814995Reproducibility std SR = 1476990 --gt 958 R = 413557Remarks 2 Labs rejected (46L 69L)

000 050 100 150 200 250

k-values

45L

46L

36L

70L

16L

66L

32L

19L

9L

56L

44L

34L

34L

65L

69L

Mandels k statistics(Compost 2 - TOC)

-400 -200 00 200 400 600 800 1000

Deviation from Mean

45L

46L

36L

70L

16L

66L

32L

19L

9L

56L

44L

34L

34L

65L

69L

Labo

rato

ries

Compost 2 - TOC -- Mean PARM = 1542 [gkg]

-100 000 100 200 300 400

h-values

45L

36L

16L

32L

9L

44L

34L

69L

Labo

rato

ries

Mandels h statistics(Compost 2 - TOC)

Compost 2-TOC

Unit gkg

Mandels k statistics(Sludge 1 - TOC)Mandels h statistics(Sludge 1 - TOC)

Sample Sludge 1 Sludge 1 - TOC -- Mean PARM = 2721 [gkg]

Element TOC

General calcparmT1= 169626E+04T2= 465445E+06T3= 62T4= 326T5= 10312E+03

n= variabelp= 13

N-table= 5

Mandels statistics End ResultLAB 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

69L 233000 2362 4 -347 037 Fail - - 69L - - -2488046L 2312500 2062 4 -040 032 Fail 2312500 20616 4 3 -408565L 2615500 1708 4 004 026 2615500 17078 4 3 -105566L 2627200 8268 4 006 128 2627200 82678 4 3 -93836L 2664041 4976 3 011 077 2664041 49758 3 2 -56935L 2671500 3533 6 013 055 2671500 35331 6 5 -49556L 2692298 0874 6 016 014 Fail 2692298 08738 6 5 -28732L 2717500 6185 4 019 096 Fail 2717500 61847 4 3 -03519L 2753333 7819 6 025 121 Fail 2753333 78189 6 5 32470L 2814600 - 1 034 Fail 2814600 - 1 9369L 2853667 0398 6 039 006 Fail 2853667 03983 6 5 132716L 2860000 1673 6 040 026 Fail 2860000 16733 6 5 139045L 2884433 7033 6 044 109 Fail 2884433 70331 6 5 163544L 2906167 1129 6 047 017 Fail 2906167 11286 6 5 185234L 3186874 17674 6 089 274 Fail - - 34L - - 4659

Totgem 258617 4692 gkg 1-level 232 (176) 13 2720980 (34L 69L) 13 12Totstd= 67800 4610 5-level 186 (152) 2

72RESULTS Mean = 27209799 gkg

Repeatability variance S2r = 2104538Repeatability std Sr = 458752 --gt 169 r = 128451Between lab variance S2L = 23618387Reproducibility var S2R = 25722925Reproducibility std SR = 1603837 --gt 589 R = 449074Remarks 2 Labs rejected (34L 69L)

000 050 100 150 200 250 300

k-values

69L

46L

65L

66L

36L

35L

56L

32L

19L

70L

9L

16L

45L

44L

34L

Mandels k statistics(Sludge 1 - TOC)

-2500 -2000 -1500 -1000 -500 00 500

Deviation from Mean

69L

46L

65L

66L

36L

35L

56L

32L

19L

70L

9L

16L

45L

44L

34L

Labo

rato

ries

Sludge 1 - TOC -- Mean PARM = 2721 [gkg]

-400 -300 -200 -100 000 100

h-values

69L

65L

36L

56L

19L

9L

45L

34L

Labo

rato

ries

Mandels h statistics(Sludge 1 - TOC)

Sludge 1-TOC

68 Unit gkg

Mandels k statistics(Sludge 2 - TOC)Mandels h statistics(Sludge 2 - TOC)

Sample Sludge 2 Sludge 2 - TOC -- Mean PARM = 2207 [gkg]

Element TOC

General calcparmT1= 128601E+04T2= 285689E+06T3= 58T4= 310T5= 97826E+02

n= variabelp= 12

N-table= 5

Mandels statistics End ResultLAB 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

46L 182500 0500 4 -333 008 Fail - - 46L - - -2024466L 2029475 5267 4 -012 084 2029475 52674 4 3 -177436L 2072609 2222 3 -005 035 2072609 22222 3 2 -134365L 2084750 3865 4 -002 062 2084750 38647 4 3 -122135L 2140333 3119 6 007 050 2140333 31194 6 5 -66556L 2188021 1282 6 015 020 2188021 12822 6 5 -18819L 2223667 7916 6 022 126 Fail 2223667 79157 6 5 16832L 2242500 3096 4 025 049 Fail 2242500 30957 4 3 35645L 2266600 8322 6 029 132 Fail 2266600 83216 6 5 59770L 2272460 - 1 030 Fail 2272460 - 1 65616L 2291667 3869 6 033 062 Fail 2291667 38687 6 5 84844L 2302667 1546 6 035 025 Fail 2302667 15462 6 5 9589L 2367667 1296 6 047 021 Fail 2367667 12956 6 5 160834L 2718591 17124 6 108 273 Fail - - 34L - - 5117

Totgem 209882 4571 gkg 1-level 230 (176) 12 2206868 (34L 46L) 12 11Totstd= 57628 4485 5-level 185 (151) 2

68RESULTS Mean = 22068679 gkg

Repeatability variance S2r = 2126659Repeatability std Sr = 461157 --gt 209 r = 129124Between lab variance S2L = 9960432Reproducibility var S2R = 12087091Reproducibility std SR = 1099413 --gt 498 R = 307836Remarks 2 Labs rejected (34L 46L)

000 050 100 150 200 250 300

k-values

46L

66L

36L

65L

35L

56L

19L

32L

45L

70L

16L

44L

9L

34L

Mandels k statistics(Sludge 2 - TOC)

-2500 -2000 -1500 -1000 -500 00 500 1000

Deviation from Mean

46L

66L

36L

65L

35L

56L

19L

32L

45L

70L

16L

44L

9L

34L

Labo

rato

ries

Sludge 2 - TOC -- Mean PARM = 2207 [gkg]

-400 -300 -200 -100 000 100 200

h-values

46L

66L

36L

65L

35L

56L

19L

32L

45L

70L

16L

44L

9L

34L

Labo

rato

ries

Mandels h statistics(Sludge 2 - TOC)

Sludge 2-TOC

Unit gkg

Mandels k statistics(Soil 4 - TOC)Mandels h statistics(Soil 4 - TOC)

Sample Soil 4 Soil 4 - TOC -- Mean PARM = 1641 [gkg]

Element TOC

General calcparmT1= 102171E+03T2= 168700E+04T3= 62T4= 338T5= 94040E+00

n= variabelp= 12

N-table= 5

Mandels statistics End ResultLAB 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

36L 147161 0470 3 -036 068 Fail 147161 04702 3 2 -16965L 155250 0591 4 -032 085 Fail 155250 05909 4 3 -08844L 157900 0115 6 -031 017 Fail 157900 01152 6 5 -06232L 159250 0359 4 -031 052 Fail 159250 03594 4 3 -0489L 160500 0315 6 -030 045 Fail 160500 03146 6 5 -03656L 164927 0113 6 -028 016 Fail 164927 01127 6 5 00835L 165000 0261 6 -028 038 Fail 165000 02608 6 5 00919L 166667 0505 6 -027 073 Fail 166667 05046 6 5 02645L 168850 0763 6 -026 110 Fail 168850 07628 6 5 04816L 173333 0516 6 -024 074 Fail 173333 05164 6 5 09334L 174761 0346 6 -024 050 Fail 174761 03462 6 5 10730L 175333 0473 3 -024 068 Fail 175333 04726 3 2 11366L 189375 2035 4 -017 294 Fail - - 66L - - 25346L 227500 0500 4 000 072 - - 46L - - 63470L 1040400 - 1 360 Fail - - 70L - - 8763

Totgem 22841 0526 gkg 1-level 232 (176) 12 164078 (46L 66L70L) 12 11Totstd= 22541 0469 5-level 186 (152) 3

71RESULTS Mean = 1640777 gkg

Repeatability variance S2r = 018808Repeatability std Sr = 043368 --gt 264 r = 12143Between lab variance S2L = 054747Reproducibility var S2R = 073555Reproducibility std SR = 085764 --gt 523 R = 24014Remarks 3 Labs rejected (46L 66L70L)

000 050 100 150 200 250 300

k-values

36L

65L

44L

32L

9L

56L

35L

19L

45L

16L

34L

30L

66L

46L

70L

Mandels k statistics(Soil 4 - TOC)

-100 00 100 200 300 400 500 600 700 800 900

Deviation from Mean

36L

65L

44L

32L

9L

56L

35L

19L

45L

16L

34L

30L

66L

46L

70L

Labo

rato

ries

Soil 4 - TOC -- Mean PARM = 1641 [gkg]

-100 000 100 200 300 400

h-values

36L

44L

9L

35L

45L

34L

66L

70L

Labo

rato

ries

Mandels h statistics(Soil 4 - TOC)

Soil 4-TOC

Unit gkg

Mandels k statistics(Soil 5 - TOC)Mandels h statistics(Soil 5 - TOC)

Sample Soil 5 Soil 5 - TOC -- Mean PARM = 2102 [gkg]

Element TOC

General calcparmT1= 113661E+03T2= 240201E+04T3= 54T4= 300T5= 51756E+01

n= variabelp= 10

N-table= 5

Mandels statistics End ResultLAB 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

44L 164383 14708 6 -036 325 Fail - - 44L - - -45865L 181250 0830 4 -033 018 Fail 181250 08302 4 3 -29045L 200317 1116 6 -029 025 Fail 200317 11163 6 5 -09935L 201833 1828 6 -029 040 Fail 201833 18280 6 5 -08432L 203250 0585 4 -029 013 Fail 203250 05852 4 3 -07016L 209000 0959 6 -028 021 Fail 209000 09592 6 5 -0129L 211667 0427 6 -027 009 Fail 211667 04274 6 5 01556L 214030 0887 6 -027 020 Fail 214030 08868 6 5 03819L 216000 0795 6 -026 018 Fail 216000 07950 6 5 05834L 226009 1308 6 -024 029 Fail 226009 13076 6 5 15836L 228783 4310 3 -024 095 Fail - - 36L - - 18666L 238750 1234 4 -022 027 Fail 238750 12340 4 3 28570L 2213900 - 1 333 Fail - - 70L - - 20037

Totgem 36224 2416 gkg 1-level 227 (175) 10 210211 (36L44L 70L) 10 9Totstd= 55669 4003 5-level 184 (151) 3

64RESULTS Mean = 2102106 gkg

Repeatability variance S2r = 117627Repeatability std Sr = 108456 --gt 516 r = 30368Between lab variance S2L = 176699Reproducibility var S2R = 294326Reproducibility std SR = 171559 --gt 816 R = 48037Remarks 3 Labs rejected (36L44L 70L)

000 050 100 150 200 250 300 350

k-values

44L

65L

45L

35L

32L

16L

9L

56L

19L

34L

36L

66L

70L

Mandels k statistics(Soil 5 - TOC)

-500 00 500 1000 1500 2000 2500

Deviation from Mean

44L

65L

45L

35L

32L

16L

9L

56L

19L

34L

36L

66L

70L

Labo

rato

ries

Soil 5 - TOC -- Mean PARM = 2102 [gkg]

-100 000 100 200 300 400

h-values

44L

65L

45L

35L

32L

16L

9L

56L

19L

34L

36L

66L

70L

Labo

rato

ries

Mandels h statistics(Soil 5 - TOC)

Soil 5-TOC

17

Annex 4

Raw data submitted

Sample Compost 1 Sample Compost 2 Sample Sewage Sludge 1Element TOC [gkg] Element TOC [gkg] Element TOC [gkg]

LAB PARM LAB PARM LAB PARM30L 2600 19L 1691 19L 286730L 2580 19L 1634 19L 281430L 2560 19L 1619 19L 276934L 2969 19L 1604 19L 272034L 2936 19L 1499 19L 268834L 2958 19L 1414 19L 266234L 2994 34L 1527 34L 315234L 3199 34L 1622 34L 314934L 3024 34L 1519 34L 343035L 2306 34L 1753 34L 336535L 2300 34L 1636 34L 304235L 2298 34L 1874 34L 298335L 2296 35L 1506 35L 270735L 2291 35L 1312 35L 270335L 2259 35L 1294 35L 268836L 2546 35L 1279 35L 267436L 2527 35L 1191 35L 263136L 2470 35L 1177 35L 262644L 2583 36L 1418 36L 271344L 2581 36L 1408 36L 266544L 2578 36L 1320 36L 261444L 2539 44L 1719 44L 292044L 2528 44L 1664 44L 291644L 2525 44L 1654 44L 291245L 2658 44L 1637 44L 290045L 2600 44L 1624 44L 289645L 2546 44L 1620 44L 289345L 2461 45L 1428 45L 297645L 2409 45L 1325 45L 295245L 2350 45L 1323 45L 288546L 2460 45L 1321 45L 286646L 2400 45L 1309 45L 284046L 2370 45L 1253 45L 278746L 2350 46L 1580 46L 233056L 2436 46L 1550 46L 233056L 2435 46L 1170 46L 230056L 2405 46L 1120 46L 229056L 2397 56L 1642 56L 270256L 2375 56L 1626 56L 270156L 2358 56L 1622 56L 269465L 2587 56L 1571 56L 269365L 2542 56L 1561 56L 268465L 2483 56L 1545 56L 268066L 2454 65L 1933 65L 264166L 2429 65L 1838 65L 260966L 2365 65L 1693 65L 260766L 2262 65L 1562 65L 260569L 2730 66L 1561 66L 270169L 2250 66L 1545 66L 267469L 1440 66L 1420 66L 261969L 1420 66L 1417 66L 251470L 2435 69L 2700 69L 2639L 2594 69L 2660 69L 2409L 2570 69L 2170 69L 2199L 2565 69L 2130 69L 2109L 2563 70L 1414 70L 28159L 2562 9L 1644 9L 28579L 2555 9L 1641 9L 2856

32L 2290 9L 1602 9L 285532L 2390 9L 1589 9L 285532L 2510 9L 1526 9L 285332L 2470 9L 1492 9L 284616L 2380 32L 1470 32L 265016L 2530 32L 1520 32L 271016L 2400 32L 1540 32L 271016L 2500 32L 1600 32L 280016L 2420 16L 1400 16L 284016L 2410 16L 1440 16L 2840

16L 1470 16L 286016L 1510 16L 287016L 1360 16L 287016L 1390 16L 2880

Sample Sewage Sludge 2 Sample Soil 4 Sample Soil 5Element TOC [gkg] Element TOC [gkg] Element TOC [gkg]

LAB PARM LAB PARM LAB PARM19L 2308 19L 1720 19L 225019L 2303 19L 1700 19L 223019L 2239 19L 1690 19L 221019L 2204 19L 1670 19L 211019L 2192 19L 1640 19L 210019L 2096 19L 1580 19L 206034L 2631 30L 1790 34L 244334L 2471 30L 1770 34L 233434L 2977 30L 1700 34L 231534L 2785 34L 1740 34L 222134L 2780 34L 1692 34L 217634L 2668 34L 1727 34L 207335L 2179 34L 1767 35L 233035L 2160 34L 1777 35L 208035L 2158 34L 1783 35L 201035L 2132 35L 1700 35L 198035L 2119 35L 1650 35L 193035L 2094 35L 1650 35L 178036L 2096 35L 1640 36L 254036L 2069 35L 1630 36L 253436L 2052 35L 1630 36L 179044L 2325 36L 1500 44L 302144L 2309 36L 1497 44L 298244L 2307 36L 1417 44L 295644L 2305 44L 1594 44L 30744L 2287 44L 1587 44L 30044L 2283 44L 1584 44L 29745L 2331 44L 1574 45L 214945L 2327 44L 1573 45L 209245L 2308 44L 1562 45L 203345L 2287 45L 1827 45L 197145L 2234 45L 1709 45L 193345L 2113 45L 1666 45L 184146L 190 45L 1665 56L 223746L 180 45L 1664 56L 222246L 180 45L 1600 56L 220346L 180 46L 2300 56L 206956L 2204 46L 2300 56L 206856L 2197 46L 2300 56L 204456L 2193 46L 2200 65L 192056L 2185 56L 1668 65L 182056L 2183 56L 1654 65L 179056L 2167 56L 1653 65L 172065L 2136 56L 1643 66L 254365L 2091 56L 1639 66L 242465L 2065 56L 1638 66L 232165L 2047 65L 1630 66L 226266L 2105 65L 1560 70L 2213966L 2022 65L 1530 9L 218066L 2009 65L 1490 9L 214066L 1983 66L 2179 9L 213070L 2272 66L 1900 9L 21109L 2385 66L 1762 9L 20709L 2377 66L 1734 9L 20709L 2375 70L 10404 32L 20509L 2359 9L 1640 32L 21009L 2356 9L 1640 32L 20209L 2354 9L 1610 32L 1960

32L 2240 9L 1590 16L 210032L 2260 9L 1590 16L 220032L 2200 9L 1560 16L 220032L 2270 32L 1640 16L 206016L 2300 32L 1600 16L 197016L 2310 32L 1560 16L 201016L 2350 32L 157016L 2260 16L 170016L 2290 16L 180016L 2240 16L 1700

16L 180016L 170016L 1700

European Commission EUR 23012 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on total organic carbon Author(s) E Sobiecka H van der Sloot K Andersen B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 50 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07412-7 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 total organic carbon (TOC) in soils sludge and treated bio-waste 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

-23012-EN

-C

14

14

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

15

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

16

Annex 3

Statistical calculations

Unit gkg

Mandels k statistics(Compost 1 - TOC)Mandels h statistics(Compost 1 - TOC)

Sample Compost 1 Compost 1 - TOC -- Mean PARM = 2463 [gkg]

Element TOC

General calcparmT1= 142643E+04T2= 351264E+06T3= 58T4= 292T5= 16501E+03

n= variabelp= 13

N-table= 5

Mandels statistics End ResultLAB 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

69L 1960000 64265 4 -235 352 Fail - - 69L - - -502735L 2291667 1674 6 -081 009 2291667 16741 6 5 -171066L 2377425 8552 4 -041 047 2377425 85518 4 3 -85346L 2395000 4796 4 -033 026 2395000 47958 4 3 -67756L 2401227 3133 6 -030 017 2401227 31330 6 5 -61432L 2415000 9713 4 -024 053 2415000 97125 4 3 -47770L 2435100 - 1 -014 2435100 - 1 -27616L 2440000 6033 6 -012 033 2440000 60332 6 5 -22745L 2503800 11759 6 018 064 2503800 117589 6 5 41136L 2514416 3994 3 023 022 2514416 39937 3 2 51765L 2537333 5216 3 033 029 2537333 52157 3 2 74744L 2555667 2783 6 042 015 2555667 27826 6 5 9309L 2568167 1356 6 048 007 2568167 13556 6 5 105530L 2580000 2000 3 053 011 2580000 20000 3 2 117334L 3013269 9580 6 255 053 Fail - - 34L - - 5506

Totgem 246587 9632 gkg 1-level 232 (176) 13 2462677 (34L 69L) 13 12Totstd= 21507 16070 5-level 186 (152) 2

68RESULTS Mean = 24626770 gkg

Repeatability variance S2r = 3666797Repeatability std Sr = 605541 --gt 246 r = 169551Between lab variance S2L = 7715586Reproducibility var S2R = 11382383Reproducibility std SR = 1066882 --gt 433 R = 298727Remarks 2 Labs rejected (34L 69L)

000 050 100 150 200 250 300 350 400

k-values

69L

35L

66L

46L

56L

32L

70L

16L

45L

36L

65L

44L

9L

30L

34L

Mandels k statistics(Compost 1 - TOC)

-600 -400 -200 00 200 400 600

Deviation from Mean

69L

35L

66L

46L

56L

32L

70L

16L

45L

36L

65L

44L

9L

30L

34L

Labo

rato

ries

Compost 1 - TOC -- Mean PARM = 2463 [gkg]

-300 -200 -100 000 100 200 300

h-values

69L

66L

56L

70L

45L

65L

9L

34L

Labo

rato

ries

Mandels h statistics(Compost 1 - TOC)

Compost 1-TOC

Unit gkg

Mandels k statistics(Compost 2 - TOC)Mandels h statistics(Compost 2 - TOC)

Sample Compost 2 Compost 2 - TOC -- Mean PARM = 1542 [gkg]

Element TOC

General calcparmT1= 994897E+03T2= 155556E+06T3= 64T4= 346T5= 41738E+03

n= variabelp= 13

N-table= 5

Mandels statistics End ResultLAB 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

45L 1326733 5665 6 -100 042 Fail 1326733 56646 6 5 -215046L 1355000 24365 4 -089 181 Fail - - 46L - - -186736L 1381949 5407 3 -078 040 Fail 1381949 54070 3 2 -159870L 1414120 - 1 -066 Fail 1414120 - 1 -127616L 1428333 5565 6 -061 041 1428333 55648 6 5 -113466L 1485550 7805 4 -039 058 1485550 78047 4 3 -56232L 1532500 5377 4 -021 040 1532500 53774 4 3 -09219L 1576833 10138 6 -004 075 1576833 101381 6 5 3519L 1582333 6166 6 -002 046 1582333 61659 6 5 40656L 1594432 4046 6 003 030 1594432 40463 6 5 52744L 1653000 3651 6 025 027 1653000 36508 6 5 111334L 1655127 13717 6 026 102 1655127 137168 6 5 113434L 1655127 13717 6 026 102 1655127 137168 6 5 113465L 1756500 16295 4 065 121 Fail 1756500 162949 4 3 214869L 2415000 30687 4 316 228 Fail - - 69L - - 8733

Totgem 158750 10900 gkg 1-level 232 (176) 13 1541734 (46L 69L) 13 12Totstd= 26187 8164 5-level 186 (152) 2

72RESULTS Mean = 15417337 gkg

Repeatability variance S2r = 8183950Repeatability std Sr = 904652 --gt 587 r = 253303Between lab variance S2L = 13631046Reproducibility var S2R = 21814995Reproducibility std SR = 1476990 --gt 958 R = 413557Remarks 2 Labs rejected (46L 69L)

000 050 100 150 200 250

k-values

45L

46L

36L

70L

16L

66L

32L

19L

9L

56L

44L

34L

34L

65L

69L

Mandels k statistics(Compost 2 - TOC)

-400 -200 00 200 400 600 800 1000

Deviation from Mean

45L

46L

36L

70L

16L

66L

32L

19L

9L

56L

44L

34L

34L

65L

69L

Labo

rato

ries

Compost 2 - TOC -- Mean PARM = 1542 [gkg]

-100 000 100 200 300 400

h-values

45L

36L

16L

32L

9L

44L

34L

69L

Labo

rato

ries

Mandels h statistics(Compost 2 - TOC)

Compost 2-TOC

Unit gkg

Mandels k statistics(Sludge 1 - TOC)Mandels h statistics(Sludge 1 - TOC)

Sample Sludge 1 Sludge 1 - TOC -- Mean PARM = 2721 [gkg]

Element TOC

General calcparmT1= 169626E+04T2= 465445E+06T3= 62T4= 326T5= 10312E+03

n= variabelp= 13

N-table= 5

Mandels statistics End ResultLAB 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

69L 233000 2362 4 -347 037 Fail - - 69L - - -2488046L 2312500 2062 4 -040 032 Fail 2312500 20616 4 3 -408565L 2615500 1708 4 004 026 2615500 17078 4 3 -105566L 2627200 8268 4 006 128 2627200 82678 4 3 -93836L 2664041 4976 3 011 077 2664041 49758 3 2 -56935L 2671500 3533 6 013 055 2671500 35331 6 5 -49556L 2692298 0874 6 016 014 Fail 2692298 08738 6 5 -28732L 2717500 6185 4 019 096 Fail 2717500 61847 4 3 -03519L 2753333 7819 6 025 121 Fail 2753333 78189 6 5 32470L 2814600 - 1 034 Fail 2814600 - 1 9369L 2853667 0398 6 039 006 Fail 2853667 03983 6 5 132716L 2860000 1673 6 040 026 Fail 2860000 16733 6 5 139045L 2884433 7033 6 044 109 Fail 2884433 70331 6 5 163544L 2906167 1129 6 047 017 Fail 2906167 11286 6 5 185234L 3186874 17674 6 089 274 Fail - - 34L - - 4659

Totgem 258617 4692 gkg 1-level 232 (176) 13 2720980 (34L 69L) 13 12Totstd= 67800 4610 5-level 186 (152) 2

72RESULTS Mean = 27209799 gkg

Repeatability variance S2r = 2104538Repeatability std Sr = 458752 --gt 169 r = 128451Between lab variance S2L = 23618387Reproducibility var S2R = 25722925Reproducibility std SR = 1603837 --gt 589 R = 449074Remarks 2 Labs rejected (34L 69L)

000 050 100 150 200 250 300

k-values

69L

46L

65L

66L

36L

35L

56L

32L

19L

70L

9L

16L

45L

44L

34L

Mandels k statistics(Sludge 1 - TOC)

-2500 -2000 -1500 -1000 -500 00 500

Deviation from Mean

69L

46L

65L

66L

36L

35L

56L

32L

19L

70L

9L

16L

45L

44L

34L

Labo

rato

ries

Sludge 1 - TOC -- Mean PARM = 2721 [gkg]

-400 -300 -200 -100 000 100

h-values

69L

65L

36L

56L

19L

9L

45L

34L

Labo

rato

ries

Mandels h statistics(Sludge 1 - TOC)

Sludge 1-TOC

68 Unit gkg

Mandels k statistics(Sludge 2 - TOC)Mandels h statistics(Sludge 2 - TOC)

Sample Sludge 2 Sludge 2 - TOC -- Mean PARM = 2207 [gkg]

Element TOC

General calcparmT1= 128601E+04T2= 285689E+06T3= 58T4= 310T5= 97826E+02

n= variabelp= 12

N-table= 5

Mandels statistics End ResultLAB 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

46L 182500 0500 4 -333 008 Fail - - 46L - - -2024466L 2029475 5267 4 -012 084 2029475 52674 4 3 -177436L 2072609 2222 3 -005 035 2072609 22222 3 2 -134365L 2084750 3865 4 -002 062 2084750 38647 4 3 -122135L 2140333 3119 6 007 050 2140333 31194 6 5 -66556L 2188021 1282 6 015 020 2188021 12822 6 5 -18819L 2223667 7916 6 022 126 Fail 2223667 79157 6 5 16832L 2242500 3096 4 025 049 Fail 2242500 30957 4 3 35645L 2266600 8322 6 029 132 Fail 2266600 83216 6 5 59770L 2272460 - 1 030 Fail 2272460 - 1 65616L 2291667 3869 6 033 062 Fail 2291667 38687 6 5 84844L 2302667 1546 6 035 025 Fail 2302667 15462 6 5 9589L 2367667 1296 6 047 021 Fail 2367667 12956 6 5 160834L 2718591 17124 6 108 273 Fail - - 34L - - 5117

Totgem 209882 4571 gkg 1-level 230 (176) 12 2206868 (34L 46L) 12 11Totstd= 57628 4485 5-level 185 (151) 2

68RESULTS Mean = 22068679 gkg

Repeatability variance S2r = 2126659Repeatability std Sr = 461157 --gt 209 r = 129124Between lab variance S2L = 9960432Reproducibility var S2R = 12087091Reproducibility std SR = 1099413 --gt 498 R = 307836Remarks 2 Labs rejected (34L 46L)

000 050 100 150 200 250 300

k-values

46L

66L

36L

65L

35L

56L

19L

32L

45L

70L

16L

44L

9L

34L

Mandels k statistics(Sludge 2 - TOC)

-2500 -2000 -1500 -1000 -500 00 500 1000

Deviation from Mean

46L

66L

36L

65L

35L

56L

19L

32L

45L

70L

16L

44L

9L

34L

Labo

rato

ries

Sludge 2 - TOC -- Mean PARM = 2207 [gkg]

-400 -300 -200 -100 000 100 200

h-values

46L

66L

36L

65L

35L

56L

19L

32L

45L

70L

16L

44L

9L

34L

Labo

rato

ries

Mandels h statistics(Sludge 2 - TOC)

Sludge 2-TOC

Unit gkg

Mandels k statistics(Soil 4 - TOC)Mandels h statistics(Soil 4 - TOC)

Sample Soil 4 Soil 4 - TOC -- Mean PARM = 1641 [gkg]

Element TOC

General calcparmT1= 102171E+03T2= 168700E+04T3= 62T4= 338T5= 94040E+00

n= variabelp= 12

N-table= 5

Mandels statistics End ResultLAB 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

36L 147161 0470 3 -036 068 Fail 147161 04702 3 2 -16965L 155250 0591 4 -032 085 Fail 155250 05909 4 3 -08844L 157900 0115 6 -031 017 Fail 157900 01152 6 5 -06232L 159250 0359 4 -031 052 Fail 159250 03594 4 3 -0489L 160500 0315 6 -030 045 Fail 160500 03146 6 5 -03656L 164927 0113 6 -028 016 Fail 164927 01127 6 5 00835L 165000 0261 6 -028 038 Fail 165000 02608 6 5 00919L 166667 0505 6 -027 073 Fail 166667 05046 6 5 02645L 168850 0763 6 -026 110 Fail 168850 07628 6 5 04816L 173333 0516 6 -024 074 Fail 173333 05164 6 5 09334L 174761 0346 6 -024 050 Fail 174761 03462 6 5 10730L 175333 0473 3 -024 068 Fail 175333 04726 3 2 11366L 189375 2035 4 -017 294 Fail - - 66L - - 25346L 227500 0500 4 000 072 - - 46L - - 63470L 1040400 - 1 360 Fail - - 70L - - 8763

Totgem 22841 0526 gkg 1-level 232 (176) 12 164078 (46L 66L70L) 12 11Totstd= 22541 0469 5-level 186 (152) 3

71RESULTS Mean = 1640777 gkg

Repeatability variance S2r = 018808Repeatability std Sr = 043368 --gt 264 r = 12143Between lab variance S2L = 054747Reproducibility var S2R = 073555Reproducibility std SR = 085764 --gt 523 R = 24014Remarks 3 Labs rejected (46L 66L70L)

000 050 100 150 200 250 300

k-values

36L

65L

44L

32L

9L

56L

35L

19L

45L

16L

34L

30L

66L

46L

70L

Mandels k statistics(Soil 4 - TOC)

-100 00 100 200 300 400 500 600 700 800 900

Deviation from Mean

36L

65L

44L

32L

9L

56L

35L

19L

45L

16L

34L

30L

66L

46L

70L

Labo

rato

ries

Soil 4 - TOC -- Mean PARM = 1641 [gkg]

-100 000 100 200 300 400

h-values

36L

44L

9L

35L

45L

34L

66L

70L

Labo

rato

ries

Mandels h statistics(Soil 4 - TOC)

Soil 4-TOC

Unit gkg

Mandels k statistics(Soil 5 - TOC)Mandels h statistics(Soil 5 - TOC)

Sample Soil 5 Soil 5 - TOC -- Mean PARM = 2102 [gkg]

Element TOC

General calcparmT1= 113661E+03T2= 240201E+04T3= 54T4= 300T5= 51756E+01

n= variabelp= 10

N-table= 5

Mandels statistics End ResultLAB 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

44L 164383 14708 6 -036 325 Fail - - 44L - - -45865L 181250 0830 4 -033 018 Fail 181250 08302 4 3 -29045L 200317 1116 6 -029 025 Fail 200317 11163 6 5 -09935L 201833 1828 6 -029 040 Fail 201833 18280 6 5 -08432L 203250 0585 4 -029 013 Fail 203250 05852 4 3 -07016L 209000 0959 6 -028 021 Fail 209000 09592 6 5 -0129L 211667 0427 6 -027 009 Fail 211667 04274 6 5 01556L 214030 0887 6 -027 020 Fail 214030 08868 6 5 03819L 216000 0795 6 -026 018 Fail 216000 07950 6 5 05834L 226009 1308 6 -024 029 Fail 226009 13076 6 5 15836L 228783 4310 3 -024 095 Fail - - 36L - - 18666L 238750 1234 4 -022 027 Fail 238750 12340 4 3 28570L 2213900 - 1 333 Fail - - 70L - - 20037

Totgem 36224 2416 gkg 1-level 227 (175) 10 210211 (36L44L 70L) 10 9Totstd= 55669 4003 5-level 184 (151) 3

64RESULTS Mean = 2102106 gkg

Repeatability variance S2r = 117627Repeatability std Sr = 108456 --gt 516 r = 30368Between lab variance S2L = 176699Reproducibility var S2R = 294326Reproducibility std SR = 171559 --gt 816 R = 48037Remarks 3 Labs rejected (36L44L 70L)

000 050 100 150 200 250 300 350

k-values

44L

65L

45L

35L

32L

16L

9L

56L

19L

34L

36L

66L

70L

Mandels k statistics(Soil 5 - TOC)

-500 00 500 1000 1500 2000 2500

Deviation from Mean

44L

65L

45L

35L

32L

16L

9L

56L

19L

34L

36L

66L

70L

Labo

rato

ries

Soil 5 - TOC -- Mean PARM = 2102 [gkg]

-100 000 100 200 300 400

h-values

44L

65L

45L

35L

32L

16L

9L

56L

19L

34L

36L

66L

70L

Labo

rato

ries

Mandels h statistics(Soil 5 - TOC)

Soil 5-TOC

17

Annex 4

Raw data submitted

Sample Compost 1 Sample Compost 2 Sample Sewage Sludge 1Element TOC [gkg] Element TOC [gkg] Element TOC [gkg]

LAB PARM LAB PARM LAB PARM30L 2600 19L 1691 19L 286730L 2580 19L 1634 19L 281430L 2560 19L 1619 19L 276934L 2969 19L 1604 19L 272034L 2936 19L 1499 19L 268834L 2958 19L 1414 19L 266234L 2994 34L 1527 34L 315234L 3199 34L 1622 34L 314934L 3024 34L 1519 34L 343035L 2306 34L 1753 34L 336535L 2300 34L 1636 34L 304235L 2298 34L 1874 34L 298335L 2296 35L 1506 35L 270735L 2291 35L 1312 35L 270335L 2259 35L 1294 35L 268836L 2546 35L 1279 35L 267436L 2527 35L 1191 35L 263136L 2470 35L 1177 35L 262644L 2583 36L 1418 36L 271344L 2581 36L 1408 36L 266544L 2578 36L 1320 36L 261444L 2539 44L 1719 44L 292044L 2528 44L 1664 44L 291644L 2525 44L 1654 44L 291245L 2658 44L 1637 44L 290045L 2600 44L 1624 44L 289645L 2546 44L 1620 44L 289345L 2461 45L 1428 45L 297645L 2409 45L 1325 45L 295245L 2350 45L 1323 45L 288546L 2460 45L 1321 45L 286646L 2400 45L 1309 45L 284046L 2370 45L 1253 45L 278746L 2350 46L 1580 46L 233056L 2436 46L 1550 46L 233056L 2435 46L 1170 46L 230056L 2405 46L 1120 46L 229056L 2397 56L 1642 56L 270256L 2375 56L 1626 56L 270156L 2358 56L 1622 56L 269465L 2587 56L 1571 56L 269365L 2542 56L 1561 56L 268465L 2483 56L 1545 56L 268066L 2454 65L 1933 65L 264166L 2429 65L 1838 65L 260966L 2365 65L 1693 65L 260766L 2262 65L 1562 65L 260569L 2730 66L 1561 66L 270169L 2250 66L 1545 66L 267469L 1440 66L 1420 66L 261969L 1420 66L 1417 66L 251470L 2435 69L 2700 69L 2639L 2594 69L 2660 69L 2409L 2570 69L 2170 69L 2199L 2565 69L 2130 69L 2109L 2563 70L 1414 70L 28159L 2562 9L 1644 9L 28579L 2555 9L 1641 9L 2856

32L 2290 9L 1602 9L 285532L 2390 9L 1589 9L 285532L 2510 9L 1526 9L 285332L 2470 9L 1492 9L 284616L 2380 32L 1470 32L 265016L 2530 32L 1520 32L 271016L 2400 32L 1540 32L 271016L 2500 32L 1600 32L 280016L 2420 16L 1400 16L 284016L 2410 16L 1440 16L 2840

16L 1470 16L 286016L 1510 16L 287016L 1360 16L 287016L 1390 16L 2880

Sample Sewage Sludge 2 Sample Soil 4 Sample Soil 5Element TOC [gkg] Element TOC [gkg] Element TOC [gkg]

LAB PARM LAB PARM LAB PARM19L 2308 19L 1720 19L 225019L 2303 19L 1700 19L 223019L 2239 19L 1690 19L 221019L 2204 19L 1670 19L 211019L 2192 19L 1640 19L 210019L 2096 19L 1580 19L 206034L 2631 30L 1790 34L 244334L 2471 30L 1770 34L 233434L 2977 30L 1700 34L 231534L 2785 34L 1740 34L 222134L 2780 34L 1692 34L 217634L 2668 34L 1727 34L 207335L 2179 34L 1767 35L 233035L 2160 34L 1777 35L 208035L 2158 34L 1783 35L 201035L 2132 35L 1700 35L 198035L 2119 35L 1650 35L 193035L 2094 35L 1650 35L 178036L 2096 35L 1640 36L 254036L 2069 35L 1630 36L 253436L 2052 35L 1630 36L 179044L 2325 36L 1500 44L 302144L 2309 36L 1497 44L 298244L 2307 36L 1417 44L 295644L 2305 44L 1594 44L 30744L 2287 44L 1587 44L 30044L 2283 44L 1584 44L 29745L 2331 44L 1574 45L 214945L 2327 44L 1573 45L 209245L 2308 44L 1562 45L 203345L 2287 45L 1827 45L 197145L 2234 45L 1709 45L 193345L 2113 45L 1666 45L 184146L 190 45L 1665 56L 223746L 180 45L 1664 56L 222246L 180 45L 1600 56L 220346L 180 46L 2300 56L 206956L 2204 46L 2300 56L 206856L 2197 46L 2300 56L 204456L 2193 46L 2200 65L 192056L 2185 56L 1668 65L 182056L 2183 56L 1654 65L 179056L 2167 56L 1653 65L 172065L 2136 56L 1643 66L 254365L 2091 56L 1639 66L 242465L 2065 56L 1638 66L 232165L 2047 65L 1630 66L 226266L 2105 65L 1560 70L 2213966L 2022 65L 1530 9L 218066L 2009 65L 1490 9L 214066L 1983 66L 2179 9L 213070L 2272 66L 1900 9L 21109L 2385 66L 1762 9L 20709L 2377 66L 1734 9L 20709L 2375 70L 10404 32L 20509L 2359 9L 1640 32L 21009L 2356 9L 1640 32L 20209L 2354 9L 1610 32L 1960

32L 2240 9L 1590 16L 210032L 2260 9L 1590 16L 220032L 2200 9L 1560 16L 220032L 2270 32L 1640 16L 206016L 2300 32L 1600 16L 197016L 2310 32L 1560 16L 201016L 2350 32L 157016L 2260 16L 170016L 2290 16L 180016L 2240 16L 1700

16L 180016L 170016L 1700

European Commission EUR 23012 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on total organic carbon Author(s) E Sobiecka H van der Sloot K Andersen B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 50 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07412-7 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 total organic carbon (TOC) in soils sludge and treated bio-waste 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

-23012-EN

-C

14

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

15

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

16

Annex 3

Statistical calculations

Unit gkg

Mandels k statistics(Compost 1 - TOC)Mandels h statistics(Compost 1 - TOC)

Sample Compost 1 Compost 1 - TOC -- Mean PARM = 2463 [gkg]

Element TOC

General calcparmT1= 142643E+04T2= 351264E+06T3= 58T4= 292T5= 16501E+03

n= variabelp= 13

N-table= 5

Mandels statistics End ResultLAB 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

69L 1960000 64265 4 -235 352 Fail - - 69L - - -502735L 2291667 1674 6 -081 009 2291667 16741 6 5 -171066L 2377425 8552 4 -041 047 2377425 85518 4 3 -85346L 2395000 4796 4 -033 026 2395000 47958 4 3 -67756L 2401227 3133 6 -030 017 2401227 31330 6 5 -61432L 2415000 9713 4 -024 053 2415000 97125 4 3 -47770L 2435100 - 1 -014 2435100 - 1 -27616L 2440000 6033 6 -012 033 2440000 60332 6 5 -22745L 2503800 11759 6 018 064 2503800 117589 6 5 41136L 2514416 3994 3 023 022 2514416 39937 3 2 51765L 2537333 5216 3 033 029 2537333 52157 3 2 74744L 2555667 2783 6 042 015 2555667 27826 6 5 9309L 2568167 1356 6 048 007 2568167 13556 6 5 105530L 2580000 2000 3 053 011 2580000 20000 3 2 117334L 3013269 9580 6 255 053 Fail - - 34L - - 5506

Totgem 246587 9632 gkg 1-level 232 (176) 13 2462677 (34L 69L) 13 12Totstd= 21507 16070 5-level 186 (152) 2

68RESULTS Mean = 24626770 gkg

Repeatability variance S2r = 3666797Repeatability std Sr = 605541 --gt 246 r = 169551Between lab variance S2L = 7715586Reproducibility var S2R = 11382383Reproducibility std SR = 1066882 --gt 433 R = 298727Remarks 2 Labs rejected (34L 69L)

000 050 100 150 200 250 300 350 400

k-values

69L

35L

66L

46L

56L

32L

70L

16L

45L

36L

65L

44L

9L

30L

34L

Mandels k statistics(Compost 1 - TOC)

-600 -400 -200 00 200 400 600

Deviation from Mean

69L

35L

66L

46L

56L

32L

70L

16L

45L

36L

65L

44L

9L

30L

34L

Labo

rato

ries

Compost 1 - TOC -- Mean PARM = 2463 [gkg]

-300 -200 -100 000 100 200 300

h-values

69L

66L

56L

70L

45L

65L

9L

34L

Labo

rato

ries

Mandels h statistics(Compost 1 - TOC)

Compost 1-TOC

Unit gkg

Mandels k statistics(Compost 2 - TOC)Mandels h statistics(Compost 2 - TOC)

Sample Compost 2 Compost 2 - TOC -- Mean PARM = 1542 [gkg]

Element TOC

General calcparmT1= 994897E+03T2= 155556E+06T3= 64T4= 346T5= 41738E+03

n= variabelp= 13

N-table= 5

Mandels statistics End ResultLAB 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

45L 1326733 5665 6 -100 042 Fail 1326733 56646 6 5 -215046L 1355000 24365 4 -089 181 Fail - - 46L - - -186736L 1381949 5407 3 -078 040 Fail 1381949 54070 3 2 -159870L 1414120 - 1 -066 Fail 1414120 - 1 -127616L 1428333 5565 6 -061 041 1428333 55648 6 5 -113466L 1485550 7805 4 -039 058 1485550 78047 4 3 -56232L 1532500 5377 4 -021 040 1532500 53774 4 3 -09219L 1576833 10138 6 -004 075 1576833 101381 6 5 3519L 1582333 6166 6 -002 046 1582333 61659 6 5 40656L 1594432 4046 6 003 030 1594432 40463 6 5 52744L 1653000 3651 6 025 027 1653000 36508 6 5 111334L 1655127 13717 6 026 102 1655127 137168 6 5 113434L 1655127 13717 6 026 102 1655127 137168 6 5 113465L 1756500 16295 4 065 121 Fail 1756500 162949 4 3 214869L 2415000 30687 4 316 228 Fail - - 69L - - 8733

Totgem 158750 10900 gkg 1-level 232 (176) 13 1541734 (46L 69L) 13 12Totstd= 26187 8164 5-level 186 (152) 2

72RESULTS Mean = 15417337 gkg

Repeatability variance S2r = 8183950Repeatability std Sr = 904652 --gt 587 r = 253303Between lab variance S2L = 13631046Reproducibility var S2R = 21814995Reproducibility std SR = 1476990 --gt 958 R = 413557Remarks 2 Labs rejected (46L 69L)

000 050 100 150 200 250

k-values

45L

46L

36L

70L

16L

66L

32L

19L

9L

56L

44L

34L

34L

65L

69L

Mandels k statistics(Compost 2 - TOC)

-400 -200 00 200 400 600 800 1000

Deviation from Mean

45L

46L

36L

70L

16L

66L

32L

19L

9L

56L

44L

34L

34L

65L

69L

Labo

rato

ries

Compost 2 - TOC -- Mean PARM = 1542 [gkg]

-100 000 100 200 300 400

h-values

45L

36L

16L

32L

9L

44L

34L

69L

Labo

rato

ries

Mandels h statistics(Compost 2 - TOC)

Compost 2-TOC

Unit gkg

Mandels k statistics(Sludge 1 - TOC)Mandels h statistics(Sludge 1 - TOC)

Sample Sludge 1 Sludge 1 - TOC -- Mean PARM = 2721 [gkg]

Element TOC

General calcparmT1= 169626E+04T2= 465445E+06T3= 62T4= 326T5= 10312E+03

n= variabelp= 13

N-table= 5

Mandels statistics End ResultLAB 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

69L 233000 2362 4 -347 037 Fail - - 69L - - -2488046L 2312500 2062 4 -040 032 Fail 2312500 20616 4 3 -408565L 2615500 1708 4 004 026 2615500 17078 4 3 -105566L 2627200 8268 4 006 128 2627200 82678 4 3 -93836L 2664041 4976 3 011 077 2664041 49758 3 2 -56935L 2671500 3533 6 013 055 2671500 35331 6 5 -49556L 2692298 0874 6 016 014 Fail 2692298 08738 6 5 -28732L 2717500 6185 4 019 096 Fail 2717500 61847 4 3 -03519L 2753333 7819 6 025 121 Fail 2753333 78189 6 5 32470L 2814600 - 1 034 Fail 2814600 - 1 9369L 2853667 0398 6 039 006 Fail 2853667 03983 6 5 132716L 2860000 1673 6 040 026 Fail 2860000 16733 6 5 139045L 2884433 7033 6 044 109 Fail 2884433 70331 6 5 163544L 2906167 1129 6 047 017 Fail 2906167 11286 6 5 185234L 3186874 17674 6 089 274 Fail - - 34L - - 4659

Totgem 258617 4692 gkg 1-level 232 (176) 13 2720980 (34L 69L) 13 12Totstd= 67800 4610 5-level 186 (152) 2

72RESULTS Mean = 27209799 gkg

Repeatability variance S2r = 2104538Repeatability std Sr = 458752 --gt 169 r = 128451Between lab variance S2L = 23618387Reproducibility var S2R = 25722925Reproducibility std SR = 1603837 --gt 589 R = 449074Remarks 2 Labs rejected (34L 69L)

000 050 100 150 200 250 300

k-values

69L

46L

65L

66L

36L

35L

56L

32L

19L

70L

9L

16L

45L

44L

34L

Mandels k statistics(Sludge 1 - TOC)

-2500 -2000 -1500 -1000 -500 00 500

Deviation from Mean

69L

46L

65L

66L

36L

35L

56L

32L

19L

70L

9L

16L

45L

44L

34L

Labo

rato

ries

Sludge 1 - TOC -- Mean PARM = 2721 [gkg]

-400 -300 -200 -100 000 100

h-values

69L

65L

36L

56L

19L

9L

45L

34L

Labo

rato

ries

Mandels h statistics(Sludge 1 - TOC)

Sludge 1-TOC

68 Unit gkg

Mandels k statistics(Sludge 2 - TOC)Mandels h statistics(Sludge 2 - TOC)

Sample Sludge 2 Sludge 2 - TOC -- Mean PARM = 2207 [gkg]

Element TOC

General calcparmT1= 128601E+04T2= 285689E+06T3= 58T4= 310T5= 97826E+02

n= variabelp= 12

N-table= 5

Mandels statistics End ResultLAB 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

46L 182500 0500 4 -333 008 Fail - - 46L - - -2024466L 2029475 5267 4 -012 084 2029475 52674 4 3 -177436L 2072609 2222 3 -005 035 2072609 22222 3 2 -134365L 2084750 3865 4 -002 062 2084750 38647 4 3 -122135L 2140333 3119 6 007 050 2140333 31194 6 5 -66556L 2188021 1282 6 015 020 2188021 12822 6 5 -18819L 2223667 7916 6 022 126 Fail 2223667 79157 6 5 16832L 2242500 3096 4 025 049 Fail 2242500 30957 4 3 35645L 2266600 8322 6 029 132 Fail 2266600 83216 6 5 59770L 2272460 - 1 030 Fail 2272460 - 1 65616L 2291667 3869 6 033 062 Fail 2291667 38687 6 5 84844L 2302667 1546 6 035 025 Fail 2302667 15462 6 5 9589L 2367667 1296 6 047 021 Fail 2367667 12956 6 5 160834L 2718591 17124 6 108 273 Fail - - 34L - - 5117

Totgem 209882 4571 gkg 1-level 230 (176) 12 2206868 (34L 46L) 12 11Totstd= 57628 4485 5-level 185 (151) 2

68RESULTS Mean = 22068679 gkg

Repeatability variance S2r = 2126659Repeatability std Sr = 461157 --gt 209 r = 129124Between lab variance S2L = 9960432Reproducibility var S2R = 12087091Reproducibility std SR = 1099413 --gt 498 R = 307836Remarks 2 Labs rejected (34L 46L)

000 050 100 150 200 250 300

k-values

46L

66L

36L

65L

35L

56L

19L

32L

45L

70L

16L

44L

9L

34L

Mandels k statistics(Sludge 2 - TOC)

-2500 -2000 -1500 -1000 -500 00 500 1000

Deviation from Mean

46L

66L

36L

65L

35L

56L

19L

32L

45L

70L

16L

44L

9L

34L

Labo

rato

ries

Sludge 2 - TOC -- Mean PARM = 2207 [gkg]

-400 -300 -200 -100 000 100 200

h-values

46L

66L

36L

65L

35L

56L

19L

32L

45L

70L

16L

44L

9L

34L

Labo

rato

ries

Mandels h statistics(Sludge 2 - TOC)

Sludge 2-TOC

Unit gkg

Mandels k statistics(Soil 4 - TOC)Mandels h statistics(Soil 4 - TOC)

Sample Soil 4 Soil 4 - TOC -- Mean PARM = 1641 [gkg]

Element TOC

General calcparmT1= 102171E+03T2= 168700E+04T3= 62T4= 338T5= 94040E+00

n= variabelp= 12

N-table= 5

Mandels statistics End ResultLAB 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

36L 147161 0470 3 -036 068 Fail 147161 04702 3 2 -16965L 155250 0591 4 -032 085 Fail 155250 05909 4 3 -08844L 157900 0115 6 -031 017 Fail 157900 01152 6 5 -06232L 159250 0359 4 -031 052 Fail 159250 03594 4 3 -0489L 160500 0315 6 -030 045 Fail 160500 03146 6 5 -03656L 164927 0113 6 -028 016 Fail 164927 01127 6 5 00835L 165000 0261 6 -028 038 Fail 165000 02608 6 5 00919L 166667 0505 6 -027 073 Fail 166667 05046 6 5 02645L 168850 0763 6 -026 110 Fail 168850 07628 6 5 04816L 173333 0516 6 -024 074 Fail 173333 05164 6 5 09334L 174761 0346 6 -024 050 Fail 174761 03462 6 5 10730L 175333 0473 3 -024 068 Fail 175333 04726 3 2 11366L 189375 2035 4 -017 294 Fail - - 66L - - 25346L 227500 0500 4 000 072 - - 46L - - 63470L 1040400 - 1 360 Fail - - 70L - - 8763

Totgem 22841 0526 gkg 1-level 232 (176) 12 164078 (46L 66L70L) 12 11Totstd= 22541 0469 5-level 186 (152) 3

71RESULTS Mean = 1640777 gkg

Repeatability variance S2r = 018808Repeatability std Sr = 043368 --gt 264 r = 12143Between lab variance S2L = 054747Reproducibility var S2R = 073555Reproducibility std SR = 085764 --gt 523 R = 24014Remarks 3 Labs rejected (46L 66L70L)

000 050 100 150 200 250 300

k-values

36L

65L

44L

32L

9L

56L

35L

19L

45L

16L

34L

30L

66L

46L

70L

Mandels k statistics(Soil 4 - TOC)

-100 00 100 200 300 400 500 600 700 800 900

Deviation from Mean

36L

65L

44L

32L

9L

56L

35L

19L

45L

16L

34L

30L

66L

46L

70L

Labo

rato

ries

Soil 4 - TOC -- Mean PARM = 1641 [gkg]

-100 000 100 200 300 400

h-values

36L

44L

9L

35L

45L

34L

66L

70L

Labo

rato

ries

Mandels h statistics(Soil 4 - TOC)

Soil 4-TOC

Unit gkg

Mandels k statistics(Soil 5 - TOC)Mandels h statistics(Soil 5 - TOC)

Sample Soil 5 Soil 5 - TOC -- Mean PARM = 2102 [gkg]

Element TOC

General calcparmT1= 113661E+03T2= 240201E+04T3= 54T4= 300T5= 51756E+01

n= variabelp= 10

N-table= 5

Mandels statistics End ResultLAB 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

44L 164383 14708 6 -036 325 Fail - - 44L - - -45865L 181250 0830 4 -033 018 Fail 181250 08302 4 3 -29045L 200317 1116 6 -029 025 Fail 200317 11163 6 5 -09935L 201833 1828 6 -029 040 Fail 201833 18280 6 5 -08432L 203250 0585 4 -029 013 Fail 203250 05852 4 3 -07016L 209000 0959 6 -028 021 Fail 209000 09592 6 5 -0129L 211667 0427 6 -027 009 Fail 211667 04274 6 5 01556L 214030 0887 6 -027 020 Fail 214030 08868 6 5 03819L 216000 0795 6 -026 018 Fail 216000 07950 6 5 05834L 226009 1308 6 -024 029 Fail 226009 13076 6 5 15836L 228783 4310 3 -024 095 Fail - - 36L - - 18666L 238750 1234 4 -022 027 Fail 238750 12340 4 3 28570L 2213900 - 1 333 Fail - - 70L - - 20037

Totgem 36224 2416 gkg 1-level 227 (175) 10 210211 (36L44L 70L) 10 9Totstd= 55669 4003 5-level 184 (151) 3

64RESULTS Mean = 2102106 gkg

Repeatability variance S2r = 117627Repeatability std Sr = 108456 --gt 516 r = 30368Between lab variance S2L = 176699Reproducibility var S2R = 294326Reproducibility std SR = 171559 --gt 816 R = 48037Remarks 3 Labs rejected (36L44L 70L)

000 050 100 150 200 250 300 350

k-values

44L

65L

45L

35L

32L

16L

9L

56L

19L

34L

36L

66L

70L

Mandels k statistics(Soil 5 - TOC)

-500 00 500 1000 1500 2000 2500

Deviation from Mean

44L

65L

45L

35L

32L

16L

9L

56L

19L

34L

36L

66L

70L

Labo

rato

ries

Soil 5 - TOC -- Mean PARM = 2102 [gkg]

-100 000 100 200 300 400

h-values

44L

65L

45L

35L

32L

16L

9L

56L

19L

34L

36L

66L

70L

Labo

rato

ries

Mandels h statistics(Soil 5 - TOC)

Soil 5-TOC

17

Annex 4

Raw data submitted

Sample Compost 1 Sample Compost 2 Sample Sewage Sludge 1Element TOC [gkg] Element TOC [gkg] Element TOC [gkg]

LAB PARM LAB PARM LAB PARM30L 2600 19L 1691 19L 286730L 2580 19L 1634 19L 281430L 2560 19L 1619 19L 276934L 2969 19L 1604 19L 272034L 2936 19L 1499 19L 268834L 2958 19L 1414 19L 266234L 2994 34L 1527 34L 315234L 3199 34L 1622 34L 314934L 3024 34L 1519 34L 343035L 2306 34L 1753 34L 336535L 2300 34L 1636 34L 304235L 2298 34L 1874 34L 298335L 2296 35L 1506 35L 270735L 2291 35L 1312 35L 270335L 2259 35L 1294 35L 268836L 2546 35L 1279 35L 267436L 2527 35L 1191 35L 263136L 2470 35L 1177 35L 262644L 2583 36L 1418 36L 271344L 2581 36L 1408 36L 266544L 2578 36L 1320 36L 261444L 2539 44L 1719 44L 292044L 2528 44L 1664 44L 291644L 2525 44L 1654 44L 291245L 2658 44L 1637 44L 290045L 2600 44L 1624 44L 289645L 2546 44L 1620 44L 289345L 2461 45L 1428 45L 297645L 2409 45L 1325 45L 295245L 2350 45L 1323 45L 288546L 2460 45L 1321 45L 286646L 2400 45L 1309 45L 284046L 2370 45L 1253 45L 278746L 2350 46L 1580 46L 233056L 2436 46L 1550 46L 233056L 2435 46L 1170 46L 230056L 2405 46L 1120 46L 229056L 2397 56L 1642 56L 270256L 2375 56L 1626 56L 270156L 2358 56L 1622 56L 269465L 2587 56L 1571 56L 269365L 2542 56L 1561 56L 268465L 2483 56L 1545 56L 268066L 2454 65L 1933 65L 264166L 2429 65L 1838 65L 260966L 2365 65L 1693 65L 260766L 2262 65L 1562 65L 260569L 2730 66L 1561 66L 270169L 2250 66L 1545 66L 267469L 1440 66L 1420 66L 261969L 1420 66L 1417 66L 251470L 2435 69L 2700 69L 2639L 2594 69L 2660 69L 2409L 2570 69L 2170 69L 2199L 2565 69L 2130 69L 2109L 2563 70L 1414 70L 28159L 2562 9L 1644 9L 28579L 2555 9L 1641 9L 2856

32L 2290 9L 1602 9L 285532L 2390 9L 1589 9L 285532L 2510 9L 1526 9L 285332L 2470 9L 1492 9L 284616L 2380 32L 1470 32L 265016L 2530 32L 1520 32L 271016L 2400 32L 1540 32L 271016L 2500 32L 1600 32L 280016L 2420 16L 1400 16L 284016L 2410 16L 1440 16L 2840

16L 1470 16L 286016L 1510 16L 287016L 1360 16L 287016L 1390 16L 2880

Sample Sewage Sludge 2 Sample Soil 4 Sample Soil 5Element TOC [gkg] Element TOC [gkg] Element TOC [gkg]

LAB PARM LAB PARM LAB PARM19L 2308 19L 1720 19L 225019L 2303 19L 1700 19L 223019L 2239 19L 1690 19L 221019L 2204 19L 1670 19L 211019L 2192 19L 1640 19L 210019L 2096 19L 1580 19L 206034L 2631 30L 1790 34L 244334L 2471 30L 1770 34L 233434L 2977 30L 1700 34L 231534L 2785 34L 1740 34L 222134L 2780 34L 1692 34L 217634L 2668 34L 1727 34L 207335L 2179 34L 1767 35L 233035L 2160 34L 1777 35L 208035L 2158 34L 1783 35L 201035L 2132 35L 1700 35L 198035L 2119 35L 1650 35L 193035L 2094 35L 1650 35L 178036L 2096 35L 1640 36L 254036L 2069 35L 1630 36L 253436L 2052 35L 1630 36L 179044L 2325 36L 1500 44L 302144L 2309 36L 1497 44L 298244L 2307 36L 1417 44L 295644L 2305 44L 1594 44L 30744L 2287 44L 1587 44L 30044L 2283 44L 1584 44L 29745L 2331 44L 1574 45L 214945L 2327 44L 1573 45L 209245L 2308 44L 1562 45L 203345L 2287 45L 1827 45L 197145L 2234 45L 1709 45L 193345L 2113 45L 1666 45L 184146L 190 45L 1665 56L 223746L 180 45L 1664 56L 222246L 180 45L 1600 56L 220346L 180 46L 2300 56L 206956L 2204 46L 2300 56L 206856L 2197 46L 2300 56L 204456L 2193 46L 2200 65L 192056L 2185 56L 1668 65L 182056L 2183 56L 1654 65L 179056L 2167 56L 1653 65L 172065L 2136 56L 1643 66L 254365L 2091 56L 1639 66L 242465L 2065 56L 1638 66L 232165L 2047 65L 1630 66L 226266L 2105 65L 1560 70L 2213966L 2022 65L 1530 9L 218066L 2009 65L 1490 9L 214066L 1983 66L 2179 9L 213070L 2272 66L 1900 9L 21109L 2385 66L 1762 9L 20709L 2377 66L 1734 9L 20709L 2375 70L 10404 32L 20509L 2359 9L 1640 32L 21009L 2356 9L 1640 32L 20209L 2354 9L 1610 32L 1960

32L 2240 9L 1590 16L 210032L 2260 9L 1590 16L 220032L 2200 9L 1560 16L 220032L 2270 32L 1640 16L 206016L 2300 32L 1600 16L 197016L 2310 32L 1560 16L 201016L 2350 32L 157016L 2260 16L 170016L 2290 16L 180016L 2240 16L 1700

16L 180016L 170016L 1700

European Commission EUR 23012 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on total organic carbon Author(s) E Sobiecka H van der Sloot K Andersen B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 50 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07412-7 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 total organic carbon (TOC) in soils sludge and treated bio-waste 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

-23012-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

15

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

16

Annex 3

Statistical calculations

Unit gkg

Mandels k statistics(Compost 1 - TOC)Mandels h statistics(Compost 1 - TOC)

Sample Compost 1 Compost 1 - TOC -- Mean PARM = 2463 [gkg]

Element TOC

General calcparmT1= 142643E+04T2= 351264E+06T3= 58T4= 292T5= 16501E+03

n= variabelp= 13

N-table= 5

Mandels statistics End ResultLAB 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

69L 1960000 64265 4 -235 352 Fail - - 69L - - -502735L 2291667 1674 6 -081 009 2291667 16741 6 5 -171066L 2377425 8552 4 -041 047 2377425 85518 4 3 -85346L 2395000 4796 4 -033 026 2395000 47958 4 3 -67756L 2401227 3133 6 -030 017 2401227 31330 6 5 -61432L 2415000 9713 4 -024 053 2415000 97125 4 3 -47770L 2435100 - 1 -014 2435100 - 1 -27616L 2440000 6033 6 -012 033 2440000 60332 6 5 -22745L 2503800 11759 6 018 064 2503800 117589 6 5 41136L 2514416 3994 3 023 022 2514416 39937 3 2 51765L 2537333 5216 3 033 029 2537333 52157 3 2 74744L 2555667 2783 6 042 015 2555667 27826 6 5 9309L 2568167 1356 6 048 007 2568167 13556 6 5 105530L 2580000 2000 3 053 011 2580000 20000 3 2 117334L 3013269 9580 6 255 053 Fail - - 34L - - 5506

Totgem 246587 9632 gkg 1-level 232 (176) 13 2462677 (34L 69L) 13 12Totstd= 21507 16070 5-level 186 (152) 2

68RESULTS Mean = 24626770 gkg

Repeatability variance S2r = 3666797Repeatability std Sr = 605541 --gt 246 r = 169551Between lab variance S2L = 7715586Reproducibility var S2R = 11382383Reproducibility std SR = 1066882 --gt 433 R = 298727Remarks 2 Labs rejected (34L 69L)

000 050 100 150 200 250 300 350 400

k-values

69L

35L

66L

46L

56L

32L

70L

16L

45L

36L

65L

44L

9L

30L

34L

Mandels k statistics(Compost 1 - TOC)

-600 -400 -200 00 200 400 600

Deviation from Mean

69L

35L

66L

46L

56L

32L

70L

16L

45L

36L

65L

44L

9L

30L

34L

Labo

rato

ries

Compost 1 - TOC -- Mean PARM = 2463 [gkg]

-300 -200 -100 000 100 200 300

h-values

69L

66L

56L

70L

45L

65L

9L

34L

Labo

rato

ries

Mandels h statistics(Compost 1 - TOC)

Compost 1-TOC

Unit gkg

Mandels k statistics(Compost 2 - TOC)Mandels h statistics(Compost 2 - TOC)

Sample Compost 2 Compost 2 - TOC -- Mean PARM = 1542 [gkg]

Element TOC

General calcparmT1= 994897E+03T2= 155556E+06T3= 64T4= 346T5= 41738E+03

n= variabelp= 13

N-table= 5

Mandels statistics End ResultLAB 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

45L 1326733 5665 6 -100 042 Fail 1326733 56646 6 5 -215046L 1355000 24365 4 -089 181 Fail - - 46L - - -186736L 1381949 5407 3 -078 040 Fail 1381949 54070 3 2 -159870L 1414120 - 1 -066 Fail 1414120 - 1 -127616L 1428333 5565 6 -061 041 1428333 55648 6 5 -113466L 1485550 7805 4 -039 058 1485550 78047 4 3 -56232L 1532500 5377 4 -021 040 1532500 53774 4 3 -09219L 1576833 10138 6 -004 075 1576833 101381 6 5 3519L 1582333 6166 6 -002 046 1582333 61659 6 5 40656L 1594432 4046 6 003 030 1594432 40463 6 5 52744L 1653000 3651 6 025 027 1653000 36508 6 5 111334L 1655127 13717 6 026 102 1655127 137168 6 5 113434L 1655127 13717 6 026 102 1655127 137168 6 5 113465L 1756500 16295 4 065 121 Fail 1756500 162949 4 3 214869L 2415000 30687 4 316 228 Fail - - 69L - - 8733

Totgem 158750 10900 gkg 1-level 232 (176) 13 1541734 (46L 69L) 13 12Totstd= 26187 8164 5-level 186 (152) 2

72RESULTS Mean = 15417337 gkg

Repeatability variance S2r = 8183950Repeatability std Sr = 904652 --gt 587 r = 253303Between lab variance S2L = 13631046Reproducibility var S2R = 21814995Reproducibility std SR = 1476990 --gt 958 R = 413557Remarks 2 Labs rejected (46L 69L)

000 050 100 150 200 250

k-values

45L

46L

36L

70L

16L

66L

32L

19L

9L

56L

44L

34L

34L

65L

69L

Mandels k statistics(Compost 2 - TOC)

-400 -200 00 200 400 600 800 1000

Deviation from Mean

45L

46L

36L

70L

16L

66L

32L

19L

9L

56L

44L

34L

34L

65L

69L

Labo

rato

ries

Compost 2 - TOC -- Mean PARM = 1542 [gkg]

-100 000 100 200 300 400

h-values

45L

36L

16L

32L

9L

44L

34L

69L

Labo

rato

ries

Mandels h statistics(Compost 2 - TOC)

Compost 2-TOC

Unit gkg

Mandels k statistics(Sludge 1 - TOC)Mandels h statistics(Sludge 1 - TOC)

Sample Sludge 1 Sludge 1 - TOC -- Mean PARM = 2721 [gkg]

Element TOC

General calcparmT1= 169626E+04T2= 465445E+06T3= 62T4= 326T5= 10312E+03

n= variabelp= 13

N-table= 5

Mandels statistics End ResultLAB 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

69L 233000 2362 4 -347 037 Fail - - 69L - - -2488046L 2312500 2062 4 -040 032 Fail 2312500 20616 4 3 -408565L 2615500 1708 4 004 026 2615500 17078 4 3 -105566L 2627200 8268 4 006 128 2627200 82678 4 3 -93836L 2664041 4976 3 011 077 2664041 49758 3 2 -56935L 2671500 3533 6 013 055 2671500 35331 6 5 -49556L 2692298 0874 6 016 014 Fail 2692298 08738 6 5 -28732L 2717500 6185 4 019 096 Fail 2717500 61847 4 3 -03519L 2753333 7819 6 025 121 Fail 2753333 78189 6 5 32470L 2814600 - 1 034 Fail 2814600 - 1 9369L 2853667 0398 6 039 006 Fail 2853667 03983 6 5 132716L 2860000 1673 6 040 026 Fail 2860000 16733 6 5 139045L 2884433 7033 6 044 109 Fail 2884433 70331 6 5 163544L 2906167 1129 6 047 017 Fail 2906167 11286 6 5 185234L 3186874 17674 6 089 274 Fail - - 34L - - 4659

Totgem 258617 4692 gkg 1-level 232 (176) 13 2720980 (34L 69L) 13 12Totstd= 67800 4610 5-level 186 (152) 2

72RESULTS Mean = 27209799 gkg

Repeatability variance S2r = 2104538Repeatability std Sr = 458752 --gt 169 r = 128451Between lab variance S2L = 23618387Reproducibility var S2R = 25722925Reproducibility std SR = 1603837 --gt 589 R = 449074Remarks 2 Labs rejected (34L 69L)

000 050 100 150 200 250 300

k-values

69L

46L

65L

66L

36L

35L

56L

32L

19L

70L

9L

16L

45L

44L

34L

Mandels k statistics(Sludge 1 - TOC)

-2500 -2000 -1500 -1000 -500 00 500

Deviation from Mean

69L

46L

65L

66L

36L

35L

56L

32L

19L

70L

9L

16L

45L

44L

34L

Labo

rato

ries

Sludge 1 - TOC -- Mean PARM = 2721 [gkg]

-400 -300 -200 -100 000 100

h-values

69L

65L

36L

56L

19L

9L

45L

34L

Labo

rato

ries

Mandels h statistics(Sludge 1 - TOC)

Sludge 1-TOC

68 Unit gkg

Mandels k statistics(Sludge 2 - TOC)Mandels h statistics(Sludge 2 - TOC)

Sample Sludge 2 Sludge 2 - TOC -- Mean PARM = 2207 [gkg]

Element TOC

General calcparmT1= 128601E+04T2= 285689E+06T3= 58T4= 310T5= 97826E+02

n= variabelp= 12

N-table= 5

Mandels statistics End ResultLAB 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

46L 182500 0500 4 -333 008 Fail - - 46L - - -2024466L 2029475 5267 4 -012 084 2029475 52674 4 3 -177436L 2072609 2222 3 -005 035 2072609 22222 3 2 -134365L 2084750 3865 4 -002 062 2084750 38647 4 3 -122135L 2140333 3119 6 007 050 2140333 31194 6 5 -66556L 2188021 1282 6 015 020 2188021 12822 6 5 -18819L 2223667 7916 6 022 126 Fail 2223667 79157 6 5 16832L 2242500 3096 4 025 049 Fail 2242500 30957 4 3 35645L 2266600 8322 6 029 132 Fail 2266600 83216 6 5 59770L 2272460 - 1 030 Fail 2272460 - 1 65616L 2291667 3869 6 033 062 Fail 2291667 38687 6 5 84844L 2302667 1546 6 035 025 Fail 2302667 15462 6 5 9589L 2367667 1296 6 047 021 Fail 2367667 12956 6 5 160834L 2718591 17124 6 108 273 Fail - - 34L - - 5117

Totgem 209882 4571 gkg 1-level 230 (176) 12 2206868 (34L 46L) 12 11Totstd= 57628 4485 5-level 185 (151) 2

68RESULTS Mean = 22068679 gkg

Repeatability variance S2r = 2126659Repeatability std Sr = 461157 --gt 209 r = 129124Between lab variance S2L = 9960432Reproducibility var S2R = 12087091Reproducibility std SR = 1099413 --gt 498 R = 307836Remarks 2 Labs rejected (34L 46L)

000 050 100 150 200 250 300

k-values

46L

66L

36L

65L

35L

56L

19L

32L

45L

70L

16L

44L

9L

34L

Mandels k statistics(Sludge 2 - TOC)

-2500 -2000 -1500 -1000 -500 00 500 1000

Deviation from Mean

46L

66L

36L

65L

35L

56L

19L

32L

45L

70L

16L

44L

9L

34L

Labo

rato

ries

Sludge 2 - TOC -- Mean PARM = 2207 [gkg]

-400 -300 -200 -100 000 100 200

h-values

46L

66L

36L

65L

35L

56L

19L

32L

45L

70L

16L

44L

9L

34L

Labo

rato

ries

Mandels h statistics(Sludge 2 - TOC)

Sludge 2-TOC

Unit gkg

Mandels k statistics(Soil 4 - TOC)Mandels h statistics(Soil 4 - TOC)

Sample Soil 4 Soil 4 - TOC -- Mean PARM = 1641 [gkg]

Element TOC

General calcparmT1= 102171E+03T2= 168700E+04T3= 62T4= 338T5= 94040E+00

n= variabelp= 12

N-table= 5

Mandels statistics End ResultLAB 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

36L 147161 0470 3 -036 068 Fail 147161 04702 3 2 -16965L 155250 0591 4 -032 085 Fail 155250 05909 4 3 -08844L 157900 0115 6 -031 017 Fail 157900 01152 6 5 -06232L 159250 0359 4 -031 052 Fail 159250 03594 4 3 -0489L 160500 0315 6 -030 045 Fail 160500 03146 6 5 -03656L 164927 0113 6 -028 016 Fail 164927 01127 6 5 00835L 165000 0261 6 -028 038 Fail 165000 02608 6 5 00919L 166667 0505 6 -027 073 Fail 166667 05046 6 5 02645L 168850 0763 6 -026 110 Fail 168850 07628 6 5 04816L 173333 0516 6 -024 074 Fail 173333 05164 6 5 09334L 174761 0346 6 -024 050 Fail 174761 03462 6 5 10730L 175333 0473 3 -024 068 Fail 175333 04726 3 2 11366L 189375 2035 4 -017 294 Fail - - 66L - - 25346L 227500 0500 4 000 072 - - 46L - - 63470L 1040400 - 1 360 Fail - - 70L - - 8763

Totgem 22841 0526 gkg 1-level 232 (176) 12 164078 (46L 66L70L) 12 11Totstd= 22541 0469 5-level 186 (152) 3

71RESULTS Mean = 1640777 gkg

Repeatability variance S2r = 018808Repeatability std Sr = 043368 --gt 264 r = 12143Between lab variance S2L = 054747Reproducibility var S2R = 073555Reproducibility std SR = 085764 --gt 523 R = 24014Remarks 3 Labs rejected (46L 66L70L)

000 050 100 150 200 250 300

k-values

36L

65L

44L

32L

9L

56L

35L

19L

45L

16L

34L

30L

66L

46L

70L

Mandels k statistics(Soil 4 - TOC)

-100 00 100 200 300 400 500 600 700 800 900

Deviation from Mean

36L

65L

44L

32L

9L

56L

35L

19L

45L

16L

34L

30L

66L

46L

70L

Labo

rato

ries

Soil 4 - TOC -- Mean PARM = 1641 [gkg]

-100 000 100 200 300 400

h-values

36L

44L

9L

35L

45L

34L

66L

70L

Labo

rato

ries

Mandels h statistics(Soil 4 - TOC)

Soil 4-TOC

Unit gkg

Mandels k statistics(Soil 5 - TOC)Mandels h statistics(Soil 5 - TOC)

Sample Soil 5 Soil 5 - TOC -- Mean PARM = 2102 [gkg]

Element TOC

General calcparmT1= 113661E+03T2= 240201E+04T3= 54T4= 300T5= 51756E+01

n= variabelp= 10

N-table= 5

Mandels statistics End ResultLAB 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

44L 164383 14708 6 -036 325 Fail - - 44L - - -45865L 181250 0830 4 -033 018 Fail 181250 08302 4 3 -29045L 200317 1116 6 -029 025 Fail 200317 11163 6 5 -09935L 201833 1828 6 -029 040 Fail 201833 18280 6 5 -08432L 203250 0585 4 -029 013 Fail 203250 05852 4 3 -07016L 209000 0959 6 -028 021 Fail 209000 09592 6 5 -0129L 211667 0427 6 -027 009 Fail 211667 04274 6 5 01556L 214030 0887 6 -027 020 Fail 214030 08868 6 5 03819L 216000 0795 6 -026 018 Fail 216000 07950 6 5 05834L 226009 1308 6 -024 029 Fail 226009 13076 6 5 15836L 228783 4310 3 -024 095 Fail - - 36L - - 18666L 238750 1234 4 -022 027 Fail 238750 12340 4 3 28570L 2213900 - 1 333 Fail - - 70L - - 20037

Totgem 36224 2416 gkg 1-level 227 (175) 10 210211 (36L44L 70L) 10 9Totstd= 55669 4003 5-level 184 (151) 3

64RESULTS Mean = 2102106 gkg

Repeatability variance S2r = 117627Repeatability std Sr = 108456 --gt 516 r = 30368Between lab variance S2L = 176699Reproducibility var S2R = 294326Reproducibility std SR = 171559 --gt 816 R = 48037Remarks 3 Labs rejected (36L44L 70L)

000 050 100 150 200 250 300 350

k-values

44L

65L

45L

35L

32L

16L

9L

56L

19L

34L

36L

66L

70L

Mandels k statistics(Soil 5 - TOC)

-500 00 500 1000 1500 2000 2500

Deviation from Mean

44L

65L

45L

35L

32L

16L

9L

56L

19L

34L

36L

66L

70L

Labo

rato

ries

Soil 5 - TOC -- Mean PARM = 2102 [gkg]

-100 000 100 200 300 400

h-values

44L

65L

45L

35L

32L

16L

9L

56L

19L

34L

36L

66L

70L

Labo

rato

ries

Mandels h statistics(Soil 5 - TOC)

Soil 5-TOC

17

Annex 4

Raw data submitted

Sample Compost 1 Sample Compost 2 Sample Sewage Sludge 1Element TOC [gkg] Element TOC [gkg] Element TOC [gkg]

LAB PARM LAB PARM LAB PARM30L 2600 19L 1691 19L 286730L 2580 19L 1634 19L 281430L 2560 19L 1619 19L 276934L 2969 19L 1604 19L 272034L 2936 19L 1499 19L 268834L 2958 19L 1414 19L 266234L 2994 34L 1527 34L 315234L 3199 34L 1622 34L 314934L 3024 34L 1519 34L 343035L 2306 34L 1753 34L 336535L 2300 34L 1636 34L 304235L 2298 34L 1874 34L 298335L 2296 35L 1506 35L 270735L 2291 35L 1312 35L 270335L 2259 35L 1294 35L 268836L 2546 35L 1279 35L 267436L 2527 35L 1191 35L 263136L 2470 35L 1177 35L 262644L 2583 36L 1418 36L 271344L 2581 36L 1408 36L 266544L 2578 36L 1320 36L 261444L 2539 44L 1719 44L 292044L 2528 44L 1664 44L 291644L 2525 44L 1654 44L 291245L 2658 44L 1637 44L 290045L 2600 44L 1624 44L 289645L 2546 44L 1620 44L 289345L 2461 45L 1428 45L 297645L 2409 45L 1325 45L 295245L 2350 45L 1323 45L 288546L 2460 45L 1321 45L 286646L 2400 45L 1309 45L 284046L 2370 45L 1253 45L 278746L 2350 46L 1580 46L 233056L 2436 46L 1550 46L 233056L 2435 46L 1170 46L 230056L 2405 46L 1120 46L 229056L 2397 56L 1642 56L 270256L 2375 56L 1626 56L 270156L 2358 56L 1622 56L 269465L 2587 56L 1571 56L 269365L 2542 56L 1561 56L 268465L 2483 56L 1545 56L 268066L 2454 65L 1933 65L 264166L 2429 65L 1838 65L 260966L 2365 65L 1693 65L 260766L 2262 65L 1562 65L 260569L 2730 66L 1561 66L 270169L 2250 66L 1545 66L 267469L 1440 66L 1420 66L 261969L 1420 66L 1417 66L 251470L 2435 69L 2700 69L 2639L 2594 69L 2660 69L 2409L 2570 69L 2170 69L 2199L 2565 69L 2130 69L 2109L 2563 70L 1414 70L 28159L 2562 9L 1644 9L 28579L 2555 9L 1641 9L 2856

32L 2290 9L 1602 9L 285532L 2390 9L 1589 9L 285532L 2510 9L 1526 9L 285332L 2470 9L 1492 9L 284616L 2380 32L 1470 32L 265016L 2530 32L 1520 32L 271016L 2400 32L 1540 32L 271016L 2500 32L 1600 32L 280016L 2420 16L 1400 16L 284016L 2410 16L 1440 16L 2840

16L 1470 16L 286016L 1510 16L 287016L 1360 16L 287016L 1390 16L 2880

Sample Sewage Sludge 2 Sample Soil 4 Sample Soil 5Element TOC [gkg] Element TOC [gkg] Element TOC [gkg]

LAB PARM LAB PARM LAB PARM19L 2308 19L 1720 19L 225019L 2303 19L 1700 19L 223019L 2239 19L 1690 19L 221019L 2204 19L 1670 19L 211019L 2192 19L 1640 19L 210019L 2096 19L 1580 19L 206034L 2631 30L 1790 34L 244334L 2471 30L 1770 34L 233434L 2977 30L 1700 34L 231534L 2785 34L 1740 34L 222134L 2780 34L 1692 34L 217634L 2668 34L 1727 34L 207335L 2179 34L 1767 35L 233035L 2160 34L 1777 35L 208035L 2158 34L 1783 35L 201035L 2132 35L 1700 35L 198035L 2119 35L 1650 35L 193035L 2094 35L 1650 35L 178036L 2096 35L 1640 36L 254036L 2069 35L 1630 36L 253436L 2052 35L 1630 36L 179044L 2325 36L 1500 44L 302144L 2309 36L 1497 44L 298244L 2307 36L 1417 44L 295644L 2305 44L 1594 44L 30744L 2287 44L 1587 44L 30044L 2283 44L 1584 44L 29745L 2331 44L 1574 45L 214945L 2327 44L 1573 45L 209245L 2308 44L 1562 45L 203345L 2287 45L 1827 45L 197145L 2234 45L 1709 45L 193345L 2113 45L 1666 45L 184146L 190 45L 1665 56L 223746L 180 45L 1664 56L 222246L 180 45L 1600 56L 220346L 180 46L 2300 56L 206956L 2204 46L 2300 56L 206856L 2197 46L 2300 56L 204456L 2193 46L 2200 65L 192056L 2185 56L 1668 65L 182056L 2183 56L 1654 65L 179056L 2167 56L 1653 65L 172065L 2136 56L 1643 66L 254365L 2091 56L 1639 66L 242465L 2065 56L 1638 66L 232165L 2047 65L 1630 66L 226266L 2105 65L 1560 70L 2213966L 2022 65L 1530 9L 218066L 2009 65L 1490 9L 214066L 1983 66L 2179 9L 213070L 2272 66L 1900 9L 21109L 2385 66L 1762 9L 20709L 2377 66L 1734 9L 20709L 2375 70L 10404 32L 20509L 2359 9L 1640 32L 21009L 2356 9L 1640 32L 20209L 2354 9L 1610 32L 1960

32L 2240 9L 1590 16L 210032L 2260 9L 1590 16L 220032L 2200 9L 1560 16L 220032L 2270 32L 1640 16L 206016L 2300 32L 1600 16L 197016L 2310 32L 1560 16L 201016L 2350 32L 157016L 2260 16L 170016L 2290 16L 180016L 2240 16L 1700

16L 180016L 170016L 1700

European Commission EUR 23012 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on total organic carbon Author(s) E Sobiecka H van der Sloot K Andersen B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 50 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07412-7 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 total organic carbon (TOC) in soils sludge and treated bio-waste 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

-23012-EN

-C

15

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

16

Annex 3

Statistical calculations

Unit gkg

Mandels k statistics(Compost 1 - TOC)Mandels h statistics(Compost 1 - TOC)

Sample Compost 1 Compost 1 - TOC -- Mean PARM = 2463 [gkg]

Element TOC

General calcparmT1= 142643E+04T2= 351264E+06T3= 58T4= 292T5= 16501E+03

n= variabelp= 13

N-table= 5

Mandels statistics End ResultLAB 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

69L 1960000 64265 4 -235 352 Fail - - 69L - - -502735L 2291667 1674 6 -081 009 2291667 16741 6 5 -171066L 2377425 8552 4 -041 047 2377425 85518 4 3 -85346L 2395000 4796 4 -033 026 2395000 47958 4 3 -67756L 2401227 3133 6 -030 017 2401227 31330 6 5 -61432L 2415000 9713 4 -024 053 2415000 97125 4 3 -47770L 2435100 - 1 -014 2435100 - 1 -27616L 2440000 6033 6 -012 033 2440000 60332 6 5 -22745L 2503800 11759 6 018 064 2503800 117589 6 5 41136L 2514416 3994 3 023 022 2514416 39937 3 2 51765L 2537333 5216 3 033 029 2537333 52157 3 2 74744L 2555667 2783 6 042 015 2555667 27826 6 5 9309L 2568167 1356 6 048 007 2568167 13556 6 5 105530L 2580000 2000 3 053 011 2580000 20000 3 2 117334L 3013269 9580 6 255 053 Fail - - 34L - - 5506

Totgem 246587 9632 gkg 1-level 232 (176) 13 2462677 (34L 69L) 13 12Totstd= 21507 16070 5-level 186 (152) 2

68RESULTS Mean = 24626770 gkg

Repeatability variance S2r = 3666797Repeatability std Sr = 605541 --gt 246 r = 169551Between lab variance S2L = 7715586Reproducibility var S2R = 11382383Reproducibility std SR = 1066882 --gt 433 R = 298727Remarks 2 Labs rejected (34L 69L)

000 050 100 150 200 250 300 350 400

k-values

69L

35L

66L

46L

56L

32L

70L

16L

45L

36L

65L

44L

9L

30L

34L

Mandels k statistics(Compost 1 - TOC)

-600 -400 -200 00 200 400 600

Deviation from Mean

69L

35L

66L

46L

56L

32L

70L

16L

45L

36L

65L

44L

9L

30L

34L

Labo

rato

ries

Compost 1 - TOC -- Mean PARM = 2463 [gkg]

-300 -200 -100 000 100 200 300

h-values

69L

66L

56L

70L

45L

65L

9L

34L

Labo

rato

ries

Mandels h statistics(Compost 1 - TOC)

Compost 1-TOC

Unit gkg

Mandels k statistics(Compost 2 - TOC)Mandels h statistics(Compost 2 - TOC)

Sample Compost 2 Compost 2 - TOC -- Mean PARM = 1542 [gkg]

Element TOC

General calcparmT1= 994897E+03T2= 155556E+06T3= 64T4= 346T5= 41738E+03

n= variabelp= 13

N-table= 5

Mandels statistics End ResultLAB 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

45L 1326733 5665 6 -100 042 Fail 1326733 56646 6 5 -215046L 1355000 24365 4 -089 181 Fail - - 46L - - -186736L 1381949 5407 3 -078 040 Fail 1381949 54070 3 2 -159870L 1414120 - 1 -066 Fail 1414120 - 1 -127616L 1428333 5565 6 -061 041 1428333 55648 6 5 -113466L 1485550 7805 4 -039 058 1485550 78047 4 3 -56232L 1532500 5377 4 -021 040 1532500 53774 4 3 -09219L 1576833 10138 6 -004 075 1576833 101381 6 5 3519L 1582333 6166 6 -002 046 1582333 61659 6 5 40656L 1594432 4046 6 003 030 1594432 40463 6 5 52744L 1653000 3651 6 025 027 1653000 36508 6 5 111334L 1655127 13717 6 026 102 1655127 137168 6 5 113434L 1655127 13717 6 026 102 1655127 137168 6 5 113465L 1756500 16295 4 065 121 Fail 1756500 162949 4 3 214869L 2415000 30687 4 316 228 Fail - - 69L - - 8733

Totgem 158750 10900 gkg 1-level 232 (176) 13 1541734 (46L 69L) 13 12Totstd= 26187 8164 5-level 186 (152) 2

72RESULTS Mean = 15417337 gkg

Repeatability variance S2r = 8183950Repeatability std Sr = 904652 --gt 587 r = 253303Between lab variance S2L = 13631046Reproducibility var S2R = 21814995Reproducibility std SR = 1476990 --gt 958 R = 413557Remarks 2 Labs rejected (46L 69L)

000 050 100 150 200 250

k-values

45L

46L

36L

70L

16L

66L

32L

19L

9L

56L

44L

34L

34L

65L

69L

Mandels k statistics(Compost 2 - TOC)

-400 -200 00 200 400 600 800 1000

Deviation from Mean

45L

46L

36L

70L

16L

66L

32L

19L

9L

56L

44L

34L

34L

65L

69L

Labo

rato

ries

Compost 2 - TOC -- Mean PARM = 1542 [gkg]

-100 000 100 200 300 400

h-values

45L

36L

16L

32L

9L

44L

34L

69L

Labo

rato

ries

Mandels h statistics(Compost 2 - TOC)

Compost 2-TOC

Unit gkg

Mandels k statistics(Sludge 1 - TOC)Mandels h statistics(Sludge 1 - TOC)

Sample Sludge 1 Sludge 1 - TOC -- Mean PARM = 2721 [gkg]

Element TOC

General calcparmT1= 169626E+04T2= 465445E+06T3= 62T4= 326T5= 10312E+03

n= variabelp= 13

N-table= 5

Mandels statistics End ResultLAB 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

69L 233000 2362 4 -347 037 Fail - - 69L - - -2488046L 2312500 2062 4 -040 032 Fail 2312500 20616 4 3 -408565L 2615500 1708 4 004 026 2615500 17078 4 3 -105566L 2627200 8268 4 006 128 2627200 82678 4 3 -93836L 2664041 4976 3 011 077 2664041 49758 3 2 -56935L 2671500 3533 6 013 055 2671500 35331 6 5 -49556L 2692298 0874 6 016 014 Fail 2692298 08738 6 5 -28732L 2717500 6185 4 019 096 Fail 2717500 61847 4 3 -03519L 2753333 7819 6 025 121 Fail 2753333 78189 6 5 32470L 2814600 - 1 034 Fail 2814600 - 1 9369L 2853667 0398 6 039 006 Fail 2853667 03983 6 5 132716L 2860000 1673 6 040 026 Fail 2860000 16733 6 5 139045L 2884433 7033 6 044 109 Fail 2884433 70331 6 5 163544L 2906167 1129 6 047 017 Fail 2906167 11286 6 5 185234L 3186874 17674 6 089 274 Fail - - 34L - - 4659

Totgem 258617 4692 gkg 1-level 232 (176) 13 2720980 (34L 69L) 13 12Totstd= 67800 4610 5-level 186 (152) 2

72RESULTS Mean = 27209799 gkg

Repeatability variance S2r = 2104538Repeatability std Sr = 458752 --gt 169 r = 128451Between lab variance S2L = 23618387Reproducibility var S2R = 25722925Reproducibility std SR = 1603837 --gt 589 R = 449074Remarks 2 Labs rejected (34L 69L)

000 050 100 150 200 250 300

k-values

69L

46L

65L

66L

36L

35L

56L

32L

19L

70L

9L

16L

45L

44L

34L

Mandels k statistics(Sludge 1 - TOC)

-2500 -2000 -1500 -1000 -500 00 500

Deviation from Mean

69L

46L

65L

66L

36L

35L

56L

32L

19L

70L

9L

16L

45L

44L

34L

Labo

rato

ries

Sludge 1 - TOC -- Mean PARM = 2721 [gkg]

-400 -300 -200 -100 000 100

h-values

69L

65L

36L

56L

19L

9L

45L

34L

Labo

rato

ries

Mandels h statistics(Sludge 1 - TOC)

Sludge 1-TOC

68 Unit gkg

Mandels k statistics(Sludge 2 - TOC)Mandels h statistics(Sludge 2 - TOC)

Sample Sludge 2 Sludge 2 - TOC -- Mean PARM = 2207 [gkg]

Element TOC

General calcparmT1= 128601E+04T2= 285689E+06T3= 58T4= 310T5= 97826E+02

n= variabelp= 12

N-table= 5

Mandels statistics End ResultLAB 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

46L 182500 0500 4 -333 008 Fail - - 46L - - -2024466L 2029475 5267 4 -012 084 2029475 52674 4 3 -177436L 2072609 2222 3 -005 035 2072609 22222 3 2 -134365L 2084750 3865 4 -002 062 2084750 38647 4 3 -122135L 2140333 3119 6 007 050 2140333 31194 6 5 -66556L 2188021 1282 6 015 020 2188021 12822 6 5 -18819L 2223667 7916 6 022 126 Fail 2223667 79157 6 5 16832L 2242500 3096 4 025 049 Fail 2242500 30957 4 3 35645L 2266600 8322 6 029 132 Fail 2266600 83216 6 5 59770L 2272460 - 1 030 Fail 2272460 - 1 65616L 2291667 3869 6 033 062 Fail 2291667 38687 6 5 84844L 2302667 1546 6 035 025 Fail 2302667 15462 6 5 9589L 2367667 1296 6 047 021 Fail 2367667 12956 6 5 160834L 2718591 17124 6 108 273 Fail - - 34L - - 5117

Totgem 209882 4571 gkg 1-level 230 (176) 12 2206868 (34L 46L) 12 11Totstd= 57628 4485 5-level 185 (151) 2

68RESULTS Mean = 22068679 gkg

Repeatability variance S2r = 2126659Repeatability std Sr = 461157 --gt 209 r = 129124Between lab variance S2L = 9960432Reproducibility var S2R = 12087091Reproducibility std SR = 1099413 --gt 498 R = 307836Remarks 2 Labs rejected (34L 46L)

000 050 100 150 200 250 300

k-values

46L

66L

36L

65L

35L

56L

19L

32L

45L

70L

16L

44L

9L

34L

Mandels k statistics(Sludge 2 - TOC)

-2500 -2000 -1500 -1000 -500 00 500 1000

Deviation from Mean

46L

66L

36L

65L

35L

56L

19L

32L

45L

70L

16L

44L

9L

34L

Labo

rato

ries

Sludge 2 - TOC -- Mean PARM = 2207 [gkg]

-400 -300 -200 -100 000 100 200

h-values

46L

66L

36L

65L

35L

56L

19L

32L

45L

70L

16L

44L

9L

34L

Labo

rato

ries

Mandels h statistics(Sludge 2 - TOC)

Sludge 2-TOC

Unit gkg

Mandels k statistics(Soil 4 - TOC)Mandels h statistics(Soil 4 - TOC)

Sample Soil 4 Soil 4 - TOC -- Mean PARM = 1641 [gkg]

Element TOC

General calcparmT1= 102171E+03T2= 168700E+04T3= 62T4= 338T5= 94040E+00

n= variabelp= 12

N-table= 5

Mandels statistics End ResultLAB 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

36L 147161 0470 3 -036 068 Fail 147161 04702 3 2 -16965L 155250 0591 4 -032 085 Fail 155250 05909 4 3 -08844L 157900 0115 6 -031 017 Fail 157900 01152 6 5 -06232L 159250 0359 4 -031 052 Fail 159250 03594 4 3 -0489L 160500 0315 6 -030 045 Fail 160500 03146 6 5 -03656L 164927 0113 6 -028 016 Fail 164927 01127 6 5 00835L 165000 0261 6 -028 038 Fail 165000 02608 6 5 00919L 166667 0505 6 -027 073 Fail 166667 05046 6 5 02645L 168850 0763 6 -026 110 Fail 168850 07628 6 5 04816L 173333 0516 6 -024 074 Fail 173333 05164 6 5 09334L 174761 0346 6 -024 050 Fail 174761 03462 6 5 10730L 175333 0473 3 -024 068 Fail 175333 04726 3 2 11366L 189375 2035 4 -017 294 Fail - - 66L - - 25346L 227500 0500 4 000 072 - - 46L - - 63470L 1040400 - 1 360 Fail - - 70L - - 8763

Totgem 22841 0526 gkg 1-level 232 (176) 12 164078 (46L 66L70L) 12 11Totstd= 22541 0469 5-level 186 (152) 3

71RESULTS Mean = 1640777 gkg

Repeatability variance S2r = 018808Repeatability std Sr = 043368 --gt 264 r = 12143Between lab variance S2L = 054747Reproducibility var S2R = 073555Reproducibility std SR = 085764 --gt 523 R = 24014Remarks 3 Labs rejected (46L 66L70L)

000 050 100 150 200 250 300

k-values

36L

65L

44L

32L

9L

56L

35L

19L

45L

16L

34L

30L

66L

46L

70L

Mandels k statistics(Soil 4 - TOC)

-100 00 100 200 300 400 500 600 700 800 900

Deviation from Mean

36L

65L

44L

32L

9L

56L

35L

19L

45L

16L

34L

30L

66L

46L

70L

Labo

rato

ries

Soil 4 - TOC -- Mean PARM = 1641 [gkg]

-100 000 100 200 300 400

h-values

36L

44L

9L

35L

45L

34L

66L

70L

Labo

rato

ries

Mandels h statistics(Soil 4 - TOC)

Soil 4-TOC

Unit gkg

Mandels k statistics(Soil 5 - TOC)Mandels h statistics(Soil 5 - TOC)

Sample Soil 5 Soil 5 - TOC -- Mean PARM = 2102 [gkg]

Element TOC

General calcparmT1= 113661E+03T2= 240201E+04T3= 54T4= 300T5= 51756E+01

n= variabelp= 10

N-table= 5

Mandels statistics End ResultLAB 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

44L 164383 14708 6 -036 325 Fail - - 44L - - -45865L 181250 0830 4 -033 018 Fail 181250 08302 4 3 -29045L 200317 1116 6 -029 025 Fail 200317 11163 6 5 -09935L 201833 1828 6 -029 040 Fail 201833 18280 6 5 -08432L 203250 0585 4 -029 013 Fail 203250 05852 4 3 -07016L 209000 0959 6 -028 021 Fail 209000 09592 6 5 -0129L 211667 0427 6 -027 009 Fail 211667 04274 6 5 01556L 214030 0887 6 -027 020 Fail 214030 08868 6 5 03819L 216000 0795 6 -026 018 Fail 216000 07950 6 5 05834L 226009 1308 6 -024 029 Fail 226009 13076 6 5 15836L 228783 4310 3 -024 095 Fail - - 36L - - 18666L 238750 1234 4 -022 027 Fail 238750 12340 4 3 28570L 2213900 - 1 333 Fail - - 70L - - 20037

Totgem 36224 2416 gkg 1-level 227 (175) 10 210211 (36L44L 70L) 10 9Totstd= 55669 4003 5-level 184 (151) 3

64RESULTS Mean = 2102106 gkg

Repeatability variance S2r = 117627Repeatability std Sr = 108456 --gt 516 r = 30368Between lab variance S2L = 176699Reproducibility var S2R = 294326Reproducibility std SR = 171559 --gt 816 R = 48037Remarks 3 Labs rejected (36L44L 70L)

000 050 100 150 200 250 300 350

k-values

44L

65L

45L

35L

32L

16L

9L

56L

19L

34L

36L

66L

70L

Mandels k statistics(Soil 5 - TOC)

-500 00 500 1000 1500 2000 2500

Deviation from Mean

44L

65L

45L

35L

32L

16L

9L

56L

19L

34L

36L

66L

70L

Labo

rato

ries

Soil 5 - TOC -- Mean PARM = 2102 [gkg]

-100 000 100 200 300 400

h-values

44L

65L

45L

35L

32L

16L

9L

56L

19L

34L

36L

66L

70L

Labo

rato

ries

Mandels h statistics(Soil 5 - TOC)

Soil 5-TOC

17

Annex 4

Raw data submitted

Sample Compost 1 Sample Compost 2 Sample Sewage Sludge 1Element TOC [gkg] Element TOC [gkg] Element TOC [gkg]

LAB PARM LAB PARM LAB PARM30L 2600 19L 1691 19L 286730L 2580 19L 1634 19L 281430L 2560 19L 1619 19L 276934L 2969 19L 1604 19L 272034L 2936 19L 1499 19L 268834L 2958 19L 1414 19L 266234L 2994 34L 1527 34L 315234L 3199 34L 1622 34L 314934L 3024 34L 1519 34L 343035L 2306 34L 1753 34L 336535L 2300 34L 1636 34L 304235L 2298 34L 1874 34L 298335L 2296 35L 1506 35L 270735L 2291 35L 1312 35L 270335L 2259 35L 1294 35L 268836L 2546 35L 1279 35L 267436L 2527 35L 1191 35L 263136L 2470 35L 1177 35L 262644L 2583 36L 1418 36L 271344L 2581 36L 1408 36L 266544L 2578 36L 1320 36L 261444L 2539 44L 1719 44L 292044L 2528 44L 1664 44L 291644L 2525 44L 1654 44L 291245L 2658 44L 1637 44L 290045L 2600 44L 1624 44L 289645L 2546 44L 1620 44L 289345L 2461 45L 1428 45L 297645L 2409 45L 1325 45L 295245L 2350 45L 1323 45L 288546L 2460 45L 1321 45L 286646L 2400 45L 1309 45L 284046L 2370 45L 1253 45L 278746L 2350 46L 1580 46L 233056L 2436 46L 1550 46L 233056L 2435 46L 1170 46L 230056L 2405 46L 1120 46L 229056L 2397 56L 1642 56L 270256L 2375 56L 1626 56L 270156L 2358 56L 1622 56L 269465L 2587 56L 1571 56L 269365L 2542 56L 1561 56L 268465L 2483 56L 1545 56L 268066L 2454 65L 1933 65L 264166L 2429 65L 1838 65L 260966L 2365 65L 1693 65L 260766L 2262 65L 1562 65L 260569L 2730 66L 1561 66L 270169L 2250 66L 1545 66L 267469L 1440 66L 1420 66L 261969L 1420 66L 1417 66L 251470L 2435 69L 2700 69L 2639L 2594 69L 2660 69L 2409L 2570 69L 2170 69L 2199L 2565 69L 2130 69L 2109L 2563 70L 1414 70L 28159L 2562 9L 1644 9L 28579L 2555 9L 1641 9L 2856

32L 2290 9L 1602 9L 285532L 2390 9L 1589 9L 285532L 2510 9L 1526 9L 285332L 2470 9L 1492 9L 284616L 2380 32L 1470 32L 265016L 2530 32L 1520 32L 271016L 2400 32L 1540 32L 271016L 2500 32L 1600 32L 280016L 2420 16L 1400 16L 284016L 2410 16L 1440 16L 2840

16L 1470 16L 286016L 1510 16L 287016L 1360 16L 287016L 1390 16L 2880

Sample Sewage Sludge 2 Sample Soil 4 Sample Soil 5Element TOC [gkg] Element TOC [gkg] Element TOC [gkg]

LAB PARM LAB PARM LAB PARM19L 2308 19L 1720 19L 225019L 2303 19L 1700 19L 223019L 2239 19L 1690 19L 221019L 2204 19L 1670 19L 211019L 2192 19L 1640 19L 210019L 2096 19L 1580 19L 206034L 2631 30L 1790 34L 244334L 2471 30L 1770 34L 233434L 2977 30L 1700 34L 231534L 2785 34L 1740 34L 222134L 2780 34L 1692 34L 217634L 2668 34L 1727 34L 207335L 2179 34L 1767 35L 233035L 2160 34L 1777 35L 208035L 2158 34L 1783 35L 201035L 2132 35L 1700 35L 198035L 2119 35L 1650 35L 193035L 2094 35L 1650 35L 178036L 2096 35L 1640 36L 254036L 2069 35L 1630 36L 253436L 2052 35L 1630 36L 179044L 2325 36L 1500 44L 302144L 2309 36L 1497 44L 298244L 2307 36L 1417 44L 295644L 2305 44L 1594 44L 30744L 2287 44L 1587 44L 30044L 2283 44L 1584 44L 29745L 2331 44L 1574 45L 214945L 2327 44L 1573 45L 209245L 2308 44L 1562 45L 203345L 2287 45L 1827 45L 197145L 2234 45L 1709 45L 193345L 2113 45L 1666 45L 184146L 190 45L 1665 56L 223746L 180 45L 1664 56L 222246L 180 45L 1600 56L 220346L 180 46L 2300 56L 206956L 2204 46L 2300 56L 206856L 2197 46L 2300 56L 204456L 2193 46L 2200 65L 192056L 2185 56L 1668 65L 182056L 2183 56L 1654 65L 179056L 2167 56L 1653 65L 172065L 2136 56L 1643 66L 254365L 2091 56L 1639 66L 242465L 2065 56L 1638 66L 232165L 2047 65L 1630 66L 226266L 2105 65L 1560 70L 2213966L 2022 65L 1530 9L 218066L 2009 65L 1490 9L 214066L 1983 66L 2179 9L 213070L 2272 66L 1900 9L 21109L 2385 66L 1762 9L 20709L 2377 66L 1734 9L 20709L 2375 70L 10404 32L 20509L 2359 9L 1640 32L 21009L 2356 9L 1640 32L 20209L 2354 9L 1610 32L 1960

32L 2240 9L 1590 16L 210032L 2260 9L 1590 16L 220032L 2200 9L 1560 16L 220032L 2270 32L 1640 16L 206016L 2300 32L 1600 16L 197016L 2310 32L 1560 16L 201016L 2350 32L 157016L 2260 16L 170016L 2290 16L 180016L 2240 16L 1700

16L 180016L 170016L 1700

European Commission EUR 23012 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on total organic carbon Author(s) E Sobiecka H van der Sloot K Andersen B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 50 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07412-7 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 total organic carbon (TOC) in soils sludge and treated bio-waste 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

-23012-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

16

Annex 3

Statistical calculations

Unit gkg

Mandels k statistics(Compost 1 - TOC)Mandels h statistics(Compost 1 - TOC)

Sample Compost 1 Compost 1 - TOC -- Mean PARM = 2463 [gkg]

Element TOC

General calcparmT1= 142643E+04T2= 351264E+06T3= 58T4= 292T5= 16501E+03

n= variabelp= 13

N-table= 5

Mandels statistics End ResultLAB 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

69L 1960000 64265 4 -235 352 Fail - - 69L - - -502735L 2291667 1674 6 -081 009 2291667 16741 6 5 -171066L 2377425 8552 4 -041 047 2377425 85518 4 3 -85346L 2395000 4796 4 -033 026 2395000 47958 4 3 -67756L 2401227 3133 6 -030 017 2401227 31330 6 5 -61432L 2415000 9713 4 -024 053 2415000 97125 4 3 -47770L 2435100 - 1 -014 2435100 - 1 -27616L 2440000 6033 6 -012 033 2440000 60332 6 5 -22745L 2503800 11759 6 018 064 2503800 117589 6 5 41136L 2514416 3994 3 023 022 2514416 39937 3 2 51765L 2537333 5216 3 033 029 2537333 52157 3 2 74744L 2555667 2783 6 042 015 2555667 27826 6 5 9309L 2568167 1356 6 048 007 2568167 13556 6 5 105530L 2580000 2000 3 053 011 2580000 20000 3 2 117334L 3013269 9580 6 255 053 Fail - - 34L - - 5506

Totgem 246587 9632 gkg 1-level 232 (176) 13 2462677 (34L 69L) 13 12Totstd= 21507 16070 5-level 186 (152) 2

68RESULTS Mean = 24626770 gkg

Repeatability variance S2r = 3666797Repeatability std Sr = 605541 --gt 246 r = 169551Between lab variance S2L = 7715586Reproducibility var S2R = 11382383Reproducibility std SR = 1066882 --gt 433 R = 298727Remarks 2 Labs rejected (34L 69L)

000 050 100 150 200 250 300 350 400

k-values

69L

35L

66L

46L

56L

32L

70L

16L

45L

36L

65L

44L

9L

30L

34L

Mandels k statistics(Compost 1 - TOC)

-600 -400 -200 00 200 400 600

Deviation from Mean

69L

35L

66L

46L

56L

32L

70L

16L

45L

36L

65L

44L

9L

30L

34L

Labo

rato

ries

Compost 1 - TOC -- Mean PARM = 2463 [gkg]

-300 -200 -100 000 100 200 300

h-values

69L

66L

56L

70L

45L

65L

9L

34L

Labo

rato

ries

Mandels h statistics(Compost 1 - TOC)

Compost 1-TOC

Unit gkg

Mandels k statistics(Compost 2 - TOC)Mandels h statistics(Compost 2 - TOC)

Sample Compost 2 Compost 2 - TOC -- Mean PARM = 1542 [gkg]

Element TOC

General calcparmT1= 994897E+03T2= 155556E+06T3= 64T4= 346T5= 41738E+03

n= variabelp= 13

N-table= 5

Mandels statistics End ResultLAB 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

45L 1326733 5665 6 -100 042 Fail 1326733 56646 6 5 -215046L 1355000 24365 4 -089 181 Fail - - 46L - - -186736L 1381949 5407 3 -078 040 Fail 1381949 54070 3 2 -159870L 1414120 - 1 -066 Fail 1414120 - 1 -127616L 1428333 5565 6 -061 041 1428333 55648 6 5 -113466L 1485550 7805 4 -039 058 1485550 78047 4 3 -56232L 1532500 5377 4 -021 040 1532500 53774 4 3 -09219L 1576833 10138 6 -004 075 1576833 101381 6 5 3519L 1582333 6166 6 -002 046 1582333 61659 6 5 40656L 1594432 4046 6 003 030 1594432 40463 6 5 52744L 1653000 3651 6 025 027 1653000 36508 6 5 111334L 1655127 13717 6 026 102 1655127 137168 6 5 113434L 1655127 13717 6 026 102 1655127 137168 6 5 113465L 1756500 16295 4 065 121 Fail 1756500 162949 4 3 214869L 2415000 30687 4 316 228 Fail - - 69L - - 8733

Totgem 158750 10900 gkg 1-level 232 (176) 13 1541734 (46L 69L) 13 12Totstd= 26187 8164 5-level 186 (152) 2

72RESULTS Mean = 15417337 gkg

Repeatability variance S2r = 8183950Repeatability std Sr = 904652 --gt 587 r = 253303Between lab variance S2L = 13631046Reproducibility var S2R = 21814995Reproducibility std SR = 1476990 --gt 958 R = 413557Remarks 2 Labs rejected (46L 69L)

000 050 100 150 200 250

k-values

45L

46L

36L

70L

16L

66L

32L

19L

9L

56L

44L

34L

34L

65L

69L

Mandels k statistics(Compost 2 - TOC)

-400 -200 00 200 400 600 800 1000

Deviation from Mean

45L

46L

36L

70L

16L

66L

32L

19L

9L

56L

44L

34L

34L

65L

69L

Labo

rato

ries

Compost 2 - TOC -- Mean PARM = 1542 [gkg]

-100 000 100 200 300 400

h-values

45L

36L

16L

32L

9L

44L

34L

69L

Labo

rato

ries

Mandels h statistics(Compost 2 - TOC)

Compost 2-TOC

Unit gkg

Mandels k statistics(Sludge 1 - TOC)Mandels h statistics(Sludge 1 - TOC)

Sample Sludge 1 Sludge 1 - TOC -- Mean PARM = 2721 [gkg]

Element TOC

General calcparmT1= 169626E+04T2= 465445E+06T3= 62T4= 326T5= 10312E+03

n= variabelp= 13

N-table= 5

Mandels statistics End ResultLAB 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

69L 233000 2362 4 -347 037 Fail - - 69L - - -2488046L 2312500 2062 4 -040 032 Fail 2312500 20616 4 3 -408565L 2615500 1708 4 004 026 2615500 17078 4 3 -105566L 2627200 8268 4 006 128 2627200 82678 4 3 -93836L 2664041 4976 3 011 077 2664041 49758 3 2 -56935L 2671500 3533 6 013 055 2671500 35331 6 5 -49556L 2692298 0874 6 016 014 Fail 2692298 08738 6 5 -28732L 2717500 6185 4 019 096 Fail 2717500 61847 4 3 -03519L 2753333 7819 6 025 121 Fail 2753333 78189 6 5 32470L 2814600 - 1 034 Fail 2814600 - 1 9369L 2853667 0398 6 039 006 Fail 2853667 03983 6 5 132716L 2860000 1673 6 040 026 Fail 2860000 16733 6 5 139045L 2884433 7033 6 044 109 Fail 2884433 70331 6 5 163544L 2906167 1129 6 047 017 Fail 2906167 11286 6 5 185234L 3186874 17674 6 089 274 Fail - - 34L - - 4659

Totgem 258617 4692 gkg 1-level 232 (176) 13 2720980 (34L 69L) 13 12Totstd= 67800 4610 5-level 186 (152) 2

72RESULTS Mean = 27209799 gkg

Repeatability variance S2r = 2104538Repeatability std Sr = 458752 --gt 169 r = 128451Between lab variance S2L = 23618387Reproducibility var S2R = 25722925Reproducibility std SR = 1603837 --gt 589 R = 449074Remarks 2 Labs rejected (34L 69L)

000 050 100 150 200 250 300

k-values

69L

46L

65L

66L

36L

35L

56L

32L

19L

70L

9L

16L

45L

44L

34L

Mandels k statistics(Sludge 1 - TOC)

-2500 -2000 -1500 -1000 -500 00 500

Deviation from Mean

69L

46L

65L

66L

36L

35L

56L

32L

19L

70L

9L

16L

45L

44L

34L

Labo

rato

ries

Sludge 1 - TOC -- Mean PARM = 2721 [gkg]

-400 -300 -200 -100 000 100

h-values

69L

65L

36L

56L

19L

9L

45L

34L

Labo

rato

ries

Mandels h statistics(Sludge 1 - TOC)

Sludge 1-TOC

68 Unit gkg

Mandels k statistics(Sludge 2 - TOC)Mandels h statistics(Sludge 2 - TOC)

Sample Sludge 2 Sludge 2 - TOC -- Mean PARM = 2207 [gkg]

Element TOC

General calcparmT1= 128601E+04T2= 285689E+06T3= 58T4= 310T5= 97826E+02

n= variabelp= 12

N-table= 5

Mandels statistics End ResultLAB 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

46L 182500 0500 4 -333 008 Fail - - 46L - - -2024466L 2029475 5267 4 -012 084 2029475 52674 4 3 -177436L 2072609 2222 3 -005 035 2072609 22222 3 2 -134365L 2084750 3865 4 -002 062 2084750 38647 4 3 -122135L 2140333 3119 6 007 050 2140333 31194 6 5 -66556L 2188021 1282 6 015 020 2188021 12822 6 5 -18819L 2223667 7916 6 022 126 Fail 2223667 79157 6 5 16832L 2242500 3096 4 025 049 Fail 2242500 30957 4 3 35645L 2266600 8322 6 029 132 Fail 2266600 83216 6 5 59770L 2272460 - 1 030 Fail 2272460 - 1 65616L 2291667 3869 6 033 062 Fail 2291667 38687 6 5 84844L 2302667 1546 6 035 025 Fail 2302667 15462 6 5 9589L 2367667 1296 6 047 021 Fail 2367667 12956 6 5 160834L 2718591 17124 6 108 273 Fail - - 34L - - 5117

Totgem 209882 4571 gkg 1-level 230 (176) 12 2206868 (34L 46L) 12 11Totstd= 57628 4485 5-level 185 (151) 2

68RESULTS Mean = 22068679 gkg

Repeatability variance S2r = 2126659Repeatability std Sr = 461157 --gt 209 r = 129124Between lab variance S2L = 9960432Reproducibility var S2R = 12087091Reproducibility std SR = 1099413 --gt 498 R = 307836Remarks 2 Labs rejected (34L 46L)

000 050 100 150 200 250 300

k-values

46L

66L

36L

65L

35L

56L

19L

32L

45L

70L

16L

44L

9L

34L

Mandels k statistics(Sludge 2 - TOC)

-2500 -2000 -1500 -1000 -500 00 500 1000

Deviation from Mean

46L

66L

36L

65L

35L

56L

19L

32L

45L

70L

16L

44L

9L

34L

Labo

rato

ries

Sludge 2 - TOC -- Mean PARM = 2207 [gkg]

-400 -300 -200 -100 000 100 200

h-values

46L

66L

36L

65L

35L

56L

19L

32L

45L

70L

16L

44L

9L

34L

Labo

rato

ries

Mandels h statistics(Sludge 2 - TOC)

Sludge 2-TOC

Unit gkg

Mandels k statistics(Soil 4 - TOC)Mandels h statistics(Soil 4 - TOC)

Sample Soil 4 Soil 4 - TOC -- Mean PARM = 1641 [gkg]

Element TOC

General calcparmT1= 102171E+03T2= 168700E+04T3= 62T4= 338T5= 94040E+00

n= variabelp= 12

N-table= 5

Mandels statistics End ResultLAB 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

36L 147161 0470 3 -036 068 Fail 147161 04702 3 2 -16965L 155250 0591 4 -032 085 Fail 155250 05909 4 3 -08844L 157900 0115 6 -031 017 Fail 157900 01152 6 5 -06232L 159250 0359 4 -031 052 Fail 159250 03594 4 3 -0489L 160500 0315 6 -030 045 Fail 160500 03146 6 5 -03656L 164927 0113 6 -028 016 Fail 164927 01127 6 5 00835L 165000 0261 6 -028 038 Fail 165000 02608 6 5 00919L 166667 0505 6 -027 073 Fail 166667 05046 6 5 02645L 168850 0763 6 -026 110 Fail 168850 07628 6 5 04816L 173333 0516 6 -024 074 Fail 173333 05164 6 5 09334L 174761 0346 6 -024 050 Fail 174761 03462 6 5 10730L 175333 0473 3 -024 068 Fail 175333 04726 3 2 11366L 189375 2035 4 -017 294 Fail - - 66L - - 25346L 227500 0500 4 000 072 - - 46L - - 63470L 1040400 - 1 360 Fail - - 70L - - 8763

Totgem 22841 0526 gkg 1-level 232 (176) 12 164078 (46L 66L70L) 12 11Totstd= 22541 0469 5-level 186 (152) 3

71RESULTS Mean = 1640777 gkg

Repeatability variance S2r = 018808Repeatability std Sr = 043368 --gt 264 r = 12143Between lab variance S2L = 054747Reproducibility var S2R = 073555Reproducibility std SR = 085764 --gt 523 R = 24014Remarks 3 Labs rejected (46L 66L70L)

000 050 100 150 200 250 300

k-values

36L

65L

44L

32L

9L

56L

35L

19L

45L

16L

34L

30L

66L

46L

70L

Mandels k statistics(Soil 4 - TOC)

-100 00 100 200 300 400 500 600 700 800 900

Deviation from Mean

36L

65L

44L

32L

9L

56L

35L

19L

45L

16L

34L

30L

66L

46L

70L

Labo

rato

ries

Soil 4 - TOC -- Mean PARM = 1641 [gkg]

-100 000 100 200 300 400

h-values

36L

44L

9L

35L

45L

34L

66L

70L

Labo

rato

ries

Mandels h statistics(Soil 4 - TOC)

Soil 4-TOC

Unit gkg

Mandels k statistics(Soil 5 - TOC)Mandels h statistics(Soil 5 - TOC)

Sample Soil 5 Soil 5 - TOC -- Mean PARM = 2102 [gkg]

Element TOC

General calcparmT1= 113661E+03T2= 240201E+04T3= 54T4= 300T5= 51756E+01

n= variabelp= 10

N-table= 5

Mandels statistics End ResultLAB 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

44L 164383 14708 6 -036 325 Fail - - 44L - - -45865L 181250 0830 4 -033 018 Fail 181250 08302 4 3 -29045L 200317 1116 6 -029 025 Fail 200317 11163 6 5 -09935L 201833 1828 6 -029 040 Fail 201833 18280 6 5 -08432L 203250 0585 4 -029 013 Fail 203250 05852 4 3 -07016L 209000 0959 6 -028 021 Fail 209000 09592 6 5 -0129L 211667 0427 6 -027 009 Fail 211667 04274 6 5 01556L 214030 0887 6 -027 020 Fail 214030 08868 6 5 03819L 216000 0795 6 -026 018 Fail 216000 07950 6 5 05834L 226009 1308 6 -024 029 Fail 226009 13076 6 5 15836L 228783 4310 3 -024 095 Fail - - 36L - - 18666L 238750 1234 4 -022 027 Fail 238750 12340 4 3 28570L 2213900 - 1 333 Fail - - 70L - - 20037

Totgem 36224 2416 gkg 1-level 227 (175) 10 210211 (36L44L 70L) 10 9Totstd= 55669 4003 5-level 184 (151) 3

64RESULTS Mean = 2102106 gkg

Repeatability variance S2r = 117627Repeatability std Sr = 108456 --gt 516 r = 30368Between lab variance S2L = 176699Reproducibility var S2R = 294326Reproducibility std SR = 171559 --gt 816 R = 48037Remarks 3 Labs rejected (36L44L 70L)

000 050 100 150 200 250 300 350

k-values

44L

65L

45L

35L

32L

16L

9L

56L

19L

34L

36L

66L

70L

Mandels k statistics(Soil 5 - TOC)

-500 00 500 1000 1500 2000 2500

Deviation from Mean

44L

65L

45L

35L

32L

16L

9L

56L

19L

34L

36L

66L

70L

Labo

rato

ries

Soil 5 - TOC -- Mean PARM = 2102 [gkg]

-100 000 100 200 300 400

h-values

44L

65L

45L

35L

32L

16L

9L

56L

19L

34L

36L

66L

70L

Labo

rato

ries

Mandels h statistics(Soil 5 - TOC)

Soil 5-TOC

17

Annex 4

Raw data submitted

Sample Compost 1 Sample Compost 2 Sample Sewage Sludge 1Element TOC [gkg] Element TOC [gkg] Element TOC [gkg]

LAB PARM LAB PARM LAB PARM30L 2600 19L 1691 19L 286730L 2580 19L 1634 19L 281430L 2560 19L 1619 19L 276934L 2969 19L 1604 19L 272034L 2936 19L 1499 19L 268834L 2958 19L 1414 19L 266234L 2994 34L 1527 34L 315234L 3199 34L 1622 34L 314934L 3024 34L 1519 34L 343035L 2306 34L 1753 34L 336535L 2300 34L 1636 34L 304235L 2298 34L 1874 34L 298335L 2296 35L 1506 35L 270735L 2291 35L 1312 35L 270335L 2259 35L 1294 35L 268836L 2546 35L 1279 35L 267436L 2527 35L 1191 35L 263136L 2470 35L 1177 35L 262644L 2583 36L 1418 36L 271344L 2581 36L 1408 36L 266544L 2578 36L 1320 36L 261444L 2539 44L 1719 44L 292044L 2528 44L 1664 44L 291644L 2525 44L 1654 44L 291245L 2658 44L 1637 44L 290045L 2600 44L 1624 44L 289645L 2546 44L 1620 44L 289345L 2461 45L 1428 45L 297645L 2409 45L 1325 45L 295245L 2350 45L 1323 45L 288546L 2460 45L 1321 45L 286646L 2400 45L 1309 45L 284046L 2370 45L 1253 45L 278746L 2350 46L 1580 46L 233056L 2436 46L 1550 46L 233056L 2435 46L 1170 46L 230056L 2405 46L 1120 46L 229056L 2397 56L 1642 56L 270256L 2375 56L 1626 56L 270156L 2358 56L 1622 56L 269465L 2587 56L 1571 56L 269365L 2542 56L 1561 56L 268465L 2483 56L 1545 56L 268066L 2454 65L 1933 65L 264166L 2429 65L 1838 65L 260966L 2365 65L 1693 65L 260766L 2262 65L 1562 65L 260569L 2730 66L 1561 66L 270169L 2250 66L 1545 66L 267469L 1440 66L 1420 66L 261969L 1420 66L 1417 66L 251470L 2435 69L 2700 69L 2639L 2594 69L 2660 69L 2409L 2570 69L 2170 69L 2199L 2565 69L 2130 69L 2109L 2563 70L 1414 70L 28159L 2562 9L 1644 9L 28579L 2555 9L 1641 9L 2856

32L 2290 9L 1602 9L 285532L 2390 9L 1589 9L 285532L 2510 9L 1526 9L 285332L 2470 9L 1492 9L 284616L 2380 32L 1470 32L 265016L 2530 32L 1520 32L 271016L 2400 32L 1540 32L 271016L 2500 32L 1600 32L 280016L 2420 16L 1400 16L 284016L 2410 16L 1440 16L 2840

16L 1470 16L 286016L 1510 16L 287016L 1360 16L 287016L 1390 16L 2880

Sample Sewage Sludge 2 Sample Soil 4 Sample Soil 5Element TOC [gkg] Element TOC [gkg] Element TOC [gkg]

LAB PARM LAB PARM LAB PARM19L 2308 19L 1720 19L 225019L 2303 19L 1700 19L 223019L 2239 19L 1690 19L 221019L 2204 19L 1670 19L 211019L 2192 19L 1640 19L 210019L 2096 19L 1580 19L 206034L 2631 30L 1790 34L 244334L 2471 30L 1770 34L 233434L 2977 30L 1700 34L 231534L 2785 34L 1740 34L 222134L 2780 34L 1692 34L 217634L 2668 34L 1727 34L 207335L 2179 34L 1767 35L 233035L 2160 34L 1777 35L 208035L 2158 34L 1783 35L 201035L 2132 35L 1700 35L 198035L 2119 35L 1650 35L 193035L 2094 35L 1650 35L 178036L 2096 35L 1640 36L 254036L 2069 35L 1630 36L 253436L 2052 35L 1630 36L 179044L 2325 36L 1500 44L 302144L 2309 36L 1497 44L 298244L 2307 36L 1417 44L 295644L 2305 44L 1594 44L 30744L 2287 44L 1587 44L 30044L 2283 44L 1584 44L 29745L 2331 44L 1574 45L 214945L 2327 44L 1573 45L 209245L 2308 44L 1562 45L 203345L 2287 45L 1827 45L 197145L 2234 45L 1709 45L 193345L 2113 45L 1666 45L 184146L 190 45L 1665 56L 223746L 180 45L 1664 56L 222246L 180 45L 1600 56L 220346L 180 46L 2300 56L 206956L 2204 46L 2300 56L 206856L 2197 46L 2300 56L 204456L 2193 46L 2200 65L 192056L 2185 56L 1668 65L 182056L 2183 56L 1654 65L 179056L 2167 56L 1653 65L 172065L 2136 56L 1643 66L 254365L 2091 56L 1639 66L 242465L 2065 56L 1638 66L 232165L 2047 65L 1630 66L 226266L 2105 65L 1560 70L 2213966L 2022 65L 1530 9L 218066L 2009 65L 1490 9L 214066L 1983 66L 2179 9L 213070L 2272 66L 1900 9L 21109L 2385 66L 1762 9L 20709L 2377 66L 1734 9L 20709L 2375 70L 10404 32L 20509L 2359 9L 1640 32L 21009L 2356 9L 1640 32L 20209L 2354 9L 1610 32L 1960

32L 2240 9L 1590 16L 210032L 2260 9L 1590 16L 220032L 2200 9L 1560 16L 220032L 2270 32L 1640 16L 206016L 2300 32L 1600 16L 197016L 2310 32L 1560 16L 201016L 2350 32L 157016L 2260 16L 170016L 2290 16L 180016L 2240 16L 1700

16L 180016L 170016L 1700

European Commission EUR 23012 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on total organic carbon Author(s) E Sobiecka H van der Sloot K Andersen B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 50 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07412-7 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 total organic carbon (TOC) in soils sludge and treated bio-waste 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

-23012-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

16

Annex 3

Statistical calculations

Unit gkg

Mandels k statistics(Compost 1 - TOC)Mandels h statistics(Compost 1 - TOC)

Sample Compost 1 Compost 1 - TOC -- Mean PARM = 2463 [gkg]

Element TOC

General calcparmT1= 142643E+04T2= 351264E+06T3= 58T4= 292T5= 16501E+03

n= variabelp= 13

N-table= 5

Mandels statistics End ResultLAB 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

69L 1960000 64265 4 -235 352 Fail - - 69L - - -502735L 2291667 1674 6 -081 009 2291667 16741 6 5 -171066L 2377425 8552 4 -041 047 2377425 85518 4 3 -85346L 2395000 4796 4 -033 026 2395000 47958 4 3 -67756L 2401227 3133 6 -030 017 2401227 31330 6 5 -61432L 2415000 9713 4 -024 053 2415000 97125 4 3 -47770L 2435100 - 1 -014 2435100 - 1 -27616L 2440000 6033 6 -012 033 2440000 60332 6 5 -22745L 2503800 11759 6 018 064 2503800 117589 6 5 41136L 2514416 3994 3 023 022 2514416 39937 3 2 51765L 2537333 5216 3 033 029 2537333 52157 3 2 74744L 2555667 2783 6 042 015 2555667 27826 6 5 9309L 2568167 1356 6 048 007 2568167 13556 6 5 105530L 2580000 2000 3 053 011 2580000 20000 3 2 117334L 3013269 9580 6 255 053 Fail - - 34L - - 5506

Totgem 246587 9632 gkg 1-level 232 (176) 13 2462677 (34L 69L) 13 12Totstd= 21507 16070 5-level 186 (152) 2

68RESULTS Mean = 24626770 gkg

Repeatability variance S2r = 3666797Repeatability std Sr = 605541 --gt 246 r = 169551Between lab variance S2L = 7715586Reproducibility var S2R = 11382383Reproducibility std SR = 1066882 --gt 433 R = 298727Remarks 2 Labs rejected (34L 69L)

000 050 100 150 200 250 300 350 400

k-values

69L

35L

66L

46L

56L

32L

70L

16L

45L

36L

65L

44L

9L

30L

34L

Mandels k statistics(Compost 1 - TOC)

-600 -400 -200 00 200 400 600

Deviation from Mean

69L

35L

66L

46L

56L

32L

70L

16L

45L

36L

65L

44L

9L

30L

34L

Labo

rato

ries

Compost 1 - TOC -- Mean PARM = 2463 [gkg]

-300 -200 -100 000 100 200 300

h-values

69L

66L

56L

70L

45L

65L

9L

34L

Labo

rato

ries

Mandels h statistics(Compost 1 - TOC)

Compost 1-TOC

Unit gkg

Mandels k statistics(Compost 2 - TOC)Mandels h statistics(Compost 2 - TOC)

Sample Compost 2 Compost 2 - TOC -- Mean PARM = 1542 [gkg]

Element TOC

General calcparmT1= 994897E+03T2= 155556E+06T3= 64T4= 346T5= 41738E+03

n= variabelp= 13

N-table= 5

Mandels statistics End ResultLAB 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

45L 1326733 5665 6 -100 042 Fail 1326733 56646 6 5 -215046L 1355000 24365 4 -089 181 Fail - - 46L - - -186736L 1381949 5407 3 -078 040 Fail 1381949 54070 3 2 -159870L 1414120 - 1 -066 Fail 1414120 - 1 -127616L 1428333 5565 6 -061 041 1428333 55648 6 5 -113466L 1485550 7805 4 -039 058 1485550 78047 4 3 -56232L 1532500 5377 4 -021 040 1532500 53774 4 3 -09219L 1576833 10138 6 -004 075 1576833 101381 6 5 3519L 1582333 6166 6 -002 046 1582333 61659 6 5 40656L 1594432 4046 6 003 030 1594432 40463 6 5 52744L 1653000 3651 6 025 027 1653000 36508 6 5 111334L 1655127 13717 6 026 102 1655127 137168 6 5 113434L 1655127 13717 6 026 102 1655127 137168 6 5 113465L 1756500 16295 4 065 121 Fail 1756500 162949 4 3 214869L 2415000 30687 4 316 228 Fail - - 69L - - 8733

Totgem 158750 10900 gkg 1-level 232 (176) 13 1541734 (46L 69L) 13 12Totstd= 26187 8164 5-level 186 (152) 2

72RESULTS Mean = 15417337 gkg

Repeatability variance S2r = 8183950Repeatability std Sr = 904652 --gt 587 r = 253303Between lab variance S2L = 13631046Reproducibility var S2R = 21814995Reproducibility std SR = 1476990 --gt 958 R = 413557Remarks 2 Labs rejected (46L 69L)

000 050 100 150 200 250

k-values

45L

46L

36L

70L

16L

66L

32L

19L

9L

56L

44L

34L

34L

65L

69L

Mandels k statistics(Compost 2 - TOC)

-400 -200 00 200 400 600 800 1000

Deviation from Mean

45L

46L

36L

70L

16L

66L

32L

19L

9L

56L

44L

34L

34L

65L

69L

Labo

rato

ries

Compost 2 - TOC -- Mean PARM = 1542 [gkg]

-100 000 100 200 300 400

h-values

45L

36L

16L

32L

9L

44L

34L

69L

Labo

rato

ries

Mandels h statistics(Compost 2 - TOC)

Compost 2-TOC

Unit gkg

Mandels k statistics(Sludge 1 - TOC)Mandels h statistics(Sludge 1 - TOC)

Sample Sludge 1 Sludge 1 - TOC -- Mean PARM = 2721 [gkg]

Element TOC

General calcparmT1= 169626E+04T2= 465445E+06T3= 62T4= 326T5= 10312E+03

n= variabelp= 13

N-table= 5

Mandels statistics End ResultLAB 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

69L 233000 2362 4 -347 037 Fail - - 69L - - -2488046L 2312500 2062 4 -040 032 Fail 2312500 20616 4 3 -408565L 2615500 1708 4 004 026 2615500 17078 4 3 -105566L 2627200 8268 4 006 128 2627200 82678 4 3 -93836L 2664041 4976 3 011 077 2664041 49758 3 2 -56935L 2671500 3533 6 013 055 2671500 35331 6 5 -49556L 2692298 0874 6 016 014 Fail 2692298 08738 6 5 -28732L 2717500 6185 4 019 096 Fail 2717500 61847 4 3 -03519L 2753333 7819 6 025 121 Fail 2753333 78189 6 5 32470L 2814600 - 1 034 Fail 2814600 - 1 9369L 2853667 0398 6 039 006 Fail 2853667 03983 6 5 132716L 2860000 1673 6 040 026 Fail 2860000 16733 6 5 139045L 2884433 7033 6 044 109 Fail 2884433 70331 6 5 163544L 2906167 1129 6 047 017 Fail 2906167 11286 6 5 185234L 3186874 17674 6 089 274 Fail - - 34L - - 4659

Totgem 258617 4692 gkg 1-level 232 (176) 13 2720980 (34L 69L) 13 12Totstd= 67800 4610 5-level 186 (152) 2

72RESULTS Mean = 27209799 gkg

Repeatability variance S2r = 2104538Repeatability std Sr = 458752 --gt 169 r = 128451Between lab variance S2L = 23618387Reproducibility var S2R = 25722925Reproducibility std SR = 1603837 --gt 589 R = 449074Remarks 2 Labs rejected (34L 69L)

000 050 100 150 200 250 300

k-values

69L

46L

65L

66L

36L

35L

56L

32L

19L

70L

9L

16L

45L

44L

34L

Mandels k statistics(Sludge 1 - TOC)

-2500 -2000 -1500 -1000 -500 00 500

Deviation from Mean

69L

46L

65L

66L

36L

35L

56L

32L

19L

70L

9L

16L

45L

44L

34L

Labo

rato

ries

Sludge 1 - TOC -- Mean PARM = 2721 [gkg]

-400 -300 -200 -100 000 100

h-values

69L

65L

36L

56L

19L

9L

45L

34L

Labo

rato

ries

Mandels h statistics(Sludge 1 - TOC)

Sludge 1-TOC

68 Unit gkg

Mandels k statistics(Sludge 2 - TOC)Mandels h statistics(Sludge 2 - TOC)

Sample Sludge 2 Sludge 2 - TOC -- Mean PARM = 2207 [gkg]

Element TOC

General calcparmT1= 128601E+04T2= 285689E+06T3= 58T4= 310T5= 97826E+02

n= variabelp= 12

N-table= 5

Mandels statistics End ResultLAB 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

46L 182500 0500 4 -333 008 Fail - - 46L - - -2024466L 2029475 5267 4 -012 084 2029475 52674 4 3 -177436L 2072609 2222 3 -005 035 2072609 22222 3 2 -134365L 2084750 3865 4 -002 062 2084750 38647 4 3 -122135L 2140333 3119 6 007 050 2140333 31194 6 5 -66556L 2188021 1282 6 015 020 2188021 12822 6 5 -18819L 2223667 7916 6 022 126 Fail 2223667 79157 6 5 16832L 2242500 3096 4 025 049 Fail 2242500 30957 4 3 35645L 2266600 8322 6 029 132 Fail 2266600 83216 6 5 59770L 2272460 - 1 030 Fail 2272460 - 1 65616L 2291667 3869 6 033 062 Fail 2291667 38687 6 5 84844L 2302667 1546 6 035 025 Fail 2302667 15462 6 5 9589L 2367667 1296 6 047 021 Fail 2367667 12956 6 5 160834L 2718591 17124 6 108 273 Fail - - 34L - - 5117

Totgem 209882 4571 gkg 1-level 230 (176) 12 2206868 (34L 46L) 12 11Totstd= 57628 4485 5-level 185 (151) 2

68RESULTS Mean = 22068679 gkg

Repeatability variance S2r = 2126659Repeatability std Sr = 461157 --gt 209 r = 129124Between lab variance S2L = 9960432Reproducibility var S2R = 12087091Reproducibility std SR = 1099413 --gt 498 R = 307836Remarks 2 Labs rejected (34L 46L)

000 050 100 150 200 250 300

k-values

46L

66L

36L

65L

35L

56L

19L

32L

45L

70L

16L

44L

9L

34L

Mandels k statistics(Sludge 2 - TOC)

-2500 -2000 -1500 -1000 -500 00 500 1000

Deviation from Mean

46L

66L

36L

65L

35L

56L

19L

32L

45L

70L

16L

44L

9L

34L

Labo

rato

ries

Sludge 2 - TOC -- Mean PARM = 2207 [gkg]

-400 -300 -200 -100 000 100 200

h-values

46L

66L

36L

65L

35L

56L

19L

32L

45L

70L

16L

44L

9L

34L

Labo

rato

ries

Mandels h statistics(Sludge 2 - TOC)

Sludge 2-TOC

Unit gkg

Mandels k statistics(Soil 4 - TOC)Mandels h statistics(Soil 4 - TOC)

Sample Soil 4 Soil 4 - TOC -- Mean PARM = 1641 [gkg]

Element TOC

General calcparmT1= 102171E+03T2= 168700E+04T3= 62T4= 338T5= 94040E+00

n= variabelp= 12

N-table= 5

Mandels statistics End ResultLAB 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

36L 147161 0470 3 -036 068 Fail 147161 04702 3 2 -16965L 155250 0591 4 -032 085 Fail 155250 05909 4 3 -08844L 157900 0115 6 -031 017 Fail 157900 01152 6 5 -06232L 159250 0359 4 -031 052 Fail 159250 03594 4 3 -0489L 160500 0315 6 -030 045 Fail 160500 03146 6 5 -03656L 164927 0113 6 -028 016 Fail 164927 01127 6 5 00835L 165000 0261 6 -028 038 Fail 165000 02608 6 5 00919L 166667 0505 6 -027 073 Fail 166667 05046 6 5 02645L 168850 0763 6 -026 110 Fail 168850 07628 6 5 04816L 173333 0516 6 -024 074 Fail 173333 05164 6 5 09334L 174761 0346 6 -024 050 Fail 174761 03462 6 5 10730L 175333 0473 3 -024 068 Fail 175333 04726 3 2 11366L 189375 2035 4 -017 294 Fail - - 66L - - 25346L 227500 0500 4 000 072 - - 46L - - 63470L 1040400 - 1 360 Fail - - 70L - - 8763

Totgem 22841 0526 gkg 1-level 232 (176) 12 164078 (46L 66L70L) 12 11Totstd= 22541 0469 5-level 186 (152) 3

71RESULTS Mean = 1640777 gkg

Repeatability variance S2r = 018808Repeatability std Sr = 043368 --gt 264 r = 12143Between lab variance S2L = 054747Reproducibility var S2R = 073555Reproducibility std SR = 085764 --gt 523 R = 24014Remarks 3 Labs rejected (46L 66L70L)

000 050 100 150 200 250 300

k-values

36L

65L

44L

32L

9L

56L

35L

19L

45L

16L

34L

30L

66L

46L

70L

Mandels k statistics(Soil 4 - TOC)

-100 00 100 200 300 400 500 600 700 800 900

Deviation from Mean

36L

65L

44L

32L

9L

56L

35L

19L

45L

16L

34L

30L

66L

46L

70L

Labo

rato

ries

Soil 4 - TOC -- Mean PARM = 1641 [gkg]

-100 000 100 200 300 400

h-values

36L

44L

9L

35L

45L

34L

66L

70L

Labo

rato

ries

Mandels h statistics(Soil 4 - TOC)

Soil 4-TOC

Unit gkg

Mandels k statistics(Soil 5 - TOC)Mandels h statistics(Soil 5 - TOC)

Sample Soil 5 Soil 5 - TOC -- Mean PARM = 2102 [gkg]

Element TOC

General calcparmT1= 113661E+03T2= 240201E+04T3= 54T4= 300T5= 51756E+01

n= variabelp= 10

N-table= 5

Mandels statistics End ResultLAB 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

44L 164383 14708 6 -036 325 Fail - - 44L - - -45865L 181250 0830 4 -033 018 Fail 181250 08302 4 3 -29045L 200317 1116 6 -029 025 Fail 200317 11163 6 5 -09935L 201833 1828 6 -029 040 Fail 201833 18280 6 5 -08432L 203250 0585 4 -029 013 Fail 203250 05852 4 3 -07016L 209000 0959 6 -028 021 Fail 209000 09592 6 5 -0129L 211667 0427 6 -027 009 Fail 211667 04274 6 5 01556L 214030 0887 6 -027 020 Fail 214030 08868 6 5 03819L 216000 0795 6 -026 018 Fail 216000 07950 6 5 05834L 226009 1308 6 -024 029 Fail 226009 13076 6 5 15836L 228783 4310 3 -024 095 Fail - - 36L - - 18666L 238750 1234 4 -022 027 Fail 238750 12340 4 3 28570L 2213900 - 1 333 Fail - - 70L - - 20037

Totgem 36224 2416 gkg 1-level 227 (175) 10 210211 (36L44L 70L) 10 9Totstd= 55669 4003 5-level 184 (151) 3

64RESULTS Mean = 2102106 gkg

Repeatability variance S2r = 117627Repeatability std Sr = 108456 --gt 516 r = 30368Between lab variance S2L = 176699Reproducibility var S2R = 294326Reproducibility std SR = 171559 --gt 816 R = 48037Remarks 3 Labs rejected (36L44L 70L)

000 050 100 150 200 250 300 350

k-values

44L

65L

45L

35L

32L

16L

9L

56L

19L

34L

36L

66L

70L

Mandels k statistics(Soil 5 - TOC)

-500 00 500 1000 1500 2000 2500

Deviation from Mean

44L

65L

45L

35L

32L

16L

9L

56L

19L

34L

36L

66L

70L

Labo

rato

ries

Soil 5 - TOC -- Mean PARM = 2102 [gkg]

-100 000 100 200 300 400

h-values

44L

65L

45L

35L

32L

16L

9L

56L

19L

34L

36L

66L

70L

Labo

rato

ries

Mandels h statistics(Soil 5 - TOC)

Soil 5-TOC

17

Annex 4

Raw data submitted

Sample Compost 1 Sample Compost 2 Sample Sewage Sludge 1Element TOC [gkg] Element TOC [gkg] Element TOC [gkg]

LAB PARM LAB PARM LAB PARM30L 2600 19L 1691 19L 286730L 2580 19L 1634 19L 281430L 2560 19L 1619 19L 276934L 2969 19L 1604 19L 272034L 2936 19L 1499 19L 268834L 2958 19L 1414 19L 266234L 2994 34L 1527 34L 315234L 3199 34L 1622 34L 314934L 3024 34L 1519 34L 343035L 2306 34L 1753 34L 336535L 2300 34L 1636 34L 304235L 2298 34L 1874 34L 298335L 2296 35L 1506 35L 270735L 2291 35L 1312 35L 270335L 2259 35L 1294 35L 268836L 2546 35L 1279 35L 267436L 2527 35L 1191 35L 263136L 2470 35L 1177 35L 262644L 2583 36L 1418 36L 271344L 2581 36L 1408 36L 266544L 2578 36L 1320 36L 261444L 2539 44L 1719 44L 292044L 2528 44L 1664 44L 291644L 2525 44L 1654 44L 291245L 2658 44L 1637 44L 290045L 2600 44L 1624 44L 289645L 2546 44L 1620 44L 289345L 2461 45L 1428 45L 297645L 2409 45L 1325 45L 295245L 2350 45L 1323 45L 288546L 2460 45L 1321 45L 286646L 2400 45L 1309 45L 284046L 2370 45L 1253 45L 278746L 2350 46L 1580 46L 233056L 2436 46L 1550 46L 233056L 2435 46L 1170 46L 230056L 2405 46L 1120 46L 229056L 2397 56L 1642 56L 270256L 2375 56L 1626 56L 270156L 2358 56L 1622 56L 269465L 2587 56L 1571 56L 269365L 2542 56L 1561 56L 268465L 2483 56L 1545 56L 268066L 2454 65L 1933 65L 264166L 2429 65L 1838 65L 260966L 2365 65L 1693 65L 260766L 2262 65L 1562 65L 260569L 2730 66L 1561 66L 270169L 2250 66L 1545 66L 267469L 1440 66L 1420 66L 261969L 1420 66L 1417 66L 251470L 2435 69L 2700 69L 2639L 2594 69L 2660 69L 2409L 2570 69L 2170 69L 2199L 2565 69L 2130 69L 2109L 2563 70L 1414 70L 28159L 2562 9L 1644 9L 28579L 2555 9L 1641 9L 2856

32L 2290 9L 1602 9L 285532L 2390 9L 1589 9L 285532L 2510 9L 1526 9L 285332L 2470 9L 1492 9L 284616L 2380 32L 1470 32L 265016L 2530 32L 1520 32L 271016L 2400 32L 1540 32L 271016L 2500 32L 1600 32L 280016L 2420 16L 1400 16L 284016L 2410 16L 1440 16L 2840

16L 1470 16L 286016L 1510 16L 287016L 1360 16L 287016L 1390 16L 2880

Sample Sewage Sludge 2 Sample Soil 4 Sample Soil 5Element TOC [gkg] Element TOC [gkg] Element TOC [gkg]

LAB PARM LAB PARM LAB PARM19L 2308 19L 1720 19L 225019L 2303 19L 1700 19L 223019L 2239 19L 1690 19L 221019L 2204 19L 1670 19L 211019L 2192 19L 1640 19L 210019L 2096 19L 1580 19L 206034L 2631 30L 1790 34L 244334L 2471 30L 1770 34L 233434L 2977 30L 1700 34L 231534L 2785 34L 1740 34L 222134L 2780 34L 1692 34L 217634L 2668 34L 1727 34L 207335L 2179 34L 1767 35L 233035L 2160 34L 1777 35L 208035L 2158 34L 1783 35L 201035L 2132 35L 1700 35L 198035L 2119 35L 1650 35L 193035L 2094 35L 1650 35L 178036L 2096 35L 1640 36L 254036L 2069 35L 1630 36L 253436L 2052 35L 1630 36L 179044L 2325 36L 1500 44L 302144L 2309 36L 1497 44L 298244L 2307 36L 1417 44L 295644L 2305 44L 1594 44L 30744L 2287 44L 1587 44L 30044L 2283 44L 1584 44L 29745L 2331 44L 1574 45L 214945L 2327 44L 1573 45L 209245L 2308 44L 1562 45L 203345L 2287 45L 1827 45L 197145L 2234 45L 1709 45L 193345L 2113 45L 1666 45L 184146L 190 45L 1665 56L 223746L 180 45L 1664 56L 222246L 180 45L 1600 56L 220346L 180 46L 2300 56L 206956L 2204 46L 2300 56L 206856L 2197 46L 2300 56L 204456L 2193 46L 2200 65L 192056L 2185 56L 1668 65L 182056L 2183 56L 1654 65L 179056L 2167 56L 1653 65L 172065L 2136 56L 1643 66L 254365L 2091 56L 1639 66L 242465L 2065 56L 1638 66L 232165L 2047 65L 1630 66L 226266L 2105 65L 1560 70L 2213966L 2022 65L 1530 9L 218066L 2009 65L 1490 9L 214066L 1983 66L 2179 9L 213070L 2272 66L 1900 9L 21109L 2385 66L 1762 9L 20709L 2377 66L 1734 9L 20709L 2375 70L 10404 32L 20509L 2359 9L 1640 32L 21009L 2356 9L 1640 32L 20209L 2354 9L 1610 32L 1960

32L 2240 9L 1590 16L 210032L 2260 9L 1590 16L 220032L 2200 9L 1560 16L 220032L 2270 32L 1640 16L 206016L 2300 32L 1600 16L 197016L 2310 32L 1560 16L 201016L 2350 32L 157016L 2260 16L 170016L 2290 16L 180016L 2240 16L 1700

16L 180016L 170016L 1700

European Commission EUR 23012 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on total organic carbon Author(s) E Sobiecka H van der Sloot K Andersen B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 50 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07412-7 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 total organic carbon (TOC) in soils sludge and treated bio-waste 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

-23012-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

16

Annex 3

Statistical calculations

Unit gkg

Mandels k statistics(Compost 1 - TOC)Mandels h statistics(Compost 1 - TOC)

Sample Compost 1 Compost 1 - TOC -- Mean PARM = 2463 [gkg]

Element TOC

General calcparmT1= 142643E+04T2= 351264E+06T3= 58T4= 292T5= 16501E+03

n= variabelp= 13

N-table= 5

Mandels statistics End ResultLAB 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

69L 1960000 64265 4 -235 352 Fail - - 69L - - -502735L 2291667 1674 6 -081 009 2291667 16741 6 5 -171066L 2377425 8552 4 -041 047 2377425 85518 4 3 -85346L 2395000 4796 4 -033 026 2395000 47958 4 3 -67756L 2401227 3133 6 -030 017 2401227 31330 6 5 -61432L 2415000 9713 4 -024 053 2415000 97125 4 3 -47770L 2435100 - 1 -014 2435100 - 1 -27616L 2440000 6033 6 -012 033 2440000 60332 6 5 -22745L 2503800 11759 6 018 064 2503800 117589 6 5 41136L 2514416 3994 3 023 022 2514416 39937 3 2 51765L 2537333 5216 3 033 029 2537333 52157 3 2 74744L 2555667 2783 6 042 015 2555667 27826 6 5 9309L 2568167 1356 6 048 007 2568167 13556 6 5 105530L 2580000 2000 3 053 011 2580000 20000 3 2 117334L 3013269 9580 6 255 053 Fail - - 34L - - 5506

Totgem 246587 9632 gkg 1-level 232 (176) 13 2462677 (34L 69L) 13 12Totstd= 21507 16070 5-level 186 (152) 2

68RESULTS Mean = 24626770 gkg

Repeatability variance S2r = 3666797Repeatability std Sr = 605541 --gt 246 r = 169551Between lab variance S2L = 7715586Reproducibility var S2R = 11382383Reproducibility std SR = 1066882 --gt 433 R = 298727Remarks 2 Labs rejected (34L 69L)

000 050 100 150 200 250 300 350 400

k-values

69L

35L

66L

46L

56L

32L

70L

16L

45L

36L

65L

44L

9L

30L

34L

Mandels k statistics(Compost 1 - TOC)

-600 -400 -200 00 200 400 600

Deviation from Mean

69L

35L

66L

46L

56L

32L

70L

16L

45L

36L

65L

44L

9L

30L

34L

Labo

rato

ries

Compost 1 - TOC -- Mean PARM = 2463 [gkg]

-300 -200 -100 000 100 200 300

h-values

69L

66L

56L

70L

45L

65L

9L

34L

Labo

rato

ries

Mandels h statistics(Compost 1 - TOC)

Compost 1-TOC

Unit gkg

Mandels k statistics(Compost 2 - TOC)Mandels h statistics(Compost 2 - TOC)

Sample Compost 2 Compost 2 - TOC -- Mean PARM = 1542 [gkg]

Element TOC

General calcparmT1= 994897E+03T2= 155556E+06T3= 64T4= 346T5= 41738E+03

n= variabelp= 13

N-table= 5

Mandels statistics End ResultLAB 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

45L 1326733 5665 6 -100 042 Fail 1326733 56646 6 5 -215046L 1355000 24365 4 -089 181 Fail - - 46L - - -186736L 1381949 5407 3 -078 040 Fail 1381949 54070 3 2 -159870L 1414120 - 1 -066 Fail 1414120 - 1 -127616L 1428333 5565 6 -061 041 1428333 55648 6 5 -113466L 1485550 7805 4 -039 058 1485550 78047 4 3 -56232L 1532500 5377 4 -021 040 1532500 53774 4 3 -09219L 1576833 10138 6 -004 075 1576833 101381 6 5 3519L 1582333 6166 6 -002 046 1582333 61659 6 5 40656L 1594432 4046 6 003 030 1594432 40463 6 5 52744L 1653000 3651 6 025 027 1653000 36508 6 5 111334L 1655127 13717 6 026 102 1655127 137168 6 5 113434L 1655127 13717 6 026 102 1655127 137168 6 5 113465L 1756500 16295 4 065 121 Fail 1756500 162949 4 3 214869L 2415000 30687 4 316 228 Fail - - 69L - - 8733

Totgem 158750 10900 gkg 1-level 232 (176) 13 1541734 (46L 69L) 13 12Totstd= 26187 8164 5-level 186 (152) 2

72RESULTS Mean = 15417337 gkg

Repeatability variance S2r = 8183950Repeatability std Sr = 904652 --gt 587 r = 253303Between lab variance S2L = 13631046Reproducibility var S2R = 21814995Reproducibility std SR = 1476990 --gt 958 R = 413557Remarks 2 Labs rejected (46L 69L)

000 050 100 150 200 250

k-values

45L

46L

36L

70L

16L

66L

32L

19L

9L

56L

44L

34L

34L

65L

69L

Mandels k statistics(Compost 2 - TOC)

-400 -200 00 200 400 600 800 1000

Deviation from Mean

45L

46L

36L

70L

16L

66L

32L

19L

9L

56L

44L

34L

34L

65L

69L

Labo

rato

ries

Compost 2 - TOC -- Mean PARM = 1542 [gkg]

-100 000 100 200 300 400

h-values

45L

36L

16L

32L

9L

44L

34L

69L

Labo

rato

ries

Mandels h statistics(Compost 2 - TOC)

Compost 2-TOC

Unit gkg

Mandels k statistics(Sludge 1 - TOC)Mandels h statistics(Sludge 1 - TOC)

Sample Sludge 1 Sludge 1 - TOC -- Mean PARM = 2721 [gkg]

Element TOC

General calcparmT1= 169626E+04T2= 465445E+06T3= 62T4= 326T5= 10312E+03

n= variabelp= 13

N-table= 5

Mandels statistics End ResultLAB 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

69L 233000 2362 4 -347 037 Fail - - 69L - - -2488046L 2312500 2062 4 -040 032 Fail 2312500 20616 4 3 -408565L 2615500 1708 4 004 026 2615500 17078 4 3 -105566L 2627200 8268 4 006 128 2627200 82678 4 3 -93836L 2664041 4976 3 011 077 2664041 49758 3 2 -56935L 2671500 3533 6 013 055 2671500 35331 6 5 -49556L 2692298 0874 6 016 014 Fail 2692298 08738 6 5 -28732L 2717500 6185 4 019 096 Fail 2717500 61847 4 3 -03519L 2753333 7819 6 025 121 Fail 2753333 78189 6 5 32470L 2814600 - 1 034 Fail 2814600 - 1 9369L 2853667 0398 6 039 006 Fail 2853667 03983 6 5 132716L 2860000 1673 6 040 026 Fail 2860000 16733 6 5 139045L 2884433 7033 6 044 109 Fail 2884433 70331 6 5 163544L 2906167 1129 6 047 017 Fail 2906167 11286 6 5 185234L 3186874 17674 6 089 274 Fail - - 34L - - 4659

Totgem 258617 4692 gkg 1-level 232 (176) 13 2720980 (34L 69L) 13 12Totstd= 67800 4610 5-level 186 (152) 2

72RESULTS Mean = 27209799 gkg

Repeatability variance S2r = 2104538Repeatability std Sr = 458752 --gt 169 r = 128451Between lab variance S2L = 23618387Reproducibility var S2R = 25722925Reproducibility std SR = 1603837 --gt 589 R = 449074Remarks 2 Labs rejected (34L 69L)

000 050 100 150 200 250 300

k-values

69L

46L

65L

66L

36L

35L

56L

32L

19L

70L

9L

16L

45L

44L

34L

Mandels k statistics(Sludge 1 - TOC)

-2500 -2000 -1500 -1000 -500 00 500

Deviation from Mean

69L

46L

65L

66L

36L

35L

56L

32L

19L

70L

9L

16L

45L

44L

34L

Labo

rato

ries

Sludge 1 - TOC -- Mean PARM = 2721 [gkg]

-400 -300 -200 -100 000 100

h-values

69L

65L

36L

56L

19L

9L

45L

34L

Labo

rato

ries

Mandels h statistics(Sludge 1 - TOC)

Sludge 1-TOC

68 Unit gkg

Mandels k statistics(Sludge 2 - TOC)Mandels h statistics(Sludge 2 - TOC)

Sample Sludge 2 Sludge 2 - TOC -- Mean PARM = 2207 [gkg]

Element TOC

General calcparmT1= 128601E+04T2= 285689E+06T3= 58T4= 310T5= 97826E+02

n= variabelp= 12

N-table= 5

Mandels statistics End ResultLAB 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

46L 182500 0500 4 -333 008 Fail - - 46L - - -2024466L 2029475 5267 4 -012 084 2029475 52674 4 3 -177436L 2072609 2222 3 -005 035 2072609 22222 3 2 -134365L 2084750 3865 4 -002 062 2084750 38647 4 3 -122135L 2140333 3119 6 007 050 2140333 31194 6 5 -66556L 2188021 1282 6 015 020 2188021 12822 6 5 -18819L 2223667 7916 6 022 126 Fail 2223667 79157 6 5 16832L 2242500 3096 4 025 049 Fail 2242500 30957 4 3 35645L 2266600 8322 6 029 132 Fail 2266600 83216 6 5 59770L 2272460 - 1 030 Fail 2272460 - 1 65616L 2291667 3869 6 033 062 Fail 2291667 38687 6 5 84844L 2302667 1546 6 035 025 Fail 2302667 15462 6 5 9589L 2367667 1296 6 047 021 Fail 2367667 12956 6 5 160834L 2718591 17124 6 108 273 Fail - - 34L - - 5117

Totgem 209882 4571 gkg 1-level 230 (176) 12 2206868 (34L 46L) 12 11Totstd= 57628 4485 5-level 185 (151) 2

68RESULTS Mean = 22068679 gkg

Repeatability variance S2r = 2126659Repeatability std Sr = 461157 --gt 209 r = 129124Between lab variance S2L = 9960432Reproducibility var S2R = 12087091Reproducibility std SR = 1099413 --gt 498 R = 307836Remarks 2 Labs rejected (34L 46L)

000 050 100 150 200 250 300

k-values

46L

66L

36L

65L

35L

56L

19L

32L

45L

70L

16L

44L

9L

34L

Mandels k statistics(Sludge 2 - TOC)

-2500 -2000 -1500 -1000 -500 00 500 1000

Deviation from Mean

46L

66L

36L

65L

35L

56L

19L

32L

45L

70L

16L

44L

9L

34L

Labo

rato

ries

Sludge 2 - TOC -- Mean PARM = 2207 [gkg]

-400 -300 -200 -100 000 100 200

h-values

46L

66L

36L

65L

35L

56L

19L

32L

45L

70L

16L

44L

9L

34L

Labo

rato

ries

Mandels h statistics(Sludge 2 - TOC)

Sludge 2-TOC

Unit gkg

Mandels k statistics(Soil 4 - TOC)Mandels h statistics(Soil 4 - TOC)

Sample Soil 4 Soil 4 - TOC -- Mean PARM = 1641 [gkg]

Element TOC

General calcparmT1= 102171E+03T2= 168700E+04T3= 62T4= 338T5= 94040E+00

n= variabelp= 12

N-table= 5

Mandels statistics End ResultLAB 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

36L 147161 0470 3 -036 068 Fail 147161 04702 3 2 -16965L 155250 0591 4 -032 085 Fail 155250 05909 4 3 -08844L 157900 0115 6 -031 017 Fail 157900 01152 6 5 -06232L 159250 0359 4 -031 052 Fail 159250 03594 4 3 -0489L 160500 0315 6 -030 045 Fail 160500 03146 6 5 -03656L 164927 0113 6 -028 016 Fail 164927 01127 6 5 00835L 165000 0261 6 -028 038 Fail 165000 02608 6 5 00919L 166667 0505 6 -027 073 Fail 166667 05046 6 5 02645L 168850 0763 6 -026 110 Fail 168850 07628 6 5 04816L 173333 0516 6 -024 074 Fail 173333 05164 6 5 09334L 174761 0346 6 -024 050 Fail 174761 03462 6 5 10730L 175333 0473 3 -024 068 Fail 175333 04726 3 2 11366L 189375 2035 4 -017 294 Fail - - 66L - - 25346L 227500 0500 4 000 072 - - 46L - - 63470L 1040400 - 1 360 Fail - - 70L - - 8763

Totgem 22841 0526 gkg 1-level 232 (176) 12 164078 (46L 66L70L) 12 11Totstd= 22541 0469 5-level 186 (152) 3

71RESULTS Mean = 1640777 gkg

Repeatability variance S2r = 018808Repeatability std Sr = 043368 --gt 264 r = 12143Between lab variance S2L = 054747Reproducibility var S2R = 073555Reproducibility std SR = 085764 --gt 523 R = 24014Remarks 3 Labs rejected (46L 66L70L)

000 050 100 150 200 250 300

k-values

36L

65L

44L

32L

9L

56L

35L

19L

45L

16L

34L

30L

66L

46L

70L

Mandels k statistics(Soil 4 - TOC)

-100 00 100 200 300 400 500 600 700 800 900

Deviation from Mean

36L

65L

44L

32L

9L

56L

35L

19L

45L

16L

34L

30L

66L

46L

70L

Labo

rato

ries

Soil 4 - TOC -- Mean PARM = 1641 [gkg]

-100 000 100 200 300 400

h-values

36L

44L

9L

35L

45L

34L

66L

70L

Labo

rato

ries

Mandels h statistics(Soil 4 - TOC)

Soil 4-TOC

Unit gkg

Mandels k statistics(Soil 5 - TOC)Mandels h statistics(Soil 5 - TOC)

Sample Soil 5 Soil 5 - TOC -- Mean PARM = 2102 [gkg]

Element TOC

General calcparmT1= 113661E+03T2= 240201E+04T3= 54T4= 300T5= 51756E+01

n= variabelp= 10

N-table= 5

Mandels statistics End ResultLAB 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

44L 164383 14708 6 -036 325 Fail - - 44L - - -45865L 181250 0830 4 -033 018 Fail 181250 08302 4 3 -29045L 200317 1116 6 -029 025 Fail 200317 11163 6 5 -09935L 201833 1828 6 -029 040 Fail 201833 18280 6 5 -08432L 203250 0585 4 -029 013 Fail 203250 05852 4 3 -07016L 209000 0959 6 -028 021 Fail 209000 09592 6 5 -0129L 211667 0427 6 -027 009 Fail 211667 04274 6 5 01556L 214030 0887 6 -027 020 Fail 214030 08868 6 5 03819L 216000 0795 6 -026 018 Fail 216000 07950 6 5 05834L 226009 1308 6 -024 029 Fail 226009 13076 6 5 15836L 228783 4310 3 -024 095 Fail - - 36L - - 18666L 238750 1234 4 -022 027 Fail 238750 12340 4 3 28570L 2213900 - 1 333 Fail - - 70L - - 20037

Totgem 36224 2416 gkg 1-level 227 (175) 10 210211 (36L44L 70L) 10 9Totstd= 55669 4003 5-level 184 (151) 3

64RESULTS Mean = 2102106 gkg

Repeatability variance S2r = 117627Repeatability std Sr = 108456 --gt 516 r = 30368Between lab variance S2L = 176699Reproducibility var S2R = 294326Reproducibility std SR = 171559 --gt 816 R = 48037Remarks 3 Labs rejected (36L44L 70L)

000 050 100 150 200 250 300 350

k-values

44L

65L

45L

35L

32L

16L

9L

56L

19L

34L

36L

66L

70L

Mandels k statistics(Soil 5 - TOC)

-500 00 500 1000 1500 2000 2500

Deviation from Mean

44L

65L

45L

35L

32L

16L

9L

56L

19L

34L

36L

66L

70L

Labo

rato

ries

Soil 5 - TOC -- Mean PARM = 2102 [gkg]

-100 000 100 200 300 400

h-values

44L

65L

45L

35L

32L

16L

9L

56L

19L

34L

36L

66L

70L

Labo

rato

ries

Mandels h statistics(Soil 5 - TOC)

Soil 5-TOC

17

Annex 4

Raw data submitted

Sample Compost 1 Sample Compost 2 Sample Sewage Sludge 1Element TOC [gkg] Element TOC [gkg] Element TOC [gkg]

LAB PARM LAB PARM LAB PARM30L 2600 19L 1691 19L 286730L 2580 19L 1634 19L 281430L 2560 19L 1619 19L 276934L 2969 19L 1604 19L 272034L 2936 19L 1499 19L 268834L 2958 19L 1414 19L 266234L 2994 34L 1527 34L 315234L 3199 34L 1622 34L 314934L 3024 34L 1519 34L 343035L 2306 34L 1753 34L 336535L 2300 34L 1636 34L 304235L 2298 34L 1874 34L 298335L 2296 35L 1506 35L 270735L 2291 35L 1312 35L 270335L 2259 35L 1294 35L 268836L 2546 35L 1279 35L 267436L 2527 35L 1191 35L 263136L 2470 35L 1177 35L 262644L 2583 36L 1418 36L 271344L 2581 36L 1408 36L 266544L 2578 36L 1320 36L 261444L 2539 44L 1719 44L 292044L 2528 44L 1664 44L 291644L 2525 44L 1654 44L 291245L 2658 44L 1637 44L 290045L 2600 44L 1624 44L 289645L 2546 44L 1620 44L 289345L 2461 45L 1428 45L 297645L 2409 45L 1325 45L 295245L 2350 45L 1323 45L 288546L 2460 45L 1321 45L 286646L 2400 45L 1309 45L 284046L 2370 45L 1253 45L 278746L 2350 46L 1580 46L 233056L 2436 46L 1550 46L 233056L 2435 46L 1170 46L 230056L 2405 46L 1120 46L 229056L 2397 56L 1642 56L 270256L 2375 56L 1626 56L 270156L 2358 56L 1622 56L 269465L 2587 56L 1571 56L 269365L 2542 56L 1561 56L 268465L 2483 56L 1545 56L 268066L 2454 65L 1933 65L 264166L 2429 65L 1838 65L 260966L 2365 65L 1693 65L 260766L 2262 65L 1562 65L 260569L 2730 66L 1561 66L 270169L 2250 66L 1545 66L 267469L 1440 66L 1420 66L 261969L 1420 66L 1417 66L 251470L 2435 69L 2700 69L 2639L 2594 69L 2660 69L 2409L 2570 69L 2170 69L 2199L 2565 69L 2130 69L 2109L 2563 70L 1414 70L 28159L 2562 9L 1644 9L 28579L 2555 9L 1641 9L 2856

32L 2290 9L 1602 9L 285532L 2390 9L 1589 9L 285532L 2510 9L 1526 9L 285332L 2470 9L 1492 9L 284616L 2380 32L 1470 32L 265016L 2530 32L 1520 32L 271016L 2400 32L 1540 32L 271016L 2500 32L 1600 32L 280016L 2420 16L 1400 16L 284016L 2410 16L 1440 16L 2840

16L 1470 16L 286016L 1510 16L 287016L 1360 16L 287016L 1390 16L 2880

Sample Sewage Sludge 2 Sample Soil 4 Sample Soil 5Element TOC [gkg] Element TOC [gkg] Element TOC [gkg]

LAB PARM LAB PARM LAB PARM19L 2308 19L 1720 19L 225019L 2303 19L 1700 19L 223019L 2239 19L 1690 19L 221019L 2204 19L 1670 19L 211019L 2192 19L 1640 19L 210019L 2096 19L 1580 19L 206034L 2631 30L 1790 34L 244334L 2471 30L 1770 34L 233434L 2977 30L 1700 34L 231534L 2785 34L 1740 34L 222134L 2780 34L 1692 34L 217634L 2668 34L 1727 34L 207335L 2179 34L 1767 35L 233035L 2160 34L 1777 35L 208035L 2158 34L 1783 35L 201035L 2132 35L 1700 35L 198035L 2119 35L 1650 35L 193035L 2094 35L 1650 35L 178036L 2096 35L 1640 36L 254036L 2069 35L 1630 36L 253436L 2052 35L 1630 36L 179044L 2325 36L 1500 44L 302144L 2309 36L 1497 44L 298244L 2307 36L 1417 44L 295644L 2305 44L 1594 44L 30744L 2287 44L 1587 44L 30044L 2283 44L 1584 44L 29745L 2331 44L 1574 45L 214945L 2327 44L 1573 45L 209245L 2308 44L 1562 45L 203345L 2287 45L 1827 45L 197145L 2234 45L 1709 45L 193345L 2113 45L 1666 45L 184146L 190 45L 1665 56L 223746L 180 45L 1664 56L 222246L 180 45L 1600 56L 220346L 180 46L 2300 56L 206956L 2204 46L 2300 56L 206856L 2197 46L 2300 56L 204456L 2193 46L 2200 65L 192056L 2185 56L 1668 65L 182056L 2183 56L 1654 65L 179056L 2167 56L 1653 65L 172065L 2136 56L 1643 66L 254365L 2091 56L 1639 66L 242465L 2065 56L 1638 66L 232165L 2047 65L 1630 66L 226266L 2105 65L 1560 70L 2213966L 2022 65L 1530 9L 218066L 2009 65L 1490 9L 214066L 1983 66L 2179 9L 213070L 2272 66L 1900 9L 21109L 2385 66L 1762 9L 20709L 2377 66L 1734 9L 20709L 2375 70L 10404 32L 20509L 2359 9L 1640 32L 21009L 2356 9L 1640 32L 20209L 2354 9L 1610 32L 1960

32L 2240 9L 1590 16L 210032L 2260 9L 1590 16L 220032L 2200 9L 1560 16L 220032L 2270 32L 1640 16L 206016L 2300 32L 1600 16L 197016L 2310 32L 1560 16L 201016L 2350 32L 157016L 2260 16L 170016L 2290 16L 180016L 2240 16L 1700

16L 180016L 170016L 1700

European Commission EUR 23012 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on total organic carbon Author(s) E Sobiecka H van der Sloot K Andersen B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 50 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07412-7 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 total organic carbon (TOC) in soils sludge and treated bio-waste 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

-23012-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

16

Annex 3

Statistical calculations

Unit gkg

Mandels k statistics(Compost 1 - TOC)Mandels h statistics(Compost 1 - TOC)

Sample Compost 1 Compost 1 - TOC -- Mean PARM = 2463 [gkg]

Element TOC

General calcparmT1= 142643E+04T2= 351264E+06T3= 58T4= 292T5= 16501E+03

n= variabelp= 13

N-table= 5

Mandels statistics End ResultLAB 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

69L 1960000 64265 4 -235 352 Fail - - 69L - - -502735L 2291667 1674 6 -081 009 2291667 16741 6 5 -171066L 2377425 8552 4 -041 047 2377425 85518 4 3 -85346L 2395000 4796 4 -033 026 2395000 47958 4 3 -67756L 2401227 3133 6 -030 017 2401227 31330 6 5 -61432L 2415000 9713 4 -024 053 2415000 97125 4 3 -47770L 2435100 - 1 -014 2435100 - 1 -27616L 2440000 6033 6 -012 033 2440000 60332 6 5 -22745L 2503800 11759 6 018 064 2503800 117589 6 5 41136L 2514416 3994 3 023 022 2514416 39937 3 2 51765L 2537333 5216 3 033 029 2537333 52157 3 2 74744L 2555667 2783 6 042 015 2555667 27826 6 5 9309L 2568167 1356 6 048 007 2568167 13556 6 5 105530L 2580000 2000 3 053 011 2580000 20000 3 2 117334L 3013269 9580 6 255 053 Fail - - 34L - - 5506

Totgem 246587 9632 gkg 1-level 232 (176) 13 2462677 (34L 69L) 13 12Totstd= 21507 16070 5-level 186 (152) 2

68RESULTS Mean = 24626770 gkg

Repeatability variance S2r = 3666797Repeatability std Sr = 605541 --gt 246 r = 169551Between lab variance S2L = 7715586Reproducibility var S2R = 11382383Reproducibility std SR = 1066882 --gt 433 R = 298727Remarks 2 Labs rejected (34L 69L)

000 050 100 150 200 250 300 350 400

k-values

69L

35L

66L

46L

56L

32L

70L

16L

45L

36L

65L

44L

9L

30L

34L

Mandels k statistics(Compost 1 - TOC)

-600 -400 -200 00 200 400 600

Deviation from Mean

69L

35L

66L

46L

56L

32L

70L

16L

45L

36L

65L

44L

9L

30L

34L

Labo

rato

ries

Compost 1 - TOC -- Mean PARM = 2463 [gkg]

-300 -200 -100 000 100 200 300

h-values

69L

66L

56L

70L

45L

65L

9L

34L

Labo

rato

ries

Mandels h statistics(Compost 1 - TOC)

Compost 1-TOC

Unit gkg

Mandels k statistics(Compost 2 - TOC)Mandels h statistics(Compost 2 - TOC)

Sample Compost 2 Compost 2 - TOC -- Mean PARM = 1542 [gkg]

Element TOC

General calcparmT1= 994897E+03T2= 155556E+06T3= 64T4= 346T5= 41738E+03

n= variabelp= 13

N-table= 5

Mandels statistics End ResultLAB 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

45L 1326733 5665 6 -100 042 Fail 1326733 56646 6 5 -215046L 1355000 24365 4 -089 181 Fail - - 46L - - -186736L 1381949 5407 3 -078 040 Fail 1381949 54070 3 2 -159870L 1414120 - 1 -066 Fail 1414120 - 1 -127616L 1428333 5565 6 -061 041 1428333 55648 6 5 -113466L 1485550 7805 4 -039 058 1485550 78047 4 3 -56232L 1532500 5377 4 -021 040 1532500 53774 4 3 -09219L 1576833 10138 6 -004 075 1576833 101381 6 5 3519L 1582333 6166 6 -002 046 1582333 61659 6 5 40656L 1594432 4046 6 003 030 1594432 40463 6 5 52744L 1653000 3651 6 025 027 1653000 36508 6 5 111334L 1655127 13717 6 026 102 1655127 137168 6 5 113434L 1655127 13717 6 026 102 1655127 137168 6 5 113465L 1756500 16295 4 065 121 Fail 1756500 162949 4 3 214869L 2415000 30687 4 316 228 Fail - - 69L - - 8733

Totgem 158750 10900 gkg 1-level 232 (176) 13 1541734 (46L 69L) 13 12Totstd= 26187 8164 5-level 186 (152) 2

72RESULTS Mean = 15417337 gkg

Repeatability variance S2r = 8183950Repeatability std Sr = 904652 --gt 587 r = 253303Between lab variance S2L = 13631046Reproducibility var S2R = 21814995Reproducibility std SR = 1476990 --gt 958 R = 413557Remarks 2 Labs rejected (46L 69L)

000 050 100 150 200 250

k-values

45L

46L

36L

70L

16L

66L

32L

19L

9L

56L

44L

34L

34L

65L

69L

Mandels k statistics(Compost 2 - TOC)

-400 -200 00 200 400 600 800 1000

Deviation from Mean

45L

46L

36L

70L

16L

66L

32L

19L

9L

56L

44L

34L

34L

65L

69L

Labo

rato

ries

Compost 2 - TOC -- Mean PARM = 1542 [gkg]

-100 000 100 200 300 400

h-values

45L

36L

16L

32L

9L

44L

34L

69L

Labo

rato

ries

Mandels h statistics(Compost 2 - TOC)

Compost 2-TOC

Unit gkg

Mandels k statistics(Sludge 1 - TOC)Mandels h statistics(Sludge 1 - TOC)

Sample Sludge 1 Sludge 1 - TOC -- Mean PARM = 2721 [gkg]

Element TOC

General calcparmT1= 169626E+04T2= 465445E+06T3= 62T4= 326T5= 10312E+03

n= variabelp= 13

N-table= 5

Mandels statistics End ResultLAB 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

69L 233000 2362 4 -347 037 Fail - - 69L - - -2488046L 2312500 2062 4 -040 032 Fail 2312500 20616 4 3 -408565L 2615500 1708 4 004 026 2615500 17078 4 3 -105566L 2627200 8268 4 006 128 2627200 82678 4 3 -93836L 2664041 4976 3 011 077 2664041 49758 3 2 -56935L 2671500 3533 6 013 055 2671500 35331 6 5 -49556L 2692298 0874 6 016 014 Fail 2692298 08738 6 5 -28732L 2717500 6185 4 019 096 Fail 2717500 61847 4 3 -03519L 2753333 7819 6 025 121 Fail 2753333 78189 6 5 32470L 2814600 - 1 034 Fail 2814600 - 1 9369L 2853667 0398 6 039 006 Fail 2853667 03983 6 5 132716L 2860000 1673 6 040 026 Fail 2860000 16733 6 5 139045L 2884433 7033 6 044 109 Fail 2884433 70331 6 5 163544L 2906167 1129 6 047 017 Fail 2906167 11286 6 5 185234L 3186874 17674 6 089 274 Fail - - 34L - - 4659

Totgem 258617 4692 gkg 1-level 232 (176) 13 2720980 (34L 69L) 13 12Totstd= 67800 4610 5-level 186 (152) 2

72RESULTS Mean = 27209799 gkg

Repeatability variance S2r = 2104538Repeatability std Sr = 458752 --gt 169 r = 128451Between lab variance S2L = 23618387Reproducibility var S2R = 25722925Reproducibility std SR = 1603837 --gt 589 R = 449074Remarks 2 Labs rejected (34L 69L)

000 050 100 150 200 250 300

k-values

69L

46L

65L

66L

36L

35L

56L

32L

19L

70L

9L

16L

45L

44L

34L

Mandels k statistics(Sludge 1 - TOC)

-2500 -2000 -1500 -1000 -500 00 500

Deviation from Mean

69L

46L

65L

66L

36L

35L

56L

32L

19L

70L

9L

16L

45L

44L

34L

Labo

rato

ries

Sludge 1 - TOC -- Mean PARM = 2721 [gkg]

-400 -300 -200 -100 000 100

h-values

69L

65L

36L

56L

19L

9L

45L

34L

Labo

rato

ries

Mandels h statistics(Sludge 1 - TOC)

Sludge 1-TOC

68 Unit gkg

Mandels k statistics(Sludge 2 - TOC)Mandels h statistics(Sludge 2 - TOC)

Sample Sludge 2 Sludge 2 - TOC -- Mean PARM = 2207 [gkg]

Element TOC

General calcparmT1= 128601E+04T2= 285689E+06T3= 58T4= 310T5= 97826E+02

n= variabelp= 12

N-table= 5

Mandels statistics End ResultLAB 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

46L 182500 0500 4 -333 008 Fail - - 46L - - -2024466L 2029475 5267 4 -012 084 2029475 52674 4 3 -177436L 2072609 2222 3 -005 035 2072609 22222 3 2 -134365L 2084750 3865 4 -002 062 2084750 38647 4 3 -122135L 2140333 3119 6 007 050 2140333 31194 6 5 -66556L 2188021 1282 6 015 020 2188021 12822 6 5 -18819L 2223667 7916 6 022 126 Fail 2223667 79157 6 5 16832L 2242500 3096 4 025 049 Fail 2242500 30957 4 3 35645L 2266600 8322 6 029 132 Fail 2266600 83216 6 5 59770L 2272460 - 1 030 Fail 2272460 - 1 65616L 2291667 3869 6 033 062 Fail 2291667 38687 6 5 84844L 2302667 1546 6 035 025 Fail 2302667 15462 6 5 9589L 2367667 1296 6 047 021 Fail 2367667 12956 6 5 160834L 2718591 17124 6 108 273 Fail - - 34L - - 5117

Totgem 209882 4571 gkg 1-level 230 (176) 12 2206868 (34L 46L) 12 11Totstd= 57628 4485 5-level 185 (151) 2

68RESULTS Mean = 22068679 gkg

Repeatability variance S2r = 2126659Repeatability std Sr = 461157 --gt 209 r = 129124Between lab variance S2L = 9960432Reproducibility var S2R = 12087091Reproducibility std SR = 1099413 --gt 498 R = 307836Remarks 2 Labs rejected (34L 46L)

000 050 100 150 200 250 300

k-values

46L

66L

36L

65L

35L

56L

19L

32L

45L

70L

16L

44L

9L

34L

Mandels k statistics(Sludge 2 - TOC)

-2500 -2000 -1500 -1000 -500 00 500 1000

Deviation from Mean

46L

66L

36L

65L

35L

56L

19L

32L

45L

70L

16L

44L

9L

34L

Labo

rato

ries

Sludge 2 - TOC -- Mean PARM = 2207 [gkg]

-400 -300 -200 -100 000 100 200

h-values

46L

66L

36L

65L

35L

56L

19L

32L

45L

70L

16L

44L

9L

34L

Labo

rato

ries

Mandels h statistics(Sludge 2 - TOC)

Sludge 2-TOC

Unit gkg

Mandels k statistics(Soil 4 - TOC)Mandels h statistics(Soil 4 - TOC)

Sample Soil 4 Soil 4 - TOC -- Mean PARM = 1641 [gkg]

Element TOC

General calcparmT1= 102171E+03T2= 168700E+04T3= 62T4= 338T5= 94040E+00

n= variabelp= 12

N-table= 5

Mandels statistics End ResultLAB 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

36L 147161 0470 3 -036 068 Fail 147161 04702 3 2 -16965L 155250 0591 4 -032 085 Fail 155250 05909 4 3 -08844L 157900 0115 6 -031 017 Fail 157900 01152 6 5 -06232L 159250 0359 4 -031 052 Fail 159250 03594 4 3 -0489L 160500 0315 6 -030 045 Fail 160500 03146 6 5 -03656L 164927 0113 6 -028 016 Fail 164927 01127 6 5 00835L 165000 0261 6 -028 038 Fail 165000 02608 6 5 00919L 166667 0505 6 -027 073 Fail 166667 05046 6 5 02645L 168850 0763 6 -026 110 Fail 168850 07628 6 5 04816L 173333 0516 6 -024 074 Fail 173333 05164 6 5 09334L 174761 0346 6 -024 050 Fail 174761 03462 6 5 10730L 175333 0473 3 -024 068 Fail 175333 04726 3 2 11366L 189375 2035 4 -017 294 Fail - - 66L - - 25346L 227500 0500 4 000 072 - - 46L - - 63470L 1040400 - 1 360 Fail - - 70L - - 8763

Totgem 22841 0526 gkg 1-level 232 (176) 12 164078 (46L 66L70L) 12 11Totstd= 22541 0469 5-level 186 (152) 3

71RESULTS Mean = 1640777 gkg

Repeatability variance S2r = 018808Repeatability std Sr = 043368 --gt 264 r = 12143Between lab variance S2L = 054747Reproducibility var S2R = 073555Reproducibility std SR = 085764 --gt 523 R = 24014Remarks 3 Labs rejected (46L 66L70L)

000 050 100 150 200 250 300

k-values

36L

65L

44L

32L

9L

56L

35L

19L

45L

16L

34L

30L

66L

46L

70L

Mandels k statistics(Soil 4 - TOC)

-100 00 100 200 300 400 500 600 700 800 900

Deviation from Mean

36L

65L

44L

32L

9L

56L

35L

19L

45L

16L

34L

30L

66L

46L

70L

Labo

rato

ries

Soil 4 - TOC -- Mean PARM = 1641 [gkg]

-100 000 100 200 300 400

h-values

36L

44L

9L

35L

45L

34L

66L

70L

Labo

rato

ries

Mandels h statistics(Soil 4 - TOC)

Soil 4-TOC

Unit gkg

Mandels k statistics(Soil 5 - TOC)Mandels h statistics(Soil 5 - TOC)

Sample Soil 5 Soil 5 - TOC -- Mean PARM = 2102 [gkg]

Element TOC

General calcparmT1= 113661E+03T2= 240201E+04T3= 54T4= 300T5= 51756E+01

n= variabelp= 10

N-table= 5

Mandels statistics End ResultLAB 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

44L 164383 14708 6 -036 325 Fail - - 44L - - -45865L 181250 0830 4 -033 018 Fail 181250 08302 4 3 -29045L 200317 1116 6 -029 025 Fail 200317 11163 6 5 -09935L 201833 1828 6 -029 040 Fail 201833 18280 6 5 -08432L 203250 0585 4 -029 013 Fail 203250 05852 4 3 -07016L 209000 0959 6 -028 021 Fail 209000 09592 6 5 -0129L 211667 0427 6 -027 009 Fail 211667 04274 6 5 01556L 214030 0887 6 -027 020 Fail 214030 08868 6 5 03819L 216000 0795 6 -026 018 Fail 216000 07950 6 5 05834L 226009 1308 6 -024 029 Fail 226009 13076 6 5 15836L 228783 4310 3 -024 095 Fail - - 36L - - 18666L 238750 1234 4 -022 027 Fail 238750 12340 4 3 28570L 2213900 - 1 333 Fail - - 70L - - 20037

Totgem 36224 2416 gkg 1-level 227 (175) 10 210211 (36L44L 70L) 10 9Totstd= 55669 4003 5-level 184 (151) 3

64RESULTS Mean = 2102106 gkg

Repeatability variance S2r = 117627Repeatability std Sr = 108456 --gt 516 r = 30368Between lab variance S2L = 176699Reproducibility var S2R = 294326Reproducibility std SR = 171559 --gt 816 R = 48037Remarks 3 Labs rejected (36L44L 70L)

000 050 100 150 200 250 300 350

k-values

44L

65L

45L

35L

32L

16L

9L

56L

19L

34L

36L

66L

70L

Mandels k statistics(Soil 5 - TOC)

-500 00 500 1000 1500 2000 2500

Deviation from Mean

44L

65L

45L

35L

32L

16L

9L

56L

19L

34L

36L

66L

70L

Labo

rato

ries

Soil 5 - TOC -- Mean PARM = 2102 [gkg]

-100 000 100 200 300 400

h-values

44L

65L

45L

35L

32L

16L

9L

56L

19L

34L

36L

66L

70L

Labo

rato

ries

Mandels h statistics(Soil 5 - TOC)

Soil 5-TOC

17

Annex 4

Raw data submitted

Sample Compost 1 Sample Compost 2 Sample Sewage Sludge 1Element TOC [gkg] Element TOC [gkg] Element TOC [gkg]

LAB PARM LAB PARM LAB PARM30L 2600 19L 1691 19L 286730L 2580 19L 1634 19L 281430L 2560 19L 1619 19L 276934L 2969 19L 1604 19L 272034L 2936 19L 1499 19L 268834L 2958 19L 1414 19L 266234L 2994 34L 1527 34L 315234L 3199 34L 1622 34L 314934L 3024 34L 1519 34L 343035L 2306 34L 1753 34L 336535L 2300 34L 1636 34L 304235L 2298 34L 1874 34L 298335L 2296 35L 1506 35L 270735L 2291 35L 1312 35L 270335L 2259 35L 1294 35L 268836L 2546 35L 1279 35L 267436L 2527 35L 1191 35L 263136L 2470 35L 1177 35L 262644L 2583 36L 1418 36L 271344L 2581 36L 1408 36L 266544L 2578 36L 1320 36L 261444L 2539 44L 1719 44L 292044L 2528 44L 1664 44L 291644L 2525 44L 1654 44L 291245L 2658 44L 1637 44L 290045L 2600 44L 1624 44L 289645L 2546 44L 1620 44L 289345L 2461 45L 1428 45L 297645L 2409 45L 1325 45L 295245L 2350 45L 1323 45L 288546L 2460 45L 1321 45L 286646L 2400 45L 1309 45L 284046L 2370 45L 1253 45L 278746L 2350 46L 1580 46L 233056L 2436 46L 1550 46L 233056L 2435 46L 1170 46L 230056L 2405 46L 1120 46L 229056L 2397 56L 1642 56L 270256L 2375 56L 1626 56L 270156L 2358 56L 1622 56L 269465L 2587 56L 1571 56L 269365L 2542 56L 1561 56L 268465L 2483 56L 1545 56L 268066L 2454 65L 1933 65L 264166L 2429 65L 1838 65L 260966L 2365 65L 1693 65L 260766L 2262 65L 1562 65L 260569L 2730 66L 1561 66L 270169L 2250 66L 1545 66L 267469L 1440 66L 1420 66L 261969L 1420 66L 1417 66L 251470L 2435 69L 2700 69L 2639L 2594 69L 2660 69L 2409L 2570 69L 2170 69L 2199L 2565 69L 2130 69L 2109L 2563 70L 1414 70L 28159L 2562 9L 1644 9L 28579L 2555 9L 1641 9L 2856

32L 2290 9L 1602 9L 285532L 2390 9L 1589 9L 285532L 2510 9L 1526 9L 285332L 2470 9L 1492 9L 284616L 2380 32L 1470 32L 265016L 2530 32L 1520 32L 271016L 2400 32L 1540 32L 271016L 2500 32L 1600 32L 280016L 2420 16L 1400 16L 284016L 2410 16L 1440 16L 2840

16L 1470 16L 286016L 1510 16L 287016L 1360 16L 287016L 1390 16L 2880

Sample Sewage Sludge 2 Sample Soil 4 Sample Soil 5Element TOC [gkg] Element TOC [gkg] Element TOC [gkg]

LAB PARM LAB PARM LAB PARM19L 2308 19L 1720 19L 225019L 2303 19L 1700 19L 223019L 2239 19L 1690 19L 221019L 2204 19L 1670 19L 211019L 2192 19L 1640 19L 210019L 2096 19L 1580 19L 206034L 2631 30L 1790 34L 244334L 2471 30L 1770 34L 233434L 2977 30L 1700 34L 231534L 2785 34L 1740 34L 222134L 2780 34L 1692 34L 217634L 2668 34L 1727 34L 207335L 2179 34L 1767 35L 233035L 2160 34L 1777 35L 208035L 2158 34L 1783 35L 201035L 2132 35L 1700 35L 198035L 2119 35L 1650 35L 193035L 2094 35L 1650 35L 178036L 2096 35L 1640 36L 254036L 2069 35L 1630 36L 253436L 2052 35L 1630 36L 179044L 2325 36L 1500 44L 302144L 2309 36L 1497 44L 298244L 2307 36L 1417 44L 295644L 2305 44L 1594 44L 30744L 2287 44L 1587 44L 30044L 2283 44L 1584 44L 29745L 2331 44L 1574 45L 214945L 2327 44L 1573 45L 209245L 2308 44L 1562 45L 203345L 2287 45L 1827 45L 197145L 2234 45L 1709 45L 193345L 2113 45L 1666 45L 184146L 190 45L 1665 56L 223746L 180 45L 1664 56L 222246L 180 45L 1600 56L 220346L 180 46L 2300 56L 206956L 2204 46L 2300 56L 206856L 2197 46L 2300 56L 204456L 2193 46L 2200 65L 192056L 2185 56L 1668 65L 182056L 2183 56L 1654 65L 179056L 2167 56L 1653 65L 172065L 2136 56L 1643 66L 254365L 2091 56L 1639 66L 242465L 2065 56L 1638 66L 232165L 2047 65L 1630 66L 226266L 2105 65L 1560 70L 2213966L 2022 65L 1530 9L 218066L 2009 65L 1490 9L 214066L 1983 66L 2179 9L 213070L 2272 66L 1900 9L 21109L 2385 66L 1762 9L 20709L 2377 66L 1734 9L 20709L 2375 70L 10404 32L 20509L 2359 9L 1640 32L 21009L 2356 9L 1640 32L 20209L 2354 9L 1610 32L 1960

32L 2240 9L 1590 16L 210032L 2260 9L 1590 16L 220032L 2200 9L 1560 16L 220032L 2270 32L 1640 16L 206016L 2300 32L 1600 16L 197016L 2310 32L 1560 16L 201016L 2350 32L 157016L 2260 16L 170016L 2290 16L 180016L 2240 16L 1700

16L 180016L 170016L 1700

European Commission EUR 23012 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on total organic carbon Author(s) E Sobiecka H van der Sloot K Andersen B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 50 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07412-7 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 total organic carbon (TOC) in soils sludge and treated bio-waste 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

-23012-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

16

Annex 3

Statistical calculations

Unit gkg

Mandels k statistics(Compost 1 - TOC)Mandels h statistics(Compost 1 - TOC)

Sample Compost 1 Compost 1 - TOC -- Mean PARM = 2463 [gkg]

Element TOC

General calcparmT1= 142643E+04T2= 351264E+06T3= 58T4= 292T5= 16501E+03

n= variabelp= 13

N-table= 5

Mandels statistics End ResultLAB 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

69L 1960000 64265 4 -235 352 Fail - - 69L - - -502735L 2291667 1674 6 -081 009 2291667 16741 6 5 -171066L 2377425 8552 4 -041 047 2377425 85518 4 3 -85346L 2395000 4796 4 -033 026 2395000 47958 4 3 -67756L 2401227 3133 6 -030 017 2401227 31330 6 5 -61432L 2415000 9713 4 -024 053 2415000 97125 4 3 -47770L 2435100 - 1 -014 2435100 - 1 -27616L 2440000 6033 6 -012 033 2440000 60332 6 5 -22745L 2503800 11759 6 018 064 2503800 117589 6 5 41136L 2514416 3994 3 023 022 2514416 39937 3 2 51765L 2537333 5216 3 033 029 2537333 52157 3 2 74744L 2555667 2783 6 042 015 2555667 27826 6 5 9309L 2568167 1356 6 048 007 2568167 13556 6 5 105530L 2580000 2000 3 053 011 2580000 20000 3 2 117334L 3013269 9580 6 255 053 Fail - - 34L - - 5506

Totgem 246587 9632 gkg 1-level 232 (176) 13 2462677 (34L 69L) 13 12Totstd= 21507 16070 5-level 186 (152) 2

68RESULTS Mean = 24626770 gkg

Repeatability variance S2r = 3666797Repeatability std Sr = 605541 --gt 246 r = 169551Between lab variance S2L = 7715586Reproducibility var S2R = 11382383Reproducibility std SR = 1066882 --gt 433 R = 298727Remarks 2 Labs rejected (34L 69L)

000 050 100 150 200 250 300 350 400

k-values

69L

35L

66L

46L

56L

32L

70L

16L

45L

36L

65L

44L

9L

30L

34L

Mandels k statistics(Compost 1 - TOC)

-600 -400 -200 00 200 400 600

Deviation from Mean

69L

35L

66L

46L

56L

32L

70L

16L

45L

36L

65L

44L

9L

30L

34L

Labo

rato

ries

Compost 1 - TOC -- Mean PARM = 2463 [gkg]

-300 -200 -100 000 100 200 300

h-values

69L

66L

56L

70L

45L

65L

9L

34L

Labo

rato

ries

Mandels h statistics(Compost 1 - TOC)

Compost 1-TOC

Unit gkg

Mandels k statistics(Compost 2 - TOC)Mandels h statistics(Compost 2 - TOC)

Sample Compost 2 Compost 2 - TOC -- Mean PARM = 1542 [gkg]

Element TOC

General calcparmT1= 994897E+03T2= 155556E+06T3= 64T4= 346T5= 41738E+03

n= variabelp= 13

N-table= 5

Mandels statistics End ResultLAB 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

45L 1326733 5665 6 -100 042 Fail 1326733 56646 6 5 -215046L 1355000 24365 4 -089 181 Fail - - 46L - - -186736L 1381949 5407 3 -078 040 Fail 1381949 54070 3 2 -159870L 1414120 - 1 -066 Fail 1414120 - 1 -127616L 1428333 5565 6 -061 041 1428333 55648 6 5 -113466L 1485550 7805 4 -039 058 1485550 78047 4 3 -56232L 1532500 5377 4 -021 040 1532500 53774 4 3 -09219L 1576833 10138 6 -004 075 1576833 101381 6 5 3519L 1582333 6166 6 -002 046 1582333 61659 6 5 40656L 1594432 4046 6 003 030 1594432 40463 6 5 52744L 1653000 3651 6 025 027 1653000 36508 6 5 111334L 1655127 13717 6 026 102 1655127 137168 6 5 113434L 1655127 13717 6 026 102 1655127 137168 6 5 113465L 1756500 16295 4 065 121 Fail 1756500 162949 4 3 214869L 2415000 30687 4 316 228 Fail - - 69L - - 8733

Totgem 158750 10900 gkg 1-level 232 (176) 13 1541734 (46L 69L) 13 12Totstd= 26187 8164 5-level 186 (152) 2

72RESULTS Mean = 15417337 gkg

Repeatability variance S2r = 8183950Repeatability std Sr = 904652 --gt 587 r = 253303Between lab variance S2L = 13631046Reproducibility var S2R = 21814995Reproducibility std SR = 1476990 --gt 958 R = 413557Remarks 2 Labs rejected (46L 69L)

000 050 100 150 200 250

k-values

45L

46L

36L

70L

16L

66L

32L

19L

9L

56L

44L

34L

34L

65L

69L

Mandels k statistics(Compost 2 - TOC)

-400 -200 00 200 400 600 800 1000

Deviation from Mean

45L

46L

36L

70L

16L

66L

32L

19L

9L

56L

44L

34L

34L

65L

69L

Labo

rato

ries

Compost 2 - TOC -- Mean PARM = 1542 [gkg]

-100 000 100 200 300 400

h-values

45L

36L

16L

32L

9L

44L

34L

69L

Labo

rato

ries

Mandels h statistics(Compost 2 - TOC)

Compost 2-TOC

Unit gkg

Mandels k statistics(Sludge 1 - TOC)Mandels h statistics(Sludge 1 - TOC)

Sample Sludge 1 Sludge 1 - TOC -- Mean PARM = 2721 [gkg]

Element TOC

General calcparmT1= 169626E+04T2= 465445E+06T3= 62T4= 326T5= 10312E+03

n= variabelp= 13

N-table= 5

Mandels statistics End ResultLAB 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

69L 233000 2362 4 -347 037 Fail - - 69L - - -2488046L 2312500 2062 4 -040 032 Fail 2312500 20616 4 3 -408565L 2615500 1708 4 004 026 2615500 17078 4 3 -105566L 2627200 8268 4 006 128 2627200 82678 4 3 -93836L 2664041 4976 3 011 077 2664041 49758 3 2 -56935L 2671500 3533 6 013 055 2671500 35331 6 5 -49556L 2692298 0874 6 016 014 Fail 2692298 08738 6 5 -28732L 2717500 6185 4 019 096 Fail 2717500 61847 4 3 -03519L 2753333 7819 6 025 121 Fail 2753333 78189 6 5 32470L 2814600 - 1 034 Fail 2814600 - 1 9369L 2853667 0398 6 039 006 Fail 2853667 03983 6 5 132716L 2860000 1673 6 040 026 Fail 2860000 16733 6 5 139045L 2884433 7033 6 044 109 Fail 2884433 70331 6 5 163544L 2906167 1129 6 047 017 Fail 2906167 11286 6 5 185234L 3186874 17674 6 089 274 Fail - - 34L - - 4659

Totgem 258617 4692 gkg 1-level 232 (176) 13 2720980 (34L 69L) 13 12Totstd= 67800 4610 5-level 186 (152) 2

72RESULTS Mean = 27209799 gkg

Repeatability variance S2r = 2104538Repeatability std Sr = 458752 --gt 169 r = 128451Between lab variance S2L = 23618387Reproducibility var S2R = 25722925Reproducibility std SR = 1603837 --gt 589 R = 449074Remarks 2 Labs rejected (34L 69L)

000 050 100 150 200 250 300

k-values

69L

46L

65L

66L

36L

35L

56L

32L

19L

70L

9L

16L

45L

44L

34L

Mandels k statistics(Sludge 1 - TOC)

-2500 -2000 -1500 -1000 -500 00 500

Deviation from Mean

69L

46L

65L

66L

36L

35L

56L

32L

19L

70L

9L

16L

45L

44L

34L

Labo

rato

ries

Sludge 1 - TOC -- Mean PARM = 2721 [gkg]

-400 -300 -200 -100 000 100

h-values

69L

65L

36L

56L

19L

9L

45L

34L

Labo

rato

ries

Mandels h statistics(Sludge 1 - TOC)

Sludge 1-TOC

68 Unit gkg

Mandels k statistics(Sludge 2 - TOC)Mandels h statistics(Sludge 2 - TOC)

Sample Sludge 2 Sludge 2 - TOC -- Mean PARM = 2207 [gkg]

Element TOC

General calcparmT1= 128601E+04T2= 285689E+06T3= 58T4= 310T5= 97826E+02

n= variabelp= 12

N-table= 5

Mandels statistics End ResultLAB 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

46L 182500 0500 4 -333 008 Fail - - 46L - - -2024466L 2029475 5267 4 -012 084 2029475 52674 4 3 -177436L 2072609 2222 3 -005 035 2072609 22222 3 2 -134365L 2084750 3865 4 -002 062 2084750 38647 4 3 -122135L 2140333 3119 6 007 050 2140333 31194 6 5 -66556L 2188021 1282 6 015 020 2188021 12822 6 5 -18819L 2223667 7916 6 022 126 Fail 2223667 79157 6 5 16832L 2242500 3096 4 025 049 Fail 2242500 30957 4 3 35645L 2266600 8322 6 029 132 Fail 2266600 83216 6 5 59770L 2272460 - 1 030 Fail 2272460 - 1 65616L 2291667 3869 6 033 062 Fail 2291667 38687 6 5 84844L 2302667 1546 6 035 025 Fail 2302667 15462 6 5 9589L 2367667 1296 6 047 021 Fail 2367667 12956 6 5 160834L 2718591 17124 6 108 273 Fail - - 34L - - 5117

Totgem 209882 4571 gkg 1-level 230 (176) 12 2206868 (34L 46L) 12 11Totstd= 57628 4485 5-level 185 (151) 2

68RESULTS Mean = 22068679 gkg

Repeatability variance S2r = 2126659Repeatability std Sr = 461157 --gt 209 r = 129124Between lab variance S2L = 9960432Reproducibility var S2R = 12087091Reproducibility std SR = 1099413 --gt 498 R = 307836Remarks 2 Labs rejected (34L 46L)

000 050 100 150 200 250 300

k-values

46L

66L

36L

65L

35L

56L

19L

32L

45L

70L

16L

44L

9L

34L

Mandels k statistics(Sludge 2 - TOC)

-2500 -2000 -1500 -1000 -500 00 500 1000

Deviation from Mean

46L

66L

36L

65L

35L

56L

19L

32L

45L

70L

16L

44L

9L

34L

Labo

rato

ries

Sludge 2 - TOC -- Mean PARM = 2207 [gkg]

-400 -300 -200 -100 000 100 200

h-values

46L

66L

36L

65L

35L

56L

19L

32L

45L

70L

16L

44L

9L

34L

Labo

rato

ries

Mandels h statistics(Sludge 2 - TOC)

Sludge 2-TOC

Unit gkg

Mandels k statistics(Soil 4 - TOC)Mandels h statistics(Soil 4 - TOC)

Sample Soil 4 Soil 4 - TOC -- Mean PARM = 1641 [gkg]

Element TOC

General calcparmT1= 102171E+03T2= 168700E+04T3= 62T4= 338T5= 94040E+00

n= variabelp= 12

N-table= 5

Mandels statistics End ResultLAB 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

36L 147161 0470 3 -036 068 Fail 147161 04702 3 2 -16965L 155250 0591 4 -032 085 Fail 155250 05909 4 3 -08844L 157900 0115 6 -031 017 Fail 157900 01152 6 5 -06232L 159250 0359 4 -031 052 Fail 159250 03594 4 3 -0489L 160500 0315 6 -030 045 Fail 160500 03146 6 5 -03656L 164927 0113 6 -028 016 Fail 164927 01127 6 5 00835L 165000 0261 6 -028 038 Fail 165000 02608 6 5 00919L 166667 0505 6 -027 073 Fail 166667 05046 6 5 02645L 168850 0763 6 -026 110 Fail 168850 07628 6 5 04816L 173333 0516 6 -024 074 Fail 173333 05164 6 5 09334L 174761 0346 6 -024 050 Fail 174761 03462 6 5 10730L 175333 0473 3 -024 068 Fail 175333 04726 3 2 11366L 189375 2035 4 -017 294 Fail - - 66L - - 25346L 227500 0500 4 000 072 - - 46L - - 63470L 1040400 - 1 360 Fail - - 70L - - 8763

Totgem 22841 0526 gkg 1-level 232 (176) 12 164078 (46L 66L70L) 12 11Totstd= 22541 0469 5-level 186 (152) 3

71RESULTS Mean = 1640777 gkg

Repeatability variance S2r = 018808Repeatability std Sr = 043368 --gt 264 r = 12143Between lab variance S2L = 054747Reproducibility var S2R = 073555Reproducibility std SR = 085764 --gt 523 R = 24014Remarks 3 Labs rejected (46L 66L70L)

000 050 100 150 200 250 300

k-values

36L

65L

44L

32L

9L

56L

35L

19L

45L

16L

34L

30L

66L

46L

70L

Mandels k statistics(Soil 4 - TOC)

-100 00 100 200 300 400 500 600 700 800 900

Deviation from Mean

36L

65L

44L

32L

9L

56L

35L

19L

45L

16L

34L

30L

66L

46L

70L

Labo

rato

ries

Soil 4 - TOC -- Mean PARM = 1641 [gkg]

-100 000 100 200 300 400

h-values

36L

44L

9L

35L

45L

34L

66L

70L

Labo

rato

ries

Mandels h statistics(Soil 4 - TOC)

Soil 4-TOC

Unit gkg

Mandels k statistics(Soil 5 - TOC)Mandels h statistics(Soil 5 - TOC)

Sample Soil 5 Soil 5 - TOC -- Mean PARM = 2102 [gkg]

Element TOC

General calcparmT1= 113661E+03T2= 240201E+04T3= 54T4= 300T5= 51756E+01

n= variabelp= 10

N-table= 5

Mandels statistics End ResultLAB 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

44L 164383 14708 6 -036 325 Fail - - 44L - - -45865L 181250 0830 4 -033 018 Fail 181250 08302 4 3 -29045L 200317 1116 6 -029 025 Fail 200317 11163 6 5 -09935L 201833 1828 6 -029 040 Fail 201833 18280 6 5 -08432L 203250 0585 4 -029 013 Fail 203250 05852 4 3 -07016L 209000 0959 6 -028 021 Fail 209000 09592 6 5 -0129L 211667 0427 6 -027 009 Fail 211667 04274 6 5 01556L 214030 0887 6 -027 020 Fail 214030 08868 6 5 03819L 216000 0795 6 -026 018 Fail 216000 07950 6 5 05834L 226009 1308 6 -024 029 Fail 226009 13076 6 5 15836L 228783 4310 3 -024 095 Fail - - 36L - - 18666L 238750 1234 4 -022 027 Fail 238750 12340 4 3 28570L 2213900 - 1 333 Fail - - 70L - - 20037

Totgem 36224 2416 gkg 1-level 227 (175) 10 210211 (36L44L 70L) 10 9Totstd= 55669 4003 5-level 184 (151) 3

64RESULTS Mean = 2102106 gkg

Repeatability variance S2r = 117627Repeatability std Sr = 108456 --gt 516 r = 30368Between lab variance S2L = 176699Reproducibility var S2R = 294326Reproducibility std SR = 171559 --gt 816 R = 48037Remarks 3 Labs rejected (36L44L 70L)

000 050 100 150 200 250 300 350

k-values

44L

65L

45L

35L

32L

16L

9L

56L

19L

34L

36L

66L

70L

Mandels k statistics(Soil 5 - TOC)

-500 00 500 1000 1500 2000 2500

Deviation from Mean

44L

65L

45L

35L

32L

16L

9L

56L

19L

34L

36L

66L

70L

Labo

rato

ries

Soil 5 - TOC -- Mean PARM = 2102 [gkg]

-100 000 100 200 300 400

h-values

44L

65L

45L

35L

32L

16L

9L

56L

19L

34L

36L

66L

70L

Labo

rato

ries

Mandels h statistics(Soil 5 - TOC)

Soil 5-TOC

17

Annex 4

Raw data submitted

Sample Compost 1 Sample Compost 2 Sample Sewage Sludge 1Element TOC [gkg] Element TOC [gkg] Element TOC [gkg]

LAB PARM LAB PARM LAB PARM30L 2600 19L 1691 19L 286730L 2580 19L 1634 19L 281430L 2560 19L 1619 19L 276934L 2969 19L 1604 19L 272034L 2936 19L 1499 19L 268834L 2958 19L 1414 19L 266234L 2994 34L 1527 34L 315234L 3199 34L 1622 34L 314934L 3024 34L 1519 34L 343035L 2306 34L 1753 34L 336535L 2300 34L 1636 34L 304235L 2298 34L 1874 34L 298335L 2296 35L 1506 35L 270735L 2291 35L 1312 35L 270335L 2259 35L 1294 35L 268836L 2546 35L 1279 35L 267436L 2527 35L 1191 35L 263136L 2470 35L 1177 35L 262644L 2583 36L 1418 36L 271344L 2581 36L 1408 36L 266544L 2578 36L 1320 36L 261444L 2539 44L 1719 44L 292044L 2528 44L 1664 44L 291644L 2525 44L 1654 44L 291245L 2658 44L 1637 44L 290045L 2600 44L 1624 44L 289645L 2546 44L 1620 44L 289345L 2461 45L 1428 45L 297645L 2409 45L 1325 45L 295245L 2350 45L 1323 45L 288546L 2460 45L 1321 45L 286646L 2400 45L 1309 45L 284046L 2370 45L 1253 45L 278746L 2350 46L 1580 46L 233056L 2436 46L 1550 46L 233056L 2435 46L 1170 46L 230056L 2405 46L 1120 46L 229056L 2397 56L 1642 56L 270256L 2375 56L 1626 56L 270156L 2358 56L 1622 56L 269465L 2587 56L 1571 56L 269365L 2542 56L 1561 56L 268465L 2483 56L 1545 56L 268066L 2454 65L 1933 65L 264166L 2429 65L 1838 65L 260966L 2365 65L 1693 65L 260766L 2262 65L 1562 65L 260569L 2730 66L 1561 66L 270169L 2250 66L 1545 66L 267469L 1440 66L 1420 66L 261969L 1420 66L 1417 66L 251470L 2435 69L 2700 69L 2639L 2594 69L 2660 69L 2409L 2570 69L 2170 69L 2199L 2565 69L 2130 69L 2109L 2563 70L 1414 70L 28159L 2562 9L 1644 9L 28579L 2555 9L 1641 9L 2856

32L 2290 9L 1602 9L 285532L 2390 9L 1589 9L 285532L 2510 9L 1526 9L 285332L 2470 9L 1492 9L 284616L 2380 32L 1470 32L 265016L 2530 32L 1520 32L 271016L 2400 32L 1540 32L 271016L 2500 32L 1600 32L 280016L 2420 16L 1400 16L 284016L 2410 16L 1440 16L 2840

16L 1470 16L 286016L 1510 16L 287016L 1360 16L 287016L 1390 16L 2880

Sample Sewage Sludge 2 Sample Soil 4 Sample Soil 5Element TOC [gkg] Element TOC [gkg] Element TOC [gkg]

LAB PARM LAB PARM LAB PARM19L 2308 19L 1720 19L 225019L 2303 19L 1700 19L 223019L 2239 19L 1690 19L 221019L 2204 19L 1670 19L 211019L 2192 19L 1640 19L 210019L 2096 19L 1580 19L 206034L 2631 30L 1790 34L 244334L 2471 30L 1770 34L 233434L 2977 30L 1700 34L 231534L 2785 34L 1740 34L 222134L 2780 34L 1692 34L 217634L 2668 34L 1727 34L 207335L 2179 34L 1767 35L 233035L 2160 34L 1777 35L 208035L 2158 34L 1783 35L 201035L 2132 35L 1700 35L 198035L 2119 35L 1650 35L 193035L 2094 35L 1650 35L 178036L 2096 35L 1640 36L 254036L 2069 35L 1630 36L 253436L 2052 35L 1630 36L 179044L 2325 36L 1500 44L 302144L 2309 36L 1497 44L 298244L 2307 36L 1417 44L 295644L 2305 44L 1594 44L 30744L 2287 44L 1587 44L 30044L 2283 44L 1584 44L 29745L 2331 44L 1574 45L 214945L 2327 44L 1573 45L 209245L 2308 44L 1562 45L 203345L 2287 45L 1827 45L 197145L 2234 45L 1709 45L 193345L 2113 45L 1666 45L 184146L 190 45L 1665 56L 223746L 180 45L 1664 56L 222246L 180 45L 1600 56L 220346L 180 46L 2300 56L 206956L 2204 46L 2300 56L 206856L 2197 46L 2300 56L 204456L 2193 46L 2200 65L 192056L 2185 56L 1668 65L 182056L 2183 56L 1654 65L 179056L 2167 56L 1653 65L 172065L 2136 56L 1643 66L 254365L 2091 56L 1639 66L 242465L 2065 56L 1638 66L 232165L 2047 65L 1630 66L 226266L 2105 65L 1560 70L 2213966L 2022 65L 1530 9L 218066L 2009 65L 1490 9L 214066L 1983 66L 2179 9L 213070L 2272 66L 1900 9L 21109L 2385 66L 1762 9L 20709L 2377 66L 1734 9L 20709L 2375 70L 10404 32L 20509L 2359 9L 1640 32L 21009L 2356 9L 1640 32L 20209L 2354 9L 1610 32L 1960

32L 2240 9L 1590 16L 210032L 2260 9L 1590 16L 220032L 2200 9L 1560 16L 220032L 2270 32L 1640 16L 206016L 2300 32L 1600 16L 197016L 2310 32L 1560 16L 201016L 2350 32L 157016L 2260 16L 170016L 2290 16L 180016L 2240 16L 1700

16L 180016L 170016L 1700

European Commission EUR 23012 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on total organic carbon Author(s) E Sobiecka H van der Sloot K Andersen B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 50 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07412-7 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 total organic carbon (TOC) in soils sludge and treated bio-waste 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

-23012-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

16

Annex 3

Statistical calculations

Unit gkg

Mandels k statistics(Compost 1 - TOC)Mandels h statistics(Compost 1 - TOC)

Sample Compost 1 Compost 1 - TOC -- Mean PARM = 2463 [gkg]

Element TOC

General calcparmT1= 142643E+04T2= 351264E+06T3= 58T4= 292T5= 16501E+03

n= variabelp= 13

N-table= 5

Mandels statistics End ResultLAB 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

69L 1960000 64265 4 -235 352 Fail - - 69L - - -502735L 2291667 1674 6 -081 009 2291667 16741 6 5 -171066L 2377425 8552 4 -041 047 2377425 85518 4 3 -85346L 2395000 4796 4 -033 026 2395000 47958 4 3 -67756L 2401227 3133 6 -030 017 2401227 31330 6 5 -61432L 2415000 9713 4 -024 053 2415000 97125 4 3 -47770L 2435100 - 1 -014 2435100 - 1 -27616L 2440000 6033 6 -012 033 2440000 60332 6 5 -22745L 2503800 11759 6 018 064 2503800 117589 6 5 41136L 2514416 3994 3 023 022 2514416 39937 3 2 51765L 2537333 5216 3 033 029 2537333 52157 3 2 74744L 2555667 2783 6 042 015 2555667 27826 6 5 9309L 2568167 1356 6 048 007 2568167 13556 6 5 105530L 2580000 2000 3 053 011 2580000 20000 3 2 117334L 3013269 9580 6 255 053 Fail - - 34L - - 5506

Totgem 246587 9632 gkg 1-level 232 (176) 13 2462677 (34L 69L) 13 12Totstd= 21507 16070 5-level 186 (152) 2

68RESULTS Mean = 24626770 gkg

Repeatability variance S2r = 3666797Repeatability std Sr = 605541 --gt 246 r = 169551Between lab variance S2L = 7715586Reproducibility var S2R = 11382383Reproducibility std SR = 1066882 --gt 433 R = 298727Remarks 2 Labs rejected (34L 69L)

000 050 100 150 200 250 300 350 400

k-values

69L

35L

66L

46L

56L

32L

70L

16L

45L

36L

65L

44L

9L

30L

34L

Mandels k statistics(Compost 1 - TOC)

-600 -400 -200 00 200 400 600

Deviation from Mean

69L

35L

66L

46L

56L

32L

70L

16L

45L

36L

65L

44L

9L

30L

34L

Labo

rato

ries

Compost 1 - TOC -- Mean PARM = 2463 [gkg]

-300 -200 -100 000 100 200 300

h-values

69L

66L

56L

70L

45L

65L

9L

34L

Labo

rato

ries

Mandels h statistics(Compost 1 - TOC)

Compost 1-TOC

Unit gkg

Mandels k statistics(Compost 2 - TOC)Mandels h statistics(Compost 2 - TOC)

Sample Compost 2 Compost 2 - TOC -- Mean PARM = 1542 [gkg]

Element TOC

General calcparmT1= 994897E+03T2= 155556E+06T3= 64T4= 346T5= 41738E+03

n= variabelp= 13

N-table= 5

Mandels statistics End ResultLAB 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

45L 1326733 5665 6 -100 042 Fail 1326733 56646 6 5 -215046L 1355000 24365 4 -089 181 Fail - - 46L - - -186736L 1381949 5407 3 -078 040 Fail 1381949 54070 3 2 -159870L 1414120 - 1 -066 Fail 1414120 - 1 -127616L 1428333 5565 6 -061 041 1428333 55648 6 5 -113466L 1485550 7805 4 -039 058 1485550 78047 4 3 -56232L 1532500 5377 4 -021 040 1532500 53774 4 3 -09219L 1576833 10138 6 -004 075 1576833 101381 6 5 3519L 1582333 6166 6 -002 046 1582333 61659 6 5 40656L 1594432 4046 6 003 030 1594432 40463 6 5 52744L 1653000 3651 6 025 027 1653000 36508 6 5 111334L 1655127 13717 6 026 102 1655127 137168 6 5 113434L 1655127 13717 6 026 102 1655127 137168 6 5 113465L 1756500 16295 4 065 121 Fail 1756500 162949 4 3 214869L 2415000 30687 4 316 228 Fail - - 69L - - 8733

Totgem 158750 10900 gkg 1-level 232 (176) 13 1541734 (46L 69L) 13 12Totstd= 26187 8164 5-level 186 (152) 2

72RESULTS Mean = 15417337 gkg

Repeatability variance S2r = 8183950Repeatability std Sr = 904652 --gt 587 r = 253303Between lab variance S2L = 13631046Reproducibility var S2R = 21814995Reproducibility std SR = 1476990 --gt 958 R = 413557Remarks 2 Labs rejected (46L 69L)

000 050 100 150 200 250

k-values

45L

46L

36L

70L

16L

66L

32L

19L

9L

56L

44L

34L

34L

65L

69L

Mandels k statistics(Compost 2 - TOC)

-400 -200 00 200 400 600 800 1000

Deviation from Mean

45L

46L

36L

70L

16L

66L

32L

19L

9L

56L

44L

34L

34L

65L

69L

Labo

rato

ries

Compost 2 - TOC -- Mean PARM = 1542 [gkg]

-100 000 100 200 300 400

h-values

45L

36L

16L

32L

9L

44L

34L

69L

Labo

rato

ries

Mandels h statistics(Compost 2 - TOC)

Compost 2-TOC

Unit gkg

Mandels k statistics(Sludge 1 - TOC)Mandels h statistics(Sludge 1 - TOC)

Sample Sludge 1 Sludge 1 - TOC -- Mean PARM = 2721 [gkg]

Element TOC

General calcparmT1= 169626E+04T2= 465445E+06T3= 62T4= 326T5= 10312E+03

n= variabelp= 13

N-table= 5

Mandels statistics End ResultLAB 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

69L 233000 2362 4 -347 037 Fail - - 69L - - -2488046L 2312500 2062 4 -040 032 Fail 2312500 20616 4 3 -408565L 2615500 1708 4 004 026 2615500 17078 4 3 -105566L 2627200 8268 4 006 128 2627200 82678 4 3 -93836L 2664041 4976 3 011 077 2664041 49758 3 2 -56935L 2671500 3533 6 013 055 2671500 35331 6 5 -49556L 2692298 0874 6 016 014 Fail 2692298 08738 6 5 -28732L 2717500 6185 4 019 096 Fail 2717500 61847 4 3 -03519L 2753333 7819 6 025 121 Fail 2753333 78189 6 5 32470L 2814600 - 1 034 Fail 2814600 - 1 9369L 2853667 0398 6 039 006 Fail 2853667 03983 6 5 132716L 2860000 1673 6 040 026 Fail 2860000 16733 6 5 139045L 2884433 7033 6 044 109 Fail 2884433 70331 6 5 163544L 2906167 1129 6 047 017 Fail 2906167 11286 6 5 185234L 3186874 17674 6 089 274 Fail - - 34L - - 4659

Totgem 258617 4692 gkg 1-level 232 (176) 13 2720980 (34L 69L) 13 12Totstd= 67800 4610 5-level 186 (152) 2

72RESULTS Mean = 27209799 gkg

Repeatability variance S2r = 2104538Repeatability std Sr = 458752 --gt 169 r = 128451Between lab variance S2L = 23618387Reproducibility var S2R = 25722925Reproducibility std SR = 1603837 --gt 589 R = 449074Remarks 2 Labs rejected (34L 69L)

000 050 100 150 200 250 300

k-values

69L

46L

65L

66L

36L

35L

56L

32L

19L

70L

9L

16L

45L

44L

34L

Mandels k statistics(Sludge 1 - TOC)

-2500 -2000 -1500 -1000 -500 00 500

Deviation from Mean

69L

46L

65L

66L

36L

35L

56L

32L

19L

70L

9L

16L

45L

44L

34L

Labo

rato

ries

Sludge 1 - TOC -- Mean PARM = 2721 [gkg]

-400 -300 -200 -100 000 100

h-values

69L

65L

36L

56L

19L

9L

45L

34L

Labo

rato

ries

Mandels h statistics(Sludge 1 - TOC)

Sludge 1-TOC

68 Unit gkg

Mandels k statistics(Sludge 2 - TOC)Mandels h statistics(Sludge 2 - TOC)

Sample Sludge 2 Sludge 2 - TOC -- Mean PARM = 2207 [gkg]

Element TOC

General calcparmT1= 128601E+04T2= 285689E+06T3= 58T4= 310T5= 97826E+02

n= variabelp= 12

N-table= 5

Mandels statistics End ResultLAB 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

46L 182500 0500 4 -333 008 Fail - - 46L - - -2024466L 2029475 5267 4 -012 084 2029475 52674 4 3 -177436L 2072609 2222 3 -005 035 2072609 22222 3 2 -134365L 2084750 3865 4 -002 062 2084750 38647 4 3 -122135L 2140333 3119 6 007 050 2140333 31194 6 5 -66556L 2188021 1282 6 015 020 2188021 12822 6 5 -18819L 2223667 7916 6 022 126 Fail 2223667 79157 6 5 16832L 2242500 3096 4 025 049 Fail 2242500 30957 4 3 35645L 2266600 8322 6 029 132 Fail 2266600 83216 6 5 59770L 2272460 - 1 030 Fail 2272460 - 1 65616L 2291667 3869 6 033 062 Fail 2291667 38687 6 5 84844L 2302667 1546 6 035 025 Fail 2302667 15462 6 5 9589L 2367667 1296 6 047 021 Fail 2367667 12956 6 5 160834L 2718591 17124 6 108 273 Fail - - 34L - - 5117

Totgem 209882 4571 gkg 1-level 230 (176) 12 2206868 (34L 46L) 12 11Totstd= 57628 4485 5-level 185 (151) 2

68RESULTS Mean = 22068679 gkg

Repeatability variance S2r = 2126659Repeatability std Sr = 461157 --gt 209 r = 129124Between lab variance S2L = 9960432Reproducibility var S2R = 12087091Reproducibility std SR = 1099413 --gt 498 R = 307836Remarks 2 Labs rejected (34L 46L)

000 050 100 150 200 250 300

k-values

46L

66L

36L

65L

35L

56L

19L

32L

45L

70L

16L

44L

9L

34L

Mandels k statistics(Sludge 2 - TOC)

-2500 -2000 -1500 -1000 -500 00 500 1000

Deviation from Mean

46L

66L

36L

65L

35L

56L

19L

32L

45L

70L

16L

44L

9L

34L

Labo

rato

ries

Sludge 2 - TOC -- Mean PARM = 2207 [gkg]

-400 -300 -200 -100 000 100 200

h-values

46L

66L

36L

65L

35L

56L

19L

32L

45L

70L

16L

44L

9L

34L

Labo

rato

ries

Mandels h statistics(Sludge 2 - TOC)

Sludge 2-TOC

Unit gkg

Mandels k statistics(Soil 4 - TOC)Mandels h statistics(Soil 4 - TOC)

Sample Soil 4 Soil 4 - TOC -- Mean PARM = 1641 [gkg]

Element TOC

General calcparmT1= 102171E+03T2= 168700E+04T3= 62T4= 338T5= 94040E+00

n= variabelp= 12

N-table= 5

Mandels statistics End ResultLAB 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

36L 147161 0470 3 -036 068 Fail 147161 04702 3 2 -16965L 155250 0591 4 -032 085 Fail 155250 05909 4 3 -08844L 157900 0115 6 -031 017 Fail 157900 01152 6 5 -06232L 159250 0359 4 -031 052 Fail 159250 03594 4 3 -0489L 160500 0315 6 -030 045 Fail 160500 03146 6 5 -03656L 164927 0113 6 -028 016 Fail 164927 01127 6 5 00835L 165000 0261 6 -028 038 Fail 165000 02608 6 5 00919L 166667 0505 6 -027 073 Fail 166667 05046 6 5 02645L 168850 0763 6 -026 110 Fail 168850 07628 6 5 04816L 173333 0516 6 -024 074 Fail 173333 05164 6 5 09334L 174761 0346 6 -024 050 Fail 174761 03462 6 5 10730L 175333 0473 3 -024 068 Fail 175333 04726 3 2 11366L 189375 2035 4 -017 294 Fail - - 66L - - 25346L 227500 0500 4 000 072 - - 46L - - 63470L 1040400 - 1 360 Fail - - 70L - - 8763

Totgem 22841 0526 gkg 1-level 232 (176) 12 164078 (46L 66L70L) 12 11Totstd= 22541 0469 5-level 186 (152) 3

71RESULTS Mean = 1640777 gkg

Repeatability variance S2r = 018808Repeatability std Sr = 043368 --gt 264 r = 12143Between lab variance S2L = 054747Reproducibility var S2R = 073555Reproducibility std SR = 085764 --gt 523 R = 24014Remarks 3 Labs rejected (46L 66L70L)

000 050 100 150 200 250 300

k-values

36L

65L

44L

32L

9L

56L

35L

19L

45L

16L

34L

30L

66L

46L

70L

Mandels k statistics(Soil 4 - TOC)

-100 00 100 200 300 400 500 600 700 800 900

Deviation from Mean

36L

65L

44L

32L

9L

56L

35L

19L

45L

16L

34L

30L

66L

46L

70L

Labo

rato

ries

Soil 4 - TOC -- Mean PARM = 1641 [gkg]

-100 000 100 200 300 400

h-values

36L

44L

9L

35L

45L

34L

66L

70L

Labo

rato

ries

Mandels h statistics(Soil 4 - TOC)

Soil 4-TOC

Unit gkg

Mandels k statistics(Soil 5 - TOC)Mandels h statistics(Soil 5 - TOC)

Sample Soil 5 Soil 5 - TOC -- Mean PARM = 2102 [gkg]

Element TOC

General calcparmT1= 113661E+03T2= 240201E+04T3= 54T4= 300T5= 51756E+01

n= variabelp= 10

N-table= 5

Mandels statistics End ResultLAB 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

44L 164383 14708 6 -036 325 Fail - - 44L - - -45865L 181250 0830 4 -033 018 Fail 181250 08302 4 3 -29045L 200317 1116 6 -029 025 Fail 200317 11163 6 5 -09935L 201833 1828 6 -029 040 Fail 201833 18280 6 5 -08432L 203250 0585 4 -029 013 Fail 203250 05852 4 3 -07016L 209000 0959 6 -028 021 Fail 209000 09592 6 5 -0129L 211667 0427 6 -027 009 Fail 211667 04274 6 5 01556L 214030 0887 6 -027 020 Fail 214030 08868 6 5 03819L 216000 0795 6 -026 018 Fail 216000 07950 6 5 05834L 226009 1308 6 -024 029 Fail 226009 13076 6 5 15836L 228783 4310 3 -024 095 Fail - - 36L - - 18666L 238750 1234 4 -022 027 Fail 238750 12340 4 3 28570L 2213900 - 1 333 Fail - - 70L - - 20037

Totgem 36224 2416 gkg 1-level 227 (175) 10 210211 (36L44L 70L) 10 9Totstd= 55669 4003 5-level 184 (151) 3

64RESULTS Mean = 2102106 gkg

Repeatability variance S2r = 117627Repeatability std Sr = 108456 --gt 516 r = 30368Between lab variance S2L = 176699Reproducibility var S2R = 294326Reproducibility std SR = 171559 --gt 816 R = 48037Remarks 3 Labs rejected (36L44L 70L)

000 050 100 150 200 250 300 350

k-values

44L

65L

45L

35L

32L

16L

9L

56L

19L

34L

36L

66L

70L

Mandels k statistics(Soil 5 - TOC)

-500 00 500 1000 1500 2000 2500

Deviation from Mean

44L

65L

45L

35L

32L

16L

9L

56L

19L

34L

36L

66L

70L

Labo

rato

ries

Soil 5 - TOC -- Mean PARM = 2102 [gkg]

-100 000 100 200 300 400

h-values

44L

65L

45L

35L

32L

16L

9L

56L

19L

34L

36L

66L

70L

Labo

rato

ries

Mandels h statistics(Soil 5 - TOC)

Soil 5-TOC

17

Annex 4

Raw data submitted

Sample Compost 1 Sample Compost 2 Sample Sewage Sludge 1Element TOC [gkg] Element TOC [gkg] Element TOC [gkg]

LAB PARM LAB PARM LAB PARM30L 2600 19L 1691 19L 286730L 2580 19L 1634 19L 281430L 2560 19L 1619 19L 276934L 2969 19L 1604 19L 272034L 2936 19L 1499 19L 268834L 2958 19L 1414 19L 266234L 2994 34L 1527 34L 315234L 3199 34L 1622 34L 314934L 3024 34L 1519 34L 343035L 2306 34L 1753 34L 336535L 2300 34L 1636 34L 304235L 2298 34L 1874 34L 298335L 2296 35L 1506 35L 270735L 2291 35L 1312 35L 270335L 2259 35L 1294 35L 268836L 2546 35L 1279 35L 267436L 2527 35L 1191 35L 263136L 2470 35L 1177 35L 262644L 2583 36L 1418 36L 271344L 2581 36L 1408 36L 266544L 2578 36L 1320 36L 261444L 2539 44L 1719 44L 292044L 2528 44L 1664 44L 291644L 2525 44L 1654 44L 291245L 2658 44L 1637 44L 290045L 2600 44L 1624 44L 289645L 2546 44L 1620 44L 289345L 2461 45L 1428 45L 297645L 2409 45L 1325 45L 295245L 2350 45L 1323 45L 288546L 2460 45L 1321 45L 286646L 2400 45L 1309 45L 284046L 2370 45L 1253 45L 278746L 2350 46L 1580 46L 233056L 2436 46L 1550 46L 233056L 2435 46L 1170 46L 230056L 2405 46L 1120 46L 229056L 2397 56L 1642 56L 270256L 2375 56L 1626 56L 270156L 2358 56L 1622 56L 269465L 2587 56L 1571 56L 269365L 2542 56L 1561 56L 268465L 2483 56L 1545 56L 268066L 2454 65L 1933 65L 264166L 2429 65L 1838 65L 260966L 2365 65L 1693 65L 260766L 2262 65L 1562 65L 260569L 2730 66L 1561 66L 270169L 2250 66L 1545 66L 267469L 1440 66L 1420 66L 261969L 1420 66L 1417 66L 251470L 2435 69L 2700 69L 2639L 2594 69L 2660 69L 2409L 2570 69L 2170 69L 2199L 2565 69L 2130 69L 2109L 2563 70L 1414 70L 28159L 2562 9L 1644 9L 28579L 2555 9L 1641 9L 2856

32L 2290 9L 1602 9L 285532L 2390 9L 1589 9L 285532L 2510 9L 1526 9L 285332L 2470 9L 1492 9L 284616L 2380 32L 1470 32L 265016L 2530 32L 1520 32L 271016L 2400 32L 1540 32L 271016L 2500 32L 1600 32L 280016L 2420 16L 1400 16L 284016L 2410 16L 1440 16L 2840

16L 1470 16L 286016L 1510 16L 287016L 1360 16L 287016L 1390 16L 2880

Sample Sewage Sludge 2 Sample Soil 4 Sample Soil 5Element TOC [gkg] Element TOC [gkg] Element TOC [gkg]

LAB PARM LAB PARM LAB PARM19L 2308 19L 1720 19L 225019L 2303 19L 1700 19L 223019L 2239 19L 1690 19L 221019L 2204 19L 1670 19L 211019L 2192 19L 1640 19L 210019L 2096 19L 1580 19L 206034L 2631 30L 1790 34L 244334L 2471 30L 1770 34L 233434L 2977 30L 1700 34L 231534L 2785 34L 1740 34L 222134L 2780 34L 1692 34L 217634L 2668 34L 1727 34L 207335L 2179 34L 1767 35L 233035L 2160 34L 1777 35L 208035L 2158 34L 1783 35L 201035L 2132 35L 1700 35L 198035L 2119 35L 1650 35L 193035L 2094 35L 1650 35L 178036L 2096 35L 1640 36L 254036L 2069 35L 1630 36L 253436L 2052 35L 1630 36L 179044L 2325 36L 1500 44L 302144L 2309 36L 1497 44L 298244L 2307 36L 1417 44L 295644L 2305 44L 1594 44L 30744L 2287 44L 1587 44L 30044L 2283 44L 1584 44L 29745L 2331 44L 1574 45L 214945L 2327 44L 1573 45L 209245L 2308 44L 1562 45L 203345L 2287 45L 1827 45L 197145L 2234 45L 1709 45L 193345L 2113 45L 1666 45L 184146L 190 45L 1665 56L 223746L 180 45L 1664 56L 222246L 180 45L 1600 56L 220346L 180 46L 2300 56L 206956L 2204 46L 2300 56L 206856L 2197 46L 2300 56L 204456L 2193 46L 2200 65L 192056L 2185 56L 1668 65L 182056L 2183 56L 1654 65L 179056L 2167 56L 1653 65L 172065L 2136 56L 1643 66L 254365L 2091 56L 1639 66L 242465L 2065 56L 1638 66L 232165L 2047 65L 1630 66L 226266L 2105 65L 1560 70L 2213966L 2022 65L 1530 9L 218066L 2009 65L 1490 9L 214066L 1983 66L 2179 9L 213070L 2272 66L 1900 9L 21109L 2385 66L 1762 9L 20709L 2377 66L 1734 9L 20709L 2375 70L 10404 32L 20509L 2359 9L 1640 32L 21009L 2356 9L 1640 32L 20209L 2354 9L 1610 32L 1960

32L 2240 9L 1590 16L 210032L 2260 9L 1590 16L 220032L 2200 9L 1560 16L 220032L 2270 32L 1640 16L 206016L 2300 32L 1600 16L 197016L 2310 32L 1560 16L 201016L 2350 32L 157016L 2260 16L 170016L 2290 16L 180016L 2240 16L 1700

16L 180016L 170016L 1700

European Commission EUR 23012 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on total organic carbon Author(s) E Sobiecka H van der Sloot K Andersen B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 50 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07412-7 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 total organic carbon (TOC) in soils sludge and treated bio-waste 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

-23012-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

16

Annex 3

Statistical calculations

Unit gkg

Mandels k statistics(Compost 1 - TOC)Mandels h statistics(Compost 1 - TOC)

Sample Compost 1 Compost 1 - TOC -- Mean PARM = 2463 [gkg]

Element TOC

General calcparmT1= 142643E+04T2= 351264E+06T3= 58T4= 292T5= 16501E+03

n= variabelp= 13

N-table= 5

Mandels statistics End ResultLAB 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

69L 1960000 64265 4 -235 352 Fail - - 69L - - -502735L 2291667 1674 6 -081 009 2291667 16741 6 5 -171066L 2377425 8552 4 -041 047 2377425 85518 4 3 -85346L 2395000 4796 4 -033 026 2395000 47958 4 3 -67756L 2401227 3133 6 -030 017 2401227 31330 6 5 -61432L 2415000 9713 4 -024 053 2415000 97125 4 3 -47770L 2435100 - 1 -014 2435100 - 1 -27616L 2440000 6033 6 -012 033 2440000 60332 6 5 -22745L 2503800 11759 6 018 064 2503800 117589 6 5 41136L 2514416 3994 3 023 022 2514416 39937 3 2 51765L 2537333 5216 3 033 029 2537333 52157 3 2 74744L 2555667 2783 6 042 015 2555667 27826 6 5 9309L 2568167 1356 6 048 007 2568167 13556 6 5 105530L 2580000 2000 3 053 011 2580000 20000 3 2 117334L 3013269 9580 6 255 053 Fail - - 34L - - 5506

Totgem 246587 9632 gkg 1-level 232 (176) 13 2462677 (34L 69L) 13 12Totstd= 21507 16070 5-level 186 (152) 2

68RESULTS Mean = 24626770 gkg

Repeatability variance S2r = 3666797Repeatability std Sr = 605541 --gt 246 r = 169551Between lab variance S2L = 7715586Reproducibility var S2R = 11382383Reproducibility std SR = 1066882 --gt 433 R = 298727Remarks 2 Labs rejected (34L 69L)

000 050 100 150 200 250 300 350 400

k-values

69L

35L

66L

46L

56L

32L

70L

16L

45L

36L

65L

44L

9L

30L

34L

Mandels k statistics(Compost 1 - TOC)

-600 -400 -200 00 200 400 600

Deviation from Mean

69L

35L

66L

46L

56L

32L

70L

16L

45L

36L

65L

44L

9L

30L

34L

Labo

rato

ries

Compost 1 - TOC -- Mean PARM = 2463 [gkg]

-300 -200 -100 000 100 200 300

h-values

69L

66L

56L

70L

45L

65L

9L

34L

Labo

rato

ries

Mandels h statistics(Compost 1 - TOC)

Compost 1-TOC

Unit gkg

Mandels k statistics(Compost 2 - TOC)Mandels h statistics(Compost 2 - TOC)

Sample Compost 2 Compost 2 - TOC -- Mean PARM = 1542 [gkg]

Element TOC

General calcparmT1= 994897E+03T2= 155556E+06T3= 64T4= 346T5= 41738E+03

n= variabelp= 13

N-table= 5

Mandels statistics End ResultLAB 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

45L 1326733 5665 6 -100 042 Fail 1326733 56646 6 5 -215046L 1355000 24365 4 -089 181 Fail - - 46L - - -186736L 1381949 5407 3 -078 040 Fail 1381949 54070 3 2 -159870L 1414120 - 1 -066 Fail 1414120 - 1 -127616L 1428333 5565 6 -061 041 1428333 55648 6 5 -113466L 1485550 7805 4 -039 058 1485550 78047 4 3 -56232L 1532500 5377 4 -021 040 1532500 53774 4 3 -09219L 1576833 10138 6 -004 075 1576833 101381 6 5 3519L 1582333 6166 6 -002 046 1582333 61659 6 5 40656L 1594432 4046 6 003 030 1594432 40463 6 5 52744L 1653000 3651 6 025 027 1653000 36508 6 5 111334L 1655127 13717 6 026 102 1655127 137168 6 5 113434L 1655127 13717 6 026 102 1655127 137168 6 5 113465L 1756500 16295 4 065 121 Fail 1756500 162949 4 3 214869L 2415000 30687 4 316 228 Fail - - 69L - - 8733

Totgem 158750 10900 gkg 1-level 232 (176) 13 1541734 (46L 69L) 13 12Totstd= 26187 8164 5-level 186 (152) 2

72RESULTS Mean = 15417337 gkg

Repeatability variance S2r = 8183950Repeatability std Sr = 904652 --gt 587 r = 253303Between lab variance S2L = 13631046Reproducibility var S2R = 21814995Reproducibility std SR = 1476990 --gt 958 R = 413557Remarks 2 Labs rejected (46L 69L)

000 050 100 150 200 250

k-values

45L

46L

36L

70L

16L

66L

32L

19L

9L

56L

44L

34L

34L

65L

69L

Mandels k statistics(Compost 2 - TOC)

-400 -200 00 200 400 600 800 1000

Deviation from Mean

45L

46L

36L

70L

16L

66L

32L

19L

9L

56L

44L

34L

34L

65L

69L

Labo

rato

ries

Compost 2 - TOC -- Mean PARM = 1542 [gkg]

-100 000 100 200 300 400

h-values

45L

36L

16L

32L

9L

44L

34L

69L

Labo

rato

ries

Mandels h statistics(Compost 2 - TOC)

Compost 2-TOC

Unit gkg

Mandels k statistics(Sludge 1 - TOC)Mandels h statistics(Sludge 1 - TOC)

Sample Sludge 1 Sludge 1 - TOC -- Mean PARM = 2721 [gkg]

Element TOC

General calcparmT1= 169626E+04T2= 465445E+06T3= 62T4= 326T5= 10312E+03

n= variabelp= 13

N-table= 5

Mandels statistics End ResultLAB 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

69L 233000 2362 4 -347 037 Fail - - 69L - - -2488046L 2312500 2062 4 -040 032 Fail 2312500 20616 4 3 -408565L 2615500 1708 4 004 026 2615500 17078 4 3 -105566L 2627200 8268 4 006 128 2627200 82678 4 3 -93836L 2664041 4976 3 011 077 2664041 49758 3 2 -56935L 2671500 3533 6 013 055 2671500 35331 6 5 -49556L 2692298 0874 6 016 014 Fail 2692298 08738 6 5 -28732L 2717500 6185 4 019 096 Fail 2717500 61847 4 3 -03519L 2753333 7819 6 025 121 Fail 2753333 78189 6 5 32470L 2814600 - 1 034 Fail 2814600 - 1 9369L 2853667 0398 6 039 006 Fail 2853667 03983 6 5 132716L 2860000 1673 6 040 026 Fail 2860000 16733 6 5 139045L 2884433 7033 6 044 109 Fail 2884433 70331 6 5 163544L 2906167 1129 6 047 017 Fail 2906167 11286 6 5 185234L 3186874 17674 6 089 274 Fail - - 34L - - 4659

Totgem 258617 4692 gkg 1-level 232 (176) 13 2720980 (34L 69L) 13 12Totstd= 67800 4610 5-level 186 (152) 2

72RESULTS Mean = 27209799 gkg

Repeatability variance S2r = 2104538Repeatability std Sr = 458752 --gt 169 r = 128451Between lab variance S2L = 23618387Reproducibility var S2R = 25722925Reproducibility std SR = 1603837 --gt 589 R = 449074Remarks 2 Labs rejected (34L 69L)

000 050 100 150 200 250 300

k-values

69L

46L

65L

66L

36L

35L

56L

32L

19L

70L

9L

16L

45L

44L

34L

Mandels k statistics(Sludge 1 - TOC)

-2500 -2000 -1500 -1000 -500 00 500

Deviation from Mean

69L

46L

65L

66L

36L

35L

56L

32L

19L

70L

9L

16L

45L

44L

34L

Labo

rato

ries

Sludge 1 - TOC -- Mean PARM = 2721 [gkg]

-400 -300 -200 -100 000 100

h-values

69L

65L

36L

56L

19L

9L

45L

34L

Labo

rato

ries

Mandels h statistics(Sludge 1 - TOC)

Sludge 1-TOC

68 Unit gkg

Mandels k statistics(Sludge 2 - TOC)Mandels h statistics(Sludge 2 - TOC)

Sample Sludge 2 Sludge 2 - TOC -- Mean PARM = 2207 [gkg]

Element TOC

General calcparmT1= 128601E+04T2= 285689E+06T3= 58T4= 310T5= 97826E+02

n= variabelp= 12

N-table= 5

Mandels statistics End ResultLAB 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

46L 182500 0500 4 -333 008 Fail - - 46L - - -2024466L 2029475 5267 4 -012 084 2029475 52674 4 3 -177436L 2072609 2222 3 -005 035 2072609 22222 3 2 -134365L 2084750 3865 4 -002 062 2084750 38647 4 3 -122135L 2140333 3119 6 007 050 2140333 31194 6 5 -66556L 2188021 1282 6 015 020 2188021 12822 6 5 -18819L 2223667 7916 6 022 126 Fail 2223667 79157 6 5 16832L 2242500 3096 4 025 049 Fail 2242500 30957 4 3 35645L 2266600 8322 6 029 132 Fail 2266600 83216 6 5 59770L 2272460 - 1 030 Fail 2272460 - 1 65616L 2291667 3869 6 033 062 Fail 2291667 38687 6 5 84844L 2302667 1546 6 035 025 Fail 2302667 15462 6 5 9589L 2367667 1296 6 047 021 Fail 2367667 12956 6 5 160834L 2718591 17124 6 108 273 Fail - - 34L - - 5117

Totgem 209882 4571 gkg 1-level 230 (176) 12 2206868 (34L 46L) 12 11Totstd= 57628 4485 5-level 185 (151) 2

68RESULTS Mean = 22068679 gkg

Repeatability variance S2r = 2126659Repeatability std Sr = 461157 --gt 209 r = 129124Between lab variance S2L = 9960432Reproducibility var S2R = 12087091Reproducibility std SR = 1099413 --gt 498 R = 307836Remarks 2 Labs rejected (34L 46L)

000 050 100 150 200 250 300

k-values

46L

66L

36L

65L

35L

56L

19L

32L

45L

70L

16L

44L

9L

34L

Mandels k statistics(Sludge 2 - TOC)

-2500 -2000 -1500 -1000 -500 00 500 1000

Deviation from Mean

46L

66L

36L

65L

35L

56L

19L

32L

45L

70L

16L

44L

9L

34L

Labo

rato

ries

Sludge 2 - TOC -- Mean PARM = 2207 [gkg]

-400 -300 -200 -100 000 100 200

h-values

46L

66L

36L

65L

35L

56L

19L

32L

45L

70L

16L

44L

9L

34L

Labo

rato

ries

Mandels h statistics(Sludge 2 - TOC)

Sludge 2-TOC

Unit gkg

Mandels k statistics(Soil 4 - TOC)Mandels h statistics(Soil 4 - TOC)

Sample Soil 4 Soil 4 - TOC -- Mean PARM = 1641 [gkg]

Element TOC

General calcparmT1= 102171E+03T2= 168700E+04T3= 62T4= 338T5= 94040E+00

n= variabelp= 12

N-table= 5

Mandels statistics End ResultLAB 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

36L 147161 0470 3 -036 068 Fail 147161 04702 3 2 -16965L 155250 0591 4 -032 085 Fail 155250 05909 4 3 -08844L 157900 0115 6 -031 017 Fail 157900 01152 6 5 -06232L 159250 0359 4 -031 052 Fail 159250 03594 4 3 -0489L 160500 0315 6 -030 045 Fail 160500 03146 6 5 -03656L 164927 0113 6 -028 016 Fail 164927 01127 6 5 00835L 165000 0261 6 -028 038 Fail 165000 02608 6 5 00919L 166667 0505 6 -027 073 Fail 166667 05046 6 5 02645L 168850 0763 6 -026 110 Fail 168850 07628 6 5 04816L 173333 0516 6 -024 074 Fail 173333 05164 6 5 09334L 174761 0346 6 -024 050 Fail 174761 03462 6 5 10730L 175333 0473 3 -024 068 Fail 175333 04726 3 2 11366L 189375 2035 4 -017 294 Fail - - 66L - - 25346L 227500 0500 4 000 072 - - 46L - - 63470L 1040400 - 1 360 Fail - - 70L - - 8763

Totgem 22841 0526 gkg 1-level 232 (176) 12 164078 (46L 66L70L) 12 11Totstd= 22541 0469 5-level 186 (152) 3

71RESULTS Mean = 1640777 gkg

Repeatability variance S2r = 018808Repeatability std Sr = 043368 --gt 264 r = 12143Between lab variance S2L = 054747Reproducibility var S2R = 073555Reproducibility std SR = 085764 --gt 523 R = 24014Remarks 3 Labs rejected (46L 66L70L)

000 050 100 150 200 250 300

k-values

36L

65L

44L

32L

9L

56L

35L

19L

45L

16L

34L

30L

66L

46L

70L

Mandels k statistics(Soil 4 - TOC)

-100 00 100 200 300 400 500 600 700 800 900

Deviation from Mean

36L

65L

44L

32L

9L

56L

35L

19L

45L

16L

34L

30L

66L

46L

70L

Labo

rato

ries

Soil 4 - TOC -- Mean PARM = 1641 [gkg]

-100 000 100 200 300 400

h-values

36L

44L

9L

35L

45L

34L

66L

70L

Labo

rato

ries

Mandels h statistics(Soil 4 - TOC)

Soil 4-TOC

Unit gkg

Mandels k statistics(Soil 5 - TOC)Mandels h statistics(Soil 5 - TOC)

Sample Soil 5 Soil 5 - TOC -- Mean PARM = 2102 [gkg]

Element TOC

General calcparmT1= 113661E+03T2= 240201E+04T3= 54T4= 300T5= 51756E+01

n= variabelp= 10

N-table= 5

Mandels statistics End ResultLAB 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

44L 164383 14708 6 -036 325 Fail - - 44L - - -45865L 181250 0830 4 -033 018 Fail 181250 08302 4 3 -29045L 200317 1116 6 -029 025 Fail 200317 11163 6 5 -09935L 201833 1828 6 -029 040 Fail 201833 18280 6 5 -08432L 203250 0585 4 -029 013 Fail 203250 05852 4 3 -07016L 209000 0959 6 -028 021 Fail 209000 09592 6 5 -0129L 211667 0427 6 -027 009 Fail 211667 04274 6 5 01556L 214030 0887 6 -027 020 Fail 214030 08868 6 5 03819L 216000 0795 6 -026 018 Fail 216000 07950 6 5 05834L 226009 1308 6 -024 029 Fail 226009 13076 6 5 15836L 228783 4310 3 -024 095 Fail - - 36L - - 18666L 238750 1234 4 -022 027 Fail 238750 12340 4 3 28570L 2213900 - 1 333 Fail - - 70L - - 20037

Totgem 36224 2416 gkg 1-level 227 (175) 10 210211 (36L44L 70L) 10 9Totstd= 55669 4003 5-level 184 (151) 3

64RESULTS Mean = 2102106 gkg

Repeatability variance S2r = 117627Repeatability std Sr = 108456 --gt 516 r = 30368Between lab variance S2L = 176699Reproducibility var S2R = 294326Reproducibility std SR = 171559 --gt 816 R = 48037Remarks 3 Labs rejected (36L44L 70L)

000 050 100 150 200 250 300 350

k-values

44L

65L

45L

35L

32L

16L

9L

56L

19L

34L

36L

66L

70L

Mandels k statistics(Soil 5 - TOC)

-500 00 500 1000 1500 2000 2500

Deviation from Mean

44L

65L

45L

35L

32L

16L

9L

56L

19L

34L

36L

66L

70L

Labo

rato

ries

Soil 5 - TOC -- Mean PARM = 2102 [gkg]

-100 000 100 200 300 400

h-values

44L

65L

45L

35L

32L

16L

9L

56L

19L

34L

36L

66L

70L

Labo

rato

ries

Mandels h statistics(Soil 5 - TOC)

Soil 5-TOC

17

Annex 4

Raw data submitted

Sample Compost 1 Sample Compost 2 Sample Sewage Sludge 1Element TOC [gkg] Element TOC [gkg] Element TOC [gkg]

LAB PARM LAB PARM LAB PARM30L 2600 19L 1691 19L 286730L 2580 19L 1634 19L 281430L 2560 19L 1619 19L 276934L 2969 19L 1604 19L 272034L 2936 19L 1499 19L 268834L 2958 19L 1414 19L 266234L 2994 34L 1527 34L 315234L 3199 34L 1622 34L 314934L 3024 34L 1519 34L 343035L 2306 34L 1753 34L 336535L 2300 34L 1636 34L 304235L 2298 34L 1874 34L 298335L 2296 35L 1506 35L 270735L 2291 35L 1312 35L 270335L 2259 35L 1294 35L 268836L 2546 35L 1279 35L 267436L 2527 35L 1191 35L 263136L 2470 35L 1177 35L 262644L 2583 36L 1418 36L 271344L 2581 36L 1408 36L 266544L 2578 36L 1320 36L 261444L 2539 44L 1719 44L 292044L 2528 44L 1664 44L 291644L 2525 44L 1654 44L 291245L 2658 44L 1637 44L 290045L 2600 44L 1624 44L 289645L 2546 44L 1620 44L 289345L 2461 45L 1428 45L 297645L 2409 45L 1325 45L 295245L 2350 45L 1323 45L 288546L 2460 45L 1321 45L 286646L 2400 45L 1309 45L 284046L 2370 45L 1253 45L 278746L 2350 46L 1580 46L 233056L 2436 46L 1550 46L 233056L 2435 46L 1170 46L 230056L 2405 46L 1120 46L 229056L 2397 56L 1642 56L 270256L 2375 56L 1626 56L 270156L 2358 56L 1622 56L 269465L 2587 56L 1571 56L 269365L 2542 56L 1561 56L 268465L 2483 56L 1545 56L 268066L 2454 65L 1933 65L 264166L 2429 65L 1838 65L 260966L 2365 65L 1693 65L 260766L 2262 65L 1562 65L 260569L 2730 66L 1561 66L 270169L 2250 66L 1545 66L 267469L 1440 66L 1420 66L 261969L 1420 66L 1417 66L 251470L 2435 69L 2700 69L 2639L 2594 69L 2660 69L 2409L 2570 69L 2170 69L 2199L 2565 69L 2130 69L 2109L 2563 70L 1414 70L 28159L 2562 9L 1644 9L 28579L 2555 9L 1641 9L 2856

32L 2290 9L 1602 9L 285532L 2390 9L 1589 9L 285532L 2510 9L 1526 9L 285332L 2470 9L 1492 9L 284616L 2380 32L 1470 32L 265016L 2530 32L 1520 32L 271016L 2400 32L 1540 32L 271016L 2500 32L 1600 32L 280016L 2420 16L 1400 16L 284016L 2410 16L 1440 16L 2840

16L 1470 16L 286016L 1510 16L 287016L 1360 16L 287016L 1390 16L 2880

Sample Sewage Sludge 2 Sample Soil 4 Sample Soil 5Element TOC [gkg] Element TOC [gkg] Element TOC [gkg]

LAB PARM LAB PARM LAB PARM19L 2308 19L 1720 19L 225019L 2303 19L 1700 19L 223019L 2239 19L 1690 19L 221019L 2204 19L 1670 19L 211019L 2192 19L 1640 19L 210019L 2096 19L 1580 19L 206034L 2631 30L 1790 34L 244334L 2471 30L 1770 34L 233434L 2977 30L 1700 34L 231534L 2785 34L 1740 34L 222134L 2780 34L 1692 34L 217634L 2668 34L 1727 34L 207335L 2179 34L 1767 35L 233035L 2160 34L 1777 35L 208035L 2158 34L 1783 35L 201035L 2132 35L 1700 35L 198035L 2119 35L 1650 35L 193035L 2094 35L 1650 35L 178036L 2096 35L 1640 36L 254036L 2069 35L 1630 36L 253436L 2052 35L 1630 36L 179044L 2325 36L 1500 44L 302144L 2309 36L 1497 44L 298244L 2307 36L 1417 44L 295644L 2305 44L 1594 44L 30744L 2287 44L 1587 44L 30044L 2283 44L 1584 44L 29745L 2331 44L 1574 45L 214945L 2327 44L 1573 45L 209245L 2308 44L 1562 45L 203345L 2287 45L 1827 45L 197145L 2234 45L 1709 45L 193345L 2113 45L 1666 45L 184146L 190 45L 1665 56L 223746L 180 45L 1664 56L 222246L 180 45L 1600 56L 220346L 180 46L 2300 56L 206956L 2204 46L 2300 56L 206856L 2197 46L 2300 56L 204456L 2193 46L 2200 65L 192056L 2185 56L 1668 65L 182056L 2183 56L 1654 65L 179056L 2167 56L 1653 65L 172065L 2136 56L 1643 66L 254365L 2091 56L 1639 66L 242465L 2065 56L 1638 66L 232165L 2047 65L 1630 66L 226266L 2105 65L 1560 70L 2213966L 2022 65L 1530 9L 218066L 2009 65L 1490 9L 214066L 1983 66L 2179 9L 213070L 2272 66L 1900 9L 21109L 2385 66L 1762 9L 20709L 2377 66L 1734 9L 20709L 2375 70L 10404 32L 20509L 2359 9L 1640 32L 21009L 2356 9L 1640 32L 20209L 2354 9L 1610 32L 1960

32L 2240 9L 1590 16L 210032L 2260 9L 1590 16L 220032L 2200 9L 1560 16L 220032L 2270 32L 1640 16L 206016L 2300 32L 1600 16L 197016L 2310 32L 1560 16L 201016L 2350 32L 157016L 2260 16L 170016L 2290 16L 180016L 2240 16L 1700

16L 180016L 170016L 1700

European Commission EUR 23012 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on total organic carbon Author(s) E Sobiecka H van der Sloot K Andersen B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 50 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07412-7 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 total organic carbon (TOC) in soils sludge and treated bio-waste 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

-23012-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

16

Annex 3

Statistical calculations

Unit gkg

Mandels k statistics(Compost 1 - TOC)Mandels h statistics(Compost 1 - TOC)

Sample Compost 1 Compost 1 - TOC -- Mean PARM = 2463 [gkg]

Element TOC

General calcparmT1= 142643E+04T2= 351264E+06T3= 58T4= 292T5= 16501E+03

n= variabelp= 13

N-table= 5

Mandels statistics End ResultLAB 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

69L 1960000 64265 4 -235 352 Fail - - 69L - - -502735L 2291667 1674 6 -081 009 2291667 16741 6 5 -171066L 2377425 8552 4 -041 047 2377425 85518 4 3 -85346L 2395000 4796 4 -033 026 2395000 47958 4 3 -67756L 2401227 3133 6 -030 017 2401227 31330 6 5 -61432L 2415000 9713 4 -024 053 2415000 97125 4 3 -47770L 2435100 - 1 -014 2435100 - 1 -27616L 2440000 6033 6 -012 033 2440000 60332 6 5 -22745L 2503800 11759 6 018 064 2503800 117589 6 5 41136L 2514416 3994 3 023 022 2514416 39937 3 2 51765L 2537333 5216 3 033 029 2537333 52157 3 2 74744L 2555667 2783 6 042 015 2555667 27826 6 5 9309L 2568167 1356 6 048 007 2568167 13556 6 5 105530L 2580000 2000 3 053 011 2580000 20000 3 2 117334L 3013269 9580 6 255 053 Fail - - 34L - - 5506

Totgem 246587 9632 gkg 1-level 232 (176) 13 2462677 (34L 69L) 13 12Totstd= 21507 16070 5-level 186 (152) 2

68RESULTS Mean = 24626770 gkg

Repeatability variance S2r = 3666797Repeatability std Sr = 605541 --gt 246 r = 169551Between lab variance S2L = 7715586Reproducibility var S2R = 11382383Reproducibility std SR = 1066882 --gt 433 R = 298727Remarks 2 Labs rejected (34L 69L)

000 050 100 150 200 250 300 350 400

k-values

69L

35L

66L

46L

56L

32L

70L

16L

45L

36L

65L

44L

9L

30L

34L

Mandels k statistics(Compost 1 - TOC)

-600 -400 -200 00 200 400 600

Deviation from Mean

69L

35L

66L

46L

56L

32L

70L

16L

45L

36L

65L

44L

9L

30L

34L

Labo

rato

ries

Compost 1 - TOC -- Mean PARM = 2463 [gkg]

-300 -200 -100 000 100 200 300

h-values

69L

66L

56L

70L

45L

65L

9L

34L

Labo

rato

ries

Mandels h statistics(Compost 1 - TOC)

Compost 1-TOC

Unit gkg

Mandels k statistics(Compost 2 - TOC)Mandels h statistics(Compost 2 - TOC)

Sample Compost 2 Compost 2 - TOC -- Mean PARM = 1542 [gkg]

Element TOC

General calcparmT1= 994897E+03T2= 155556E+06T3= 64T4= 346T5= 41738E+03

n= variabelp= 13

N-table= 5

Mandels statistics End ResultLAB 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

45L 1326733 5665 6 -100 042 Fail 1326733 56646 6 5 -215046L 1355000 24365 4 -089 181 Fail - - 46L - - -186736L 1381949 5407 3 -078 040 Fail 1381949 54070 3 2 -159870L 1414120 - 1 -066 Fail 1414120 - 1 -127616L 1428333 5565 6 -061 041 1428333 55648 6 5 -113466L 1485550 7805 4 -039 058 1485550 78047 4 3 -56232L 1532500 5377 4 -021 040 1532500 53774 4 3 -09219L 1576833 10138 6 -004 075 1576833 101381 6 5 3519L 1582333 6166 6 -002 046 1582333 61659 6 5 40656L 1594432 4046 6 003 030 1594432 40463 6 5 52744L 1653000 3651 6 025 027 1653000 36508 6 5 111334L 1655127 13717 6 026 102 1655127 137168 6 5 113434L 1655127 13717 6 026 102 1655127 137168 6 5 113465L 1756500 16295 4 065 121 Fail 1756500 162949 4 3 214869L 2415000 30687 4 316 228 Fail - - 69L - - 8733

Totgem 158750 10900 gkg 1-level 232 (176) 13 1541734 (46L 69L) 13 12Totstd= 26187 8164 5-level 186 (152) 2

72RESULTS Mean = 15417337 gkg

Repeatability variance S2r = 8183950Repeatability std Sr = 904652 --gt 587 r = 253303Between lab variance S2L = 13631046Reproducibility var S2R = 21814995Reproducibility std SR = 1476990 --gt 958 R = 413557Remarks 2 Labs rejected (46L 69L)

000 050 100 150 200 250

k-values

45L

46L

36L

70L

16L

66L

32L

19L

9L

56L

44L

34L

34L

65L

69L

Mandels k statistics(Compost 2 - TOC)

-400 -200 00 200 400 600 800 1000

Deviation from Mean

45L

46L

36L

70L

16L

66L

32L

19L

9L

56L

44L

34L

34L

65L

69L

Labo

rato

ries

Compost 2 - TOC -- Mean PARM = 1542 [gkg]

-100 000 100 200 300 400

h-values

45L

36L

16L

32L

9L

44L

34L

69L

Labo

rato

ries

Mandels h statistics(Compost 2 - TOC)

Compost 2-TOC

Unit gkg

Mandels k statistics(Sludge 1 - TOC)Mandels h statistics(Sludge 1 - TOC)

Sample Sludge 1 Sludge 1 - TOC -- Mean PARM = 2721 [gkg]

Element TOC

General calcparmT1= 169626E+04T2= 465445E+06T3= 62T4= 326T5= 10312E+03

n= variabelp= 13

N-table= 5

Mandels statistics End ResultLAB 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

69L 233000 2362 4 -347 037 Fail - - 69L - - -2488046L 2312500 2062 4 -040 032 Fail 2312500 20616 4 3 -408565L 2615500 1708 4 004 026 2615500 17078 4 3 -105566L 2627200 8268 4 006 128 2627200 82678 4 3 -93836L 2664041 4976 3 011 077 2664041 49758 3 2 -56935L 2671500 3533 6 013 055 2671500 35331 6 5 -49556L 2692298 0874 6 016 014 Fail 2692298 08738 6 5 -28732L 2717500 6185 4 019 096 Fail 2717500 61847 4 3 -03519L 2753333 7819 6 025 121 Fail 2753333 78189 6 5 32470L 2814600 - 1 034 Fail 2814600 - 1 9369L 2853667 0398 6 039 006 Fail 2853667 03983 6 5 132716L 2860000 1673 6 040 026 Fail 2860000 16733 6 5 139045L 2884433 7033 6 044 109 Fail 2884433 70331 6 5 163544L 2906167 1129 6 047 017 Fail 2906167 11286 6 5 185234L 3186874 17674 6 089 274 Fail - - 34L - - 4659

Totgem 258617 4692 gkg 1-level 232 (176) 13 2720980 (34L 69L) 13 12Totstd= 67800 4610 5-level 186 (152) 2

72RESULTS Mean = 27209799 gkg

Repeatability variance S2r = 2104538Repeatability std Sr = 458752 --gt 169 r = 128451Between lab variance S2L = 23618387Reproducibility var S2R = 25722925Reproducibility std SR = 1603837 --gt 589 R = 449074Remarks 2 Labs rejected (34L 69L)

000 050 100 150 200 250 300

k-values

69L

46L

65L

66L

36L

35L

56L

32L

19L

70L

9L

16L

45L

44L

34L

Mandels k statistics(Sludge 1 - TOC)

-2500 -2000 -1500 -1000 -500 00 500

Deviation from Mean

69L

46L

65L

66L

36L

35L

56L

32L

19L

70L

9L

16L

45L

44L

34L

Labo

rato

ries

Sludge 1 - TOC -- Mean PARM = 2721 [gkg]

-400 -300 -200 -100 000 100

h-values

69L

65L

36L

56L

19L

9L

45L

34L

Labo

rato

ries

Mandels h statistics(Sludge 1 - TOC)

Sludge 1-TOC

68 Unit gkg

Mandels k statistics(Sludge 2 - TOC)Mandels h statistics(Sludge 2 - TOC)

Sample Sludge 2 Sludge 2 - TOC -- Mean PARM = 2207 [gkg]

Element TOC

General calcparmT1= 128601E+04T2= 285689E+06T3= 58T4= 310T5= 97826E+02

n= variabelp= 12

N-table= 5

Mandels statistics End ResultLAB 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

46L 182500 0500 4 -333 008 Fail - - 46L - - -2024466L 2029475 5267 4 -012 084 2029475 52674 4 3 -177436L 2072609 2222 3 -005 035 2072609 22222 3 2 -134365L 2084750 3865 4 -002 062 2084750 38647 4 3 -122135L 2140333 3119 6 007 050 2140333 31194 6 5 -66556L 2188021 1282 6 015 020 2188021 12822 6 5 -18819L 2223667 7916 6 022 126 Fail 2223667 79157 6 5 16832L 2242500 3096 4 025 049 Fail 2242500 30957 4 3 35645L 2266600 8322 6 029 132 Fail 2266600 83216 6 5 59770L 2272460 - 1 030 Fail 2272460 - 1 65616L 2291667 3869 6 033 062 Fail 2291667 38687 6 5 84844L 2302667 1546 6 035 025 Fail 2302667 15462 6 5 9589L 2367667 1296 6 047 021 Fail 2367667 12956 6 5 160834L 2718591 17124 6 108 273 Fail - - 34L - - 5117

Totgem 209882 4571 gkg 1-level 230 (176) 12 2206868 (34L 46L) 12 11Totstd= 57628 4485 5-level 185 (151) 2

68RESULTS Mean = 22068679 gkg

Repeatability variance S2r = 2126659Repeatability std Sr = 461157 --gt 209 r = 129124Between lab variance S2L = 9960432Reproducibility var S2R = 12087091Reproducibility std SR = 1099413 --gt 498 R = 307836Remarks 2 Labs rejected (34L 46L)

000 050 100 150 200 250 300

k-values

46L

66L

36L

65L

35L

56L

19L

32L

45L

70L

16L

44L

9L

34L

Mandels k statistics(Sludge 2 - TOC)

-2500 -2000 -1500 -1000 -500 00 500 1000

Deviation from Mean

46L

66L

36L

65L

35L

56L

19L

32L

45L

70L

16L

44L

9L

34L

Labo

rato

ries

Sludge 2 - TOC -- Mean PARM = 2207 [gkg]

-400 -300 -200 -100 000 100 200

h-values

46L

66L

36L

65L

35L

56L

19L

32L

45L

70L

16L

44L

9L

34L

Labo

rato

ries

Mandels h statistics(Sludge 2 - TOC)

Sludge 2-TOC

Unit gkg

Mandels k statistics(Soil 4 - TOC)Mandels h statistics(Soil 4 - TOC)

Sample Soil 4 Soil 4 - TOC -- Mean PARM = 1641 [gkg]

Element TOC

General calcparmT1= 102171E+03T2= 168700E+04T3= 62T4= 338T5= 94040E+00

n= variabelp= 12

N-table= 5

Mandels statistics End ResultLAB 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

36L 147161 0470 3 -036 068 Fail 147161 04702 3 2 -16965L 155250 0591 4 -032 085 Fail 155250 05909 4 3 -08844L 157900 0115 6 -031 017 Fail 157900 01152 6 5 -06232L 159250 0359 4 -031 052 Fail 159250 03594 4 3 -0489L 160500 0315 6 -030 045 Fail 160500 03146 6 5 -03656L 164927 0113 6 -028 016 Fail 164927 01127 6 5 00835L 165000 0261 6 -028 038 Fail 165000 02608 6 5 00919L 166667 0505 6 -027 073 Fail 166667 05046 6 5 02645L 168850 0763 6 -026 110 Fail 168850 07628 6 5 04816L 173333 0516 6 -024 074 Fail 173333 05164 6 5 09334L 174761 0346 6 -024 050 Fail 174761 03462 6 5 10730L 175333 0473 3 -024 068 Fail 175333 04726 3 2 11366L 189375 2035 4 -017 294 Fail - - 66L - - 25346L 227500 0500 4 000 072 - - 46L - - 63470L 1040400 - 1 360 Fail - - 70L - - 8763

Totgem 22841 0526 gkg 1-level 232 (176) 12 164078 (46L 66L70L) 12 11Totstd= 22541 0469 5-level 186 (152) 3

71RESULTS Mean = 1640777 gkg

Repeatability variance S2r = 018808Repeatability std Sr = 043368 --gt 264 r = 12143Between lab variance S2L = 054747Reproducibility var S2R = 073555Reproducibility std SR = 085764 --gt 523 R = 24014Remarks 3 Labs rejected (46L 66L70L)

000 050 100 150 200 250 300

k-values

36L

65L

44L

32L

9L

56L

35L

19L

45L

16L

34L

30L

66L

46L

70L

Mandels k statistics(Soil 4 - TOC)

-100 00 100 200 300 400 500 600 700 800 900

Deviation from Mean

36L

65L

44L

32L

9L

56L

35L

19L

45L

16L

34L

30L

66L

46L

70L

Labo

rato

ries

Soil 4 - TOC -- Mean PARM = 1641 [gkg]

-100 000 100 200 300 400

h-values

36L

44L

9L

35L

45L

34L

66L

70L

Labo

rato

ries

Mandels h statistics(Soil 4 - TOC)

Soil 4-TOC

Unit gkg

Mandels k statistics(Soil 5 - TOC)Mandels h statistics(Soil 5 - TOC)

Sample Soil 5 Soil 5 - TOC -- Mean PARM = 2102 [gkg]

Element TOC

General calcparmT1= 113661E+03T2= 240201E+04T3= 54T4= 300T5= 51756E+01

n= variabelp= 10

N-table= 5

Mandels statistics End ResultLAB 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

44L 164383 14708 6 -036 325 Fail - - 44L - - -45865L 181250 0830 4 -033 018 Fail 181250 08302 4 3 -29045L 200317 1116 6 -029 025 Fail 200317 11163 6 5 -09935L 201833 1828 6 -029 040 Fail 201833 18280 6 5 -08432L 203250 0585 4 -029 013 Fail 203250 05852 4 3 -07016L 209000 0959 6 -028 021 Fail 209000 09592 6 5 -0129L 211667 0427 6 -027 009 Fail 211667 04274 6 5 01556L 214030 0887 6 -027 020 Fail 214030 08868 6 5 03819L 216000 0795 6 -026 018 Fail 216000 07950 6 5 05834L 226009 1308 6 -024 029 Fail 226009 13076 6 5 15836L 228783 4310 3 -024 095 Fail - - 36L - - 18666L 238750 1234 4 -022 027 Fail 238750 12340 4 3 28570L 2213900 - 1 333 Fail - - 70L - - 20037

Totgem 36224 2416 gkg 1-level 227 (175) 10 210211 (36L44L 70L) 10 9Totstd= 55669 4003 5-level 184 (151) 3

64RESULTS Mean = 2102106 gkg

Repeatability variance S2r = 117627Repeatability std Sr = 108456 --gt 516 r = 30368Between lab variance S2L = 176699Reproducibility var S2R = 294326Reproducibility std SR = 171559 --gt 816 R = 48037Remarks 3 Labs rejected (36L44L 70L)

000 050 100 150 200 250 300 350

k-values

44L

65L

45L

35L

32L

16L

9L

56L

19L

34L

36L

66L

70L

Mandels k statistics(Soil 5 - TOC)

-500 00 500 1000 1500 2000 2500

Deviation from Mean

44L

65L

45L

35L

32L

16L

9L

56L

19L

34L

36L

66L

70L

Labo

rato

ries

Soil 5 - TOC -- Mean PARM = 2102 [gkg]

-100 000 100 200 300 400

h-values

44L

65L

45L

35L

32L

16L

9L

56L

19L

34L

36L

66L

70L

Labo

rato

ries

Mandels h statistics(Soil 5 - TOC)

Soil 5-TOC

17

Annex 4

Raw data submitted

Sample Compost 1 Sample Compost 2 Sample Sewage Sludge 1Element TOC [gkg] Element TOC [gkg] Element TOC [gkg]

LAB PARM LAB PARM LAB PARM30L 2600 19L 1691 19L 286730L 2580 19L 1634 19L 281430L 2560 19L 1619 19L 276934L 2969 19L 1604 19L 272034L 2936 19L 1499 19L 268834L 2958 19L 1414 19L 266234L 2994 34L 1527 34L 315234L 3199 34L 1622 34L 314934L 3024 34L 1519 34L 343035L 2306 34L 1753 34L 336535L 2300 34L 1636 34L 304235L 2298 34L 1874 34L 298335L 2296 35L 1506 35L 270735L 2291 35L 1312 35L 270335L 2259 35L 1294 35L 268836L 2546 35L 1279 35L 267436L 2527 35L 1191 35L 263136L 2470 35L 1177 35L 262644L 2583 36L 1418 36L 271344L 2581 36L 1408 36L 266544L 2578 36L 1320 36L 261444L 2539 44L 1719 44L 292044L 2528 44L 1664 44L 291644L 2525 44L 1654 44L 291245L 2658 44L 1637 44L 290045L 2600 44L 1624 44L 289645L 2546 44L 1620 44L 289345L 2461 45L 1428 45L 297645L 2409 45L 1325 45L 295245L 2350 45L 1323 45L 288546L 2460 45L 1321 45L 286646L 2400 45L 1309 45L 284046L 2370 45L 1253 45L 278746L 2350 46L 1580 46L 233056L 2436 46L 1550 46L 233056L 2435 46L 1170 46L 230056L 2405 46L 1120 46L 229056L 2397 56L 1642 56L 270256L 2375 56L 1626 56L 270156L 2358 56L 1622 56L 269465L 2587 56L 1571 56L 269365L 2542 56L 1561 56L 268465L 2483 56L 1545 56L 268066L 2454 65L 1933 65L 264166L 2429 65L 1838 65L 260966L 2365 65L 1693 65L 260766L 2262 65L 1562 65L 260569L 2730 66L 1561 66L 270169L 2250 66L 1545 66L 267469L 1440 66L 1420 66L 261969L 1420 66L 1417 66L 251470L 2435 69L 2700 69L 2639L 2594 69L 2660 69L 2409L 2570 69L 2170 69L 2199L 2565 69L 2130 69L 2109L 2563 70L 1414 70L 28159L 2562 9L 1644 9L 28579L 2555 9L 1641 9L 2856

32L 2290 9L 1602 9L 285532L 2390 9L 1589 9L 285532L 2510 9L 1526 9L 285332L 2470 9L 1492 9L 284616L 2380 32L 1470 32L 265016L 2530 32L 1520 32L 271016L 2400 32L 1540 32L 271016L 2500 32L 1600 32L 280016L 2420 16L 1400 16L 284016L 2410 16L 1440 16L 2840

16L 1470 16L 286016L 1510 16L 287016L 1360 16L 287016L 1390 16L 2880

Sample Sewage Sludge 2 Sample Soil 4 Sample Soil 5Element TOC [gkg] Element TOC [gkg] Element TOC [gkg]

LAB PARM LAB PARM LAB PARM19L 2308 19L 1720 19L 225019L 2303 19L 1700 19L 223019L 2239 19L 1690 19L 221019L 2204 19L 1670 19L 211019L 2192 19L 1640 19L 210019L 2096 19L 1580 19L 206034L 2631 30L 1790 34L 244334L 2471 30L 1770 34L 233434L 2977 30L 1700 34L 231534L 2785 34L 1740 34L 222134L 2780 34L 1692 34L 217634L 2668 34L 1727 34L 207335L 2179 34L 1767 35L 233035L 2160 34L 1777 35L 208035L 2158 34L 1783 35L 201035L 2132 35L 1700 35L 198035L 2119 35L 1650 35L 193035L 2094 35L 1650 35L 178036L 2096 35L 1640 36L 254036L 2069 35L 1630 36L 253436L 2052 35L 1630 36L 179044L 2325 36L 1500 44L 302144L 2309 36L 1497 44L 298244L 2307 36L 1417 44L 295644L 2305 44L 1594 44L 30744L 2287 44L 1587 44L 30044L 2283 44L 1584 44L 29745L 2331 44L 1574 45L 214945L 2327 44L 1573 45L 209245L 2308 44L 1562 45L 203345L 2287 45L 1827 45L 197145L 2234 45L 1709 45L 193345L 2113 45L 1666 45L 184146L 190 45L 1665 56L 223746L 180 45L 1664 56L 222246L 180 45L 1600 56L 220346L 180 46L 2300 56L 206956L 2204 46L 2300 56L 206856L 2197 46L 2300 56L 204456L 2193 46L 2200 65L 192056L 2185 56L 1668 65L 182056L 2183 56L 1654 65L 179056L 2167 56L 1653 65L 172065L 2136 56L 1643 66L 254365L 2091 56L 1639 66L 242465L 2065 56L 1638 66L 232165L 2047 65L 1630 66L 226266L 2105 65L 1560 70L 2213966L 2022 65L 1530 9L 218066L 2009 65L 1490 9L 214066L 1983 66L 2179 9L 213070L 2272 66L 1900 9L 21109L 2385 66L 1762 9L 20709L 2377 66L 1734 9L 20709L 2375 70L 10404 32L 20509L 2359 9L 1640 32L 21009L 2356 9L 1640 32L 20209L 2354 9L 1610 32L 1960

32L 2240 9L 1590 16L 210032L 2260 9L 1590 16L 220032L 2200 9L 1560 16L 220032L 2270 32L 1640 16L 206016L 2300 32L 1600 16L 197016L 2310 32L 1560 16L 201016L 2350 32L 157016L 2260 16L 170016L 2290 16L 180016L 2240 16L 1700

16L 180016L 170016L 1700

European Commission EUR 23012 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on total organic carbon Author(s) E Sobiecka H van der Sloot K Andersen B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 50 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07412-7 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 total organic carbon (TOC) in soils sludge and treated bio-waste 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

-23012-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

16

Annex 3

Statistical calculations

Unit gkg

Mandels k statistics(Compost 1 - TOC)Mandels h statistics(Compost 1 - TOC)

Sample Compost 1 Compost 1 - TOC -- Mean PARM = 2463 [gkg]

Element TOC

General calcparmT1= 142643E+04T2= 351264E+06T3= 58T4= 292T5= 16501E+03

n= variabelp= 13

N-table= 5

Mandels statistics End ResultLAB 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

69L 1960000 64265 4 -235 352 Fail - - 69L - - -502735L 2291667 1674 6 -081 009 2291667 16741 6 5 -171066L 2377425 8552 4 -041 047 2377425 85518 4 3 -85346L 2395000 4796 4 -033 026 2395000 47958 4 3 -67756L 2401227 3133 6 -030 017 2401227 31330 6 5 -61432L 2415000 9713 4 -024 053 2415000 97125 4 3 -47770L 2435100 - 1 -014 2435100 - 1 -27616L 2440000 6033 6 -012 033 2440000 60332 6 5 -22745L 2503800 11759 6 018 064 2503800 117589 6 5 41136L 2514416 3994 3 023 022 2514416 39937 3 2 51765L 2537333 5216 3 033 029 2537333 52157 3 2 74744L 2555667 2783 6 042 015 2555667 27826 6 5 9309L 2568167 1356 6 048 007 2568167 13556 6 5 105530L 2580000 2000 3 053 011 2580000 20000 3 2 117334L 3013269 9580 6 255 053 Fail - - 34L - - 5506

Totgem 246587 9632 gkg 1-level 232 (176) 13 2462677 (34L 69L) 13 12Totstd= 21507 16070 5-level 186 (152) 2

68RESULTS Mean = 24626770 gkg

Repeatability variance S2r = 3666797Repeatability std Sr = 605541 --gt 246 r = 169551Between lab variance S2L = 7715586Reproducibility var S2R = 11382383Reproducibility std SR = 1066882 --gt 433 R = 298727Remarks 2 Labs rejected (34L 69L)

000 050 100 150 200 250 300 350 400

k-values

69L

35L

66L

46L

56L

32L

70L

16L

45L

36L

65L

44L

9L

30L

34L

Mandels k statistics(Compost 1 - TOC)

-600 -400 -200 00 200 400 600

Deviation from Mean

69L

35L

66L

46L

56L

32L

70L

16L

45L

36L

65L

44L

9L

30L

34L

Labo

rato

ries

Compost 1 - TOC -- Mean PARM = 2463 [gkg]

-300 -200 -100 000 100 200 300

h-values

69L

66L

56L

70L

45L

65L

9L

34L

Labo

rato

ries

Mandels h statistics(Compost 1 - TOC)

Compost 1-TOC

Unit gkg

Mandels k statistics(Compost 2 - TOC)Mandels h statistics(Compost 2 - TOC)

Sample Compost 2 Compost 2 - TOC -- Mean PARM = 1542 [gkg]

Element TOC

General calcparmT1= 994897E+03T2= 155556E+06T3= 64T4= 346T5= 41738E+03

n= variabelp= 13

N-table= 5

Mandels statistics End ResultLAB 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

45L 1326733 5665 6 -100 042 Fail 1326733 56646 6 5 -215046L 1355000 24365 4 -089 181 Fail - - 46L - - -186736L 1381949 5407 3 -078 040 Fail 1381949 54070 3 2 -159870L 1414120 - 1 -066 Fail 1414120 - 1 -127616L 1428333 5565 6 -061 041 1428333 55648 6 5 -113466L 1485550 7805 4 -039 058 1485550 78047 4 3 -56232L 1532500 5377 4 -021 040 1532500 53774 4 3 -09219L 1576833 10138 6 -004 075 1576833 101381 6 5 3519L 1582333 6166 6 -002 046 1582333 61659 6 5 40656L 1594432 4046 6 003 030 1594432 40463 6 5 52744L 1653000 3651 6 025 027 1653000 36508 6 5 111334L 1655127 13717 6 026 102 1655127 137168 6 5 113434L 1655127 13717 6 026 102 1655127 137168 6 5 113465L 1756500 16295 4 065 121 Fail 1756500 162949 4 3 214869L 2415000 30687 4 316 228 Fail - - 69L - - 8733

Totgem 158750 10900 gkg 1-level 232 (176) 13 1541734 (46L 69L) 13 12Totstd= 26187 8164 5-level 186 (152) 2

72RESULTS Mean = 15417337 gkg

Repeatability variance S2r = 8183950Repeatability std Sr = 904652 --gt 587 r = 253303Between lab variance S2L = 13631046Reproducibility var S2R = 21814995Reproducibility std SR = 1476990 --gt 958 R = 413557Remarks 2 Labs rejected (46L 69L)

000 050 100 150 200 250

k-values

45L

46L

36L

70L

16L

66L

32L

19L

9L

56L

44L

34L

34L

65L

69L

Mandels k statistics(Compost 2 - TOC)

-400 -200 00 200 400 600 800 1000

Deviation from Mean

45L

46L

36L

70L

16L

66L

32L

19L

9L

56L

44L

34L

34L

65L

69L

Labo

rato

ries

Compost 2 - TOC -- Mean PARM = 1542 [gkg]

-100 000 100 200 300 400

h-values

45L

36L

16L

32L

9L

44L

34L

69L

Labo

rato

ries

Mandels h statistics(Compost 2 - TOC)

Compost 2-TOC

Unit gkg

Mandels k statistics(Sludge 1 - TOC)Mandels h statistics(Sludge 1 - TOC)

Sample Sludge 1 Sludge 1 - TOC -- Mean PARM = 2721 [gkg]

Element TOC

General calcparmT1= 169626E+04T2= 465445E+06T3= 62T4= 326T5= 10312E+03

n= variabelp= 13

N-table= 5

Mandels statistics End ResultLAB 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

69L 233000 2362 4 -347 037 Fail - - 69L - - -2488046L 2312500 2062 4 -040 032 Fail 2312500 20616 4 3 -408565L 2615500 1708 4 004 026 2615500 17078 4 3 -105566L 2627200 8268 4 006 128 2627200 82678 4 3 -93836L 2664041 4976 3 011 077 2664041 49758 3 2 -56935L 2671500 3533 6 013 055 2671500 35331 6 5 -49556L 2692298 0874 6 016 014 Fail 2692298 08738 6 5 -28732L 2717500 6185 4 019 096 Fail 2717500 61847 4 3 -03519L 2753333 7819 6 025 121 Fail 2753333 78189 6 5 32470L 2814600 - 1 034 Fail 2814600 - 1 9369L 2853667 0398 6 039 006 Fail 2853667 03983 6 5 132716L 2860000 1673 6 040 026 Fail 2860000 16733 6 5 139045L 2884433 7033 6 044 109 Fail 2884433 70331 6 5 163544L 2906167 1129 6 047 017 Fail 2906167 11286 6 5 185234L 3186874 17674 6 089 274 Fail - - 34L - - 4659

Totgem 258617 4692 gkg 1-level 232 (176) 13 2720980 (34L 69L) 13 12Totstd= 67800 4610 5-level 186 (152) 2

72RESULTS Mean = 27209799 gkg

Repeatability variance S2r = 2104538Repeatability std Sr = 458752 --gt 169 r = 128451Between lab variance S2L = 23618387Reproducibility var S2R = 25722925Reproducibility std SR = 1603837 --gt 589 R = 449074Remarks 2 Labs rejected (34L 69L)

000 050 100 150 200 250 300

k-values

69L

46L

65L

66L

36L

35L

56L

32L

19L

70L

9L

16L

45L

44L

34L

Mandels k statistics(Sludge 1 - TOC)

-2500 -2000 -1500 -1000 -500 00 500

Deviation from Mean

69L

46L

65L

66L

36L

35L

56L

32L

19L

70L

9L

16L

45L

44L

34L

Labo

rato

ries

Sludge 1 - TOC -- Mean PARM = 2721 [gkg]

-400 -300 -200 -100 000 100

h-values

69L

65L

36L

56L

19L

9L

45L

34L

Labo

rato

ries

Mandels h statistics(Sludge 1 - TOC)

Sludge 1-TOC

68 Unit gkg

Mandels k statistics(Sludge 2 - TOC)Mandels h statistics(Sludge 2 - TOC)

Sample Sludge 2 Sludge 2 - TOC -- Mean PARM = 2207 [gkg]

Element TOC

General calcparmT1= 128601E+04T2= 285689E+06T3= 58T4= 310T5= 97826E+02

n= variabelp= 12

N-table= 5

Mandels statistics End ResultLAB 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

46L 182500 0500 4 -333 008 Fail - - 46L - - -2024466L 2029475 5267 4 -012 084 2029475 52674 4 3 -177436L 2072609 2222 3 -005 035 2072609 22222 3 2 -134365L 2084750 3865 4 -002 062 2084750 38647 4 3 -122135L 2140333 3119 6 007 050 2140333 31194 6 5 -66556L 2188021 1282 6 015 020 2188021 12822 6 5 -18819L 2223667 7916 6 022 126 Fail 2223667 79157 6 5 16832L 2242500 3096 4 025 049 Fail 2242500 30957 4 3 35645L 2266600 8322 6 029 132 Fail 2266600 83216 6 5 59770L 2272460 - 1 030 Fail 2272460 - 1 65616L 2291667 3869 6 033 062 Fail 2291667 38687 6 5 84844L 2302667 1546 6 035 025 Fail 2302667 15462 6 5 9589L 2367667 1296 6 047 021 Fail 2367667 12956 6 5 160834L 2718591 17124 6 108 273 Fail - - 34L - - 5117

Totgem 209882 4571 gkg 1-level 230 (176) 12 2206868 (34L 46L) 12 11Totstd= 57628 4485 5-level 185 (151) 2

68RESULTS Mean = 22068679 gkg

Repeatability variance S2r = 2126659Repeatability std Sr = 461157 --gt 209 r = 129124Between lab variance S2L = 9960432Reproducibility var S2R = 12087091Reproducibility std SR = 1099413 --gt 498 R = 307836Remarks 2 Labs rejected (34L 46L)

000 050 100 150 200 250 300

k-values

46L

66L

36L

65L

35L

56L

19L

32L

45L

70L

16L

44L

9L

34L

Mandels k statistics(Sludge 2 - TOC)

-2500 -2000 -1500 -1000 -500 00 500 1000

Deviation from Mean

46L

66L

36L

65L

35L

56L

19L

32L

45L

70L

16L

44L

9L

34L

Labo

rato

ries

Sludge 2 - TOC -- Mean PARM = 2207 [gkg]

-400 -300 -200 -100 000 100 200

h-values

46L

66L

36L

65L

35L

56L

19L

32L

45L

70L

16L

44L

9L

34L

Labo

rato

ries

Mandels h statistics(Sludge 2 - TOC)

Sludge 2-TOC

Unit gkg

Mandels k statistics(Soil 4 - TOC)Mandels h statistics(Soil 4 - TOC)

Sample Soil 4 Soil 4 - TOC -- Mean PARM = 1641 [gkg]

Element TOC

General calcparmT1= 102171E+03T2= 168700E+04T3= 62T4= 338T5= 94040E+00

n= variabelp= 12

N-table= 5

Mandels statistics End ResultLAB 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

36L 147161 0470 3 -036 068 Fail 147161 04702 3 2 -16965L 155250 0591 4 -032 085 Fail 155250 05909 4 3 -08844L 157900 0115 6 -031 017 Fail 157900 01152 6 5 -06232L 159250 0359 4 -031 052 Fail 159250 03594 4 3 -0489L 160500 0315 6 -030 045 Fail 160500 03146 6 5 -03656L 164927 0113 6 -028 016 Fail 164927 01127 6 5 00835L 165000 0261 6 -028 038 Fail 165000 02608 6 5 00919L 166667 0505 6 -027 073 Fail 166667 05046 6 5 02645L 168850 0763 6 -026 110 Fail 168850 07628 6 5 04816L 173333 0516 6 -024 074 Fail 173333 05164 6 5 09334L 174761 0346 6 -024 050 Fail 174761 03462 6 5 10730L 175333 0473 3 -024 068 Fail 175333 04726 3 2 11366L 189375 2035 4 -017 294 Fail - - 66L - - 25346L 227500 0500 4 000 072 - - 46L - - 63470L 1040400 - 1 360 Fail - - 70L - - 8763

Totgem 22841 0526 gkg 1-level 232 (176) 12 164078 (46L 66L70L) 12 11Totstd= 22541 0469 5-level 186 (152) 3

71RESULTS Mean = 1640777 gkg

Repeatability variance S2r = 018808Repeatability std Sr = 043368 --gt 264 r = 12143Between lab variance S2L = 054747Reproducibility var S2R = 073555Reproducibility std SR = 085764 --gt 523 R = 24014Remarks 3 Labs rejected (46L 66L70L)

000 050 100 150 200 250 300

k-values

36L

65L

44L

32L

9L

56L

35L

19L

45L

16L

34L

30L

66L

46L

70L

Mandels k statistics(Soil 4 - TOC)

-100 00 100 200 300 400 500 600 700 800 900

Deviation from Mean

36L

65L

44L

32L

9L

56L

35L

19L

45L

16L

34L

30L

66L

46L

70L

Labo

rato

ries

Soil 4 - TOC -- Mean PARM = 1641 [gkg]

-100 000 100 200 300 400

h-values

36L

44L

9L

35L

45L

34L

66L

70L

Labo

rato

ries

Mandels h statistics(Soil 4 - TOC)

Soil 4-TOC

Unit gkg

Mandels k statistics(Soil 5 - TOC)Mandels h statistics(Soil 5 - TOC)

Sample Soil 5 Soil 5 - TOC -- Mean PARM = 2102 [gkg]

Element TOC

General calcparmT1= 113661E+03T2= 240201E+04T3= 54T4= 300T5= 51756E+01

n= variabelp= 10

N-table= 5

Mandels statistics End ResultLAB 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

44L 164383 14708 6 -036 325 Fail - - 44L - - -45865L 181250 0830 4 -033 018 Fail 181250 08302 4 3 -29045L 200317 1116 6 -029 025 Fail 200317 11163 6 5 -09935L 201833 1828 6 -029 040 Fail 201833 18280 6 5 -08432L 203250 0585 4 -029 013 Fail 203250 05852 4 3 -07016L 209000 0959 6 -028 021 Fail 209000 09592 6 5 -0129L 211667 0427 6 -027 009 Fail 211667 04274 6 5 01556L 214030 0887 6 -027 020 Fail 214030 08868 6 5 03819L 216000 0795 6 -026 018 Fail 216000 07950 6 5 05834L 226009 1308 6 -024 029 Fail 226009 13076 6 5 15836L 228783 4310 3 -024 095 Fail - - 36L - - 18666L 238750 1234 4 -022 027 Fail 238750 12340 4 3 28570L 2213900 - 1 333 Fail - - 70L - - 20037

Totgem 36224 2416 gkg 1-level 227 (175) 10 210211 (36L44L 70L) 10 9Totstd= 55669 4003 5-level 184 (151) 3

64RESULTS Mean = 2102106 gkg

Repeatability variance S2r = 117627Repeatability std Sr = 108456 --gt 516 r = 30368Between lab variance S2L = 176699Reproducibility var S2R = 294326Reproducibility std SR = 171559 --gt 816 R = 48037Remarks 3 Labs rejected (36L44L 70L)

000 050 100 150 200 250 300 350

k-values

44L

65L

45L

35L

32L

16L

9L

56L

19L

34L

36L

66L

70L

Mandels k statistics(Soil 5 - TOC)

-500 00 500 1000 1500 2000 2500

Deviation from Mean

44L

65L

45L

35L

32L

16L

9L

56L

19L

34L

36L

66L

70L

Labo

rato

ries

Soil 5 - TOC -- Mean PARM = 2102 [gkg]

-100 000 100 200 300 400

h-values

44L

65L

45L

35L

32L

16L

9L

56L

19L

34L

36L

66L

70L

Labo

rato

ries

Mandels h statistics(Soil 5 - TOC)

Soil 5-TOC

17

Annex 4

Raw data submitted

Sample Compost 1 Sample Compost 2 Sample Sewage Sludge 1Element TOC [gkg] Element TOC [gkg] Element TOC [gkg]

LAB PARM LAB PARM LAB PARM30L 2600 19L 1691 19L 286730L 2580 19L 1634 19L 281430L 2560 19L 1619 19L 276934L 2969 19L 1604 19L 272034L 2936 19L 1499 19L 268834L 2958 19L 1414 19L 266234L 2994 34L 1527 34L 315234L 3199 34L 1622 34L 314934L 3024 34L 1519 34L 343035L 2306 34L 1753 34L 336535L 2300 34L 1636 34L 304235L 2298 34L 1874 34L 298335L 2296 35L 1506 35L 270735L 2291 35L 1312 35L 270335L 2259 35L 1294 35L 268836L 2546 35L 1279 35L 267436L 2527 35L 1191 35L 263136L 2470 35L 1177 35L 262644L 2583 36L 1418 36L 271344L 2581 36L 1408 36L 266544L 2578 36L 1320 36L 261444L 2539 44L 1719 44L 292044L 2528 44L 1664 44L 291644L 2525 44L 1654 44L 291245L 2658 44L 1637 44L 290045L 2600 44L 1624 44L 289645L 2546 44L 1620 44L 289345L 2461 45L 1428 45L 297645L 2409 45L 1325 45L 295245L 2350 45L 1323 45L 288546L 2460 45L 1321 45L 286646L 2400 45L 1309 45L 284046L 2370 45L 1253 45L 278746L 2350 46L 1580 46L 233056L 2436 46L 1550 46L 233056L 2435 46L 1170 46L 230056L 2405 46L 1120 46L 229056L 2397 56L 1642 56L 270256L 2375 56L 1626 56L 270156L 2358 56L 1622 56L 269465L 2587 56L 1571 56L 269365L 2542 56L 1561 56L 268465L 2483 56L 1545 56L 268066L 2454 65L 1933 65L 264166L 2429 65L 1838 65L 260966L 2365 65L 1693 65L 260766L 2262 65L 1562 65L 260569L 2730 66L 1561 66L 270169L 2250 66L 1545 66L 267469L 1440 66L 1420 66L 261969L 1420 66L 1417 66L 251470L 2435 69L 2700 69L 2639L 2594 69L 2660 69L 2409L 2570 69L 2170 69L 2199L 2565 69L 2130 69L 2109L 2563 70L 1414 70L 28159L 2562 9L 1644 9L 28579L 2555 9L 1641 9L 2856

32L 2290 9L 1602 9L 285532L 2390 9L 1589 9L 285532L 2510 9L 1526 9L 285332L 2470 9L 1492 9L 284616L 2380 32L 1470 32L 265016L 2530 32L 1520 32L 271016L 2400 32L 1540 32L 271016L 2500 32L 1600 32L 280016L 2420 16L 1400 16L 284016L 2410 16L 1440 16L 2840

16L 1470 16L 286016L 1510 16L 287016L 1360 16L 287016L 1390 16L 2880

Sample Sewage Sludge 2 Sample Soil 4 Sample Soil 5Element TOC [gkg] Element TOC [gkg] Element TOC [gkg]

LAB PARM LAB PARM LAB PARM19L 2308 19L 1720 19L 225019L 2303 19L 1700 19L 223019L 2239 19L 1690 19L 221019L 2204 19L 1670 19L 211019L 2192 19L 1640 19L 210019L 2096 19L 1580 19L 206034L 2631 30L 1790 34L 244334L 2471 30L 1770 34L 233434L 2977 30L 1700 34L 231534L 2785 34L 1740 34L 222134L 2780 34L 1692 34L 217634L 2668 34L 1727 34L 207335L 2179 34L 1767 35L 233035L 2160 34L 1777 35L 208035L 2158 34L 1783 35L 201035L 2132 35L 1700 35L 198035L 2119 35L 1650 35L 193035L 2094 35L 1650 35L 178036L 2096 35L 1640 36L 254036L 2069 35L 1630 36L 253436L 2052 35L 1630 36L 179044L 2325 36L 1500 44L 302144L 2309 36L 1497 44L 298244L 2307 36L 1417 44L 295644L 2305 44L 1594 44L 30744L 2287 44L 1587 44L 30044L 2283 44L 1584 44L 29745L 2331 44L 1574 45L 214945L 2327 44L 1573 45L 209245L 2308 44L 1562 45L 203345L 2287 45L 1827 45L 197145L 2234 45L 1709 45L 193345L 2113 45L 1666 45L 184146L 190 45L 1665 56L 223746L 180 45L 1664 56L 222246L 180 45L 1600 56L 220346L 180 46L 2300 56L 206956L 2204 46L 2300 56L 206856L 2197 46L 2300 56L 204456L 2193 46L 2200 65L 192056L 2185 56L 1668 65L 182056L 2183 56L 1654 65L 179056L 2167 56L 1653 65L 172065L 2136 56L 1643 66L 254365L 2091 56L 1639 66L 242465L 2065 56L 1638 66L 232165L 2047 65L 1630 66L 226266L 2105 65L 1560 70L 2213966L 2022 65L 1530 9L 218066L 2009 65L 1490 9L 214066L 1983 66L 2179 9L 213070L 2272 66L 1900 9L 21109L 2385 66L 1762 9L 20709L 2377 66L 1734 9L 20709L 2375 70L 10404 32L 20509L 2359 9L 1640 32L 21009L 2356 9L 1640 32L 20209L 2354 9L 1610 32L 1960

32L 2240 9L 1590 16L 210032L 2260 9L 1590 16L 220032L 2200 9L 1560 16L 220032L 2270 32L 1640 16L 206016L 2300 32L 1600 16L 197016L 2310 32L 1560 16L 201016L 2350 32L 157016L 2260 16L 170016L 2290 16L 180016L 2240 16L 1700

16L 180016L 170016L 1700

European Commission EUR 23012 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on total organic carbon Author(s) E Sobiecka H van der Sloot K Andersen B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 50 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07412-7 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 total organic carbon (TOC) in soils sludge and treated bio-waste 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

-23012-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

16

Annex 3

Statistical calculations

Unit gkg

Mandels k statistics(Compost 1 - TOC)Mandels h statistics(Compost 1 - TOC)

Sample Compost 1 Compost 1 - TOC -- Mean PARM = 2463 [gkg]

Element TOC

General calcparmT1= 142643E+04T2= 351264E+06T3= 58T4= 292T5= 16501E+03

n= variabelp= 13

N-table= 5

Mandels statistics End ResultLAB 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

69L 1960000 64265 4 -235 352 Fail - - 69L - - -502735L 2291667 1674 6 -081 009 2291667 16741 6 5 -171066L 2377425 8552 4 -041 047 2377425 85518 4 3 -85346L 2395000 4796 4 -033 026 2395000 47958 4 3 -67756L 2401227 3133 6 -030 017 2401227 31330 6 5 -61432L 2415000 9713 4 -024 053 2415000 97125 4 3 -47770L 2435100 - 1 -014 2435100 - 1 -27616L 2440000 6033 6 -012 033 2440000 60332 6 5 -22745L 2503800 11759 6 018 064 2503800 117589 6 5 41136L 2514416 3994 3 023 022 2514416 39937 3 2 51765L 2537333 5216 3 033 029 2537333 52157 3 2 74744L 2555667 2783 6 042 015 2555667 27826 6 5 9309L 2568167 1356 6 048 007 2568167 13556 6 5 105530L 2580000 2000 3 053 011 2580000 20000 3 2 117334L 3013269 9580 6 255 053 Fail - - 34L - - 5506

Totgem 246587 9632 gkg 1-level 232 (176) 13 2462677 (34L 69L) 13 12Totstd= 21507 16070 5-level 186 (152) 2

68RESULTS Mean = 24626770 gkg

Repeatability variance S2r = 3666797Repeatability std Sr = 605541 --gt 246 r = 169551Between lab variance S2L = 7715586Reproducibility var S2R = 11382383Reproducibility std SR = 1066882 --gt 433 R = 298727Remarks 2 Labs rejected (34L 69L)

000 050 100 150 200 250 300 350 400

k-values

69L

35L

66L

46L

56L

32L

70L

16L

45L

36L

65L

44L

9L

30L

34L

Mandels k statistics(Compost 1 - TOC)

-600 -400 -200 00 200 400 600

Deviation from Mean

69L

35L

66L

46L

56L

32L

70L

16L

45L

36L

65L

44L

9L

30L

34L

Labo

rato

ries

Compost 1 - TOC -- Mean PARM = 2463 [gkg]

-300 -200 -100 000 100 200 300

h-values

69L

66L

56L

70L

45L

65L

9L

34L

Labo

rato

ries

Mandels h statistics(Compost 1 - TOC)

Compost 1-TOC

Unit gkg

Mandels k statistics(Compost 2 - TOC)Mandels h statistics(Compost 2 - TOC)

Sample Compost 2 Compost 2 - TOC -- Mean PARM = 1542 [gkg]

Element TOC

General calcparmT1= 994897E+03T2= 155556E+06T3= 64T4= 346T5= 41738E+03

n= variabelp= 13

N-table= 5

Mandels statistics End ResultLAB 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

45L 1326733 5665 6 -100 042 Fail 1326733 56646 6 5 -215046L 1355000 24365 4 -089 181 Fail - - 46L - - -186736L 1381949 5407 3 -078 040 Fail 1381949 54070 3 2 -159870L 1414120 - 1 -066 Fail 1414120 - 1 -127616L 1428333 5565 6 -061 041 1428333 55648 6 5 -113466L 1485550 7805 4 -039 058 1485550 78047 4 3 -56232L 1532500 5377 4 -021 040 1532500 53774 4 3 -09219L 1576833 10138 6 -004 075 1576833 101381 6 5 3519L 1582333 6166 6 -002 046 1582333 61659 6 5 40656L 1594432 4046 6 003 030 1594432 40463 6 5 52744L 1653000 3651 6 025 027 1653000 36508 6 5 111334L 1655127 13717 6 026 102 1655127 137168 6 5 113434L 1655127 13717 6 026 102 1655127 137168 6 5 113465L 1756500 16295 4 065 121 Fail 1756500 162949 4 3 214869L 2415000 30687 4 316 228 Fail - - 69L - - 8733

Totgem 158750 10900 gkg 1-level 232 (176) 13 1541734 (46L 69L) 13 12Totstd= 26187 8164 5-level 186 (152) 2

72RESULTS Mean = 15417337 gkg

Repeatability variance S2r = 8183950Repeatability std Sr = 904652 --gt 587 r = 253303Between lab variance S2L = 13631046Reproducibility var S2R = 21814995Reproducibility std SR = 1476990 --gt 958 R = 413557Remarks 2 Labs rejected (46L 69L)

000 050 100 150 200 250

k-values

45L

46L

36L

70L

16L

66L

32L

19L

9L

56L

44L

34L

34L

65L

69L

Mandels k statistics(Compost 2 - TOC)

-400 -200 00 200 400 600 800 1000

Deviation from Mean

45L

46L

36L

70L

16L

66L

32L

19L

9L

56L

44L

34L

34L

65L

69L

Labo

rato

ries

Compost 2 - TOC -- Mean PARM = 1542 [gkg]

-100 000 100 200 300 400

h-values

45L

36L

16L

32L

9L

44L

34L

69L

Labo

rato

ries

Mandels h statistics(Compost 2 - TOC)

Compost 2-TOC

Unit gkg

Mandels k statistics(Sludge 1 - TOC)Mandels h statistics(Sludge 1 - TOC)

Sample Sludge 1 Sludge 1 - TOC -- Mean PARM = 2721 [gkg]

Element TOC

General calcparmT1= 169626E+04T2= 465445E+06T3= 62T4= 326T5= 10312E+03

n= variabelp= 13

N-table= 5

Mandels statistics End ResultLAB 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

69L 233000 2362 4 -347 037 Fail - - 69L - - -2488046L 2312500 2062 4 -040 032 Fail 2312500 20616 4 3 -408565L 2615500 1708 4 004 026 2615500 17078 4 3 -105566L 2627200 8268 4 006 128 2627200 82678 4 3 -93836L 2664041 4976 3 011 077 2664041 49758 3 2 -56935L 2671500 3533 6 013 055 2671500 35331 6 5 -49556L 2692298 0874 6 016 014 Fail 2692298 08738 6 5 -28732L 2717500 6185 4 019 096 Fail 2717500 61847 4 3 -03519L 2753333 7819 6 025 121 Fail 2753333 78189 6 5 32470L 2814600 - 1 034 Fail 2814600 - 1 9369L 2853667 0398 6 039 006 Fail 2853667 03983 6 5 132716L 2860000 1673 6 040 026 Fail 2860000 16733 6 5 139045L 2884433 7033 6 044 109 Fail 2884433 70331 6 5 163544L 2906167 1129 6 047 017 Fail 2906167 11286 6 5 185234L 3186874 17674 6 089 274 Fail - - 34L - - 4659

Totgem 258617 4692 gkg 1-level 232 (176) 13 2720980 (34L 69L) 13 12Totstd= 67800 4610 5-level 186 (152) 2

72RESULTS Mean = 27209799 gkg

Repeatability variance S2r = 2104538Repeatability std Sr = 458752 --gt 169 r = 128451Between lab variance S2L = 23618387Reproducibility var S2R = 25722925Reproducibility std SR = 1603837 --gt 589 R = 449074Remarks 2 Labs rejected (34L 69L)

000 050 100 150 200 250 300

k-values

69L

46L

65L

66L

36L

35L

56L

32L

19L

70L

9L

16L

45L

44L

34L

Mandels k statistics(Sludge 1 - TOC)

-2500 -2000 -1500 -1000 -500 00 500

Deviation from Mean

69L

46L

65L

66L

36L

35L

56L

32L

19L

70L

9L

16L

45L

44L

34L

Labo

rato

ries

Sludge 1 - TOC -- Mean PARM = 2721 [gkg]

-400 -300 -200 -100 000 100

h-values

69L

65L

36L

56L

19L

9L

45L

34L

Labo

rato

ries

Mandels h statistics(Sludge 1 - TOC)

Sludge 1-TOC

68 Unit gkg

Mandels k statistics(Sludge 2 - TOC)Mandels h statistics(Sludge 2 - TOC)

Sample Sludge 2 Sludge 2 - TOC -- Mean PARM = 2207 [gkg]

Element TOC

General calcparmT1= 128601E+04T2= 285689E+06T3= 58T4= 310T5= 97826E+02

n= variabelp= 12

N-table= 5

Mandels statistics End ResultLAB 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

46L 182500 0500 4 -333 008 Fail - - 46L - - -2024466L 2029475 5267 4 -012 084 2029475 52674 4 3 -177436L 2072609 2222 3 -005 035 2072609 22222 3 2 -134365L 2084750 3865 4 -002 062 2084750 38647 4 3 -122135L 2140333 3119 6 007 050 2140333 31194 6 5 -66556L 2188021 1282 6 015 020 2188021 12822 6 5 -18819L 2223667 7916 6 022 126 Fail 2223667 79157 6 5 16832L 2242500 3096 4 025 049 Fail 2242500 30957 4 3 35645L 2266600 8322 6 029 132 Fail 2266600 83216 6 5 59770L 2272460 - 1 030 Fail 2272460 - 1 65616L 2291667 3869 6 033 062 Fail 2291667 38687 6 5 84844L 2302667 1546 6 035 025 Fail 2302667 15462 6 5 9589L 2367667 1296 6 047 021 Fail 2367667 12956 6 5 160834L 2718591 17124 6 108 273 Fail - - 34L - - 5117

Totgem 209882 4571 gkg 1-level 230 (176) 12 2206868 (34L 46L) 12 11Totstd= 57628 4485 5-level 185 (151) 2

68RESULTS Mean = 22068679 gkg

Repeatability variance S2r = 2126659Repeatability std Sr = 461157 --gt 209 r = 129124Between lab variance S2L = 9960432Reproducibility var S2R = 12087091Reproducibility std SR = 1099413 --gt 498 R = 307836Remarks 2 Labs rejected (34L 46L)

000 050 100 150 200 250 300

k-values

46L

66L

36L

65L

35L

56L

19L

32L

45L

70L

16L

44L

9L

34L

Mandels k statistics(Sludge 2 - TOC)

-2500 -2000 -1500 -1000 -500 00 500 1000

Deviation from Mean

46L

66L

36L

65L

35L

56L

19L

32L

45L

70L

16L

44L

9L

34L

Labo

rato

ries

Sludge 2 - TOC -- Mean PARM = 2207 [gkg]

-400 -300 -200 -100 000 100 200

h-values

46L

66L

36L

65L

35L

56L

19L

32L

45L

70L

16L

44L

9L

34L

Labo

rato

ries

Mandels h statistics(Sludge 2 - TOC)

Sludge 2-TOC

Unit gkg

Mandels k statistics(Soil 4 - TOC)Mandels h statistics(Soil 4 - TOC)

Sample Soil 4 Soil 4 - TOC -- Mean PARM = 1641 [gkg]

Element TOC

General calcparmT1= 102171E+03T2= 168700E+04T3= 62T4= 338T5= 94040E+00

n= variabelp= 12

N-table= 5

Mandels statistics End ResultLAB 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

36L 147161 0470 3 -036 068 Fail 147161 04702 3 2 -16965L 155250 0591 4 -032 085 Fail 155250 05909 4 3 -08844L 157900 0115 6 -031 017 Fail 157900 01152 6 5 -06232L 159250 0359 4 -031 052 Fail 159250 03594 4 3 -0489L 160500 0315 6 -030 045 Fail 160500 03146 6 5 -03656L 164927 0113 6 -028 016 Fail 164927 01127 6 5 00835L 165000 0261 6 -028 038 Fail 165000 02608 6 5 00919L 166667 0505 6 -027 073 Fail 166667 05046 6 5 02645L 168850 0763 6 -026 110 Fail 168850 07628 6 5 04816L 173333 0516 6 -024 074 Fail 173333 05164 6 5 09334L 174761 0346 6 -024 050 Fail 174761 03462 6 5 10730L 175333 0473 3 -024 068 Fail 175333 04726 3 2 11366L 189375 2035 4 -017 294 Fail - - 66L - - 25346L 227500 0500 4 000 072 - - 46L - - 63470L 1040400 - 1 360 Fail - - 70L - - 8763

Totgem 22841 0526 gkg 1-level 232 (176) 12 164078 (46L 66L70L) 12 11Totstd= 22541 0469 5-level 186 (152) 3

71RESULTS Mean = 1640777 gkg

Repeatability variance S2r = 018808Repeatability std Sr = 043368 --gt 264 r = 12143Between lab variance S2L = 054747Reproducibility var S2R = 073555Reproducibility std SR = 085764 --gt 523 R = 24014Remarks 3 Labs rejected (46L 66L70L)

000 050 100 150 200 250 300

k-values

36L

65L

44L

32L

9L

56L

35L

19L

45L

16L

34L

30L

66L

46L

70L

Mandels k statistics(Soil 4 - TOC)

-100 00 100 200 300 400 500 600 700 800 900

Deviation from Mean

36L

65L

44L

32L

9L

56L

35L

19L

45L

16L

34L

30L

66L

46L

70L

Labo

rato

ries

Soil 4 - TOC -- Mean PARM = 1641 [gkg]

-100 000 100 200 300 400

h-values

36L

44L

9L

35L

45L

34L

66L

70L

Labo

rato

ries

Mandels h statistics(Soil 4 - TOC)

Soil 4-TOC

Unit gkg

Mandels k statistics(Soil 5 - TOC)Mandels h statistics(Soil 5 - TOC)

Sample Soil 5 Soil 5 - TOC -- Mean PARM = 2102 [gkg]

Element TOC

General calcparmT1= 113661E+03T2= 240201E+04T3= 54T4= 300T5= 51756E+01

n= variabelp= 10

N-table= 5

Mandels statistics End ResultLAB 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

44L 164383 14708 6 -036 325 Fail - - 44L - - -45865L 181250 0830 4 -033 018 Fail 181250 08302 4 3 -29045L 200317 1116 6 -029 025 Fail 200317 11163 6 5 -09935L 201833 1828 6 -029 040 Fail 201833 18280 6 5 -08432L 203250 0585 4 -029 013 Fail 203250 05852 4 3 -07016L 209000 0959 6 -028 021 Fail 209000 09592 6 5 -0129L 211667 0427 6 -027 009 Fail 211667 04274 6 5 01556L 214030 0887 6 -027 020 Fail 214030 08868 6 5 03819L 216000 0795 6 -026 018 Fail 216000 07950 6 5 05834L 226009 1308 6 -024 029 Fail 226009 13076 6 5 15836L 228783 4310 3 -024 095 Fail - - 36L - - 18666L 238750 1234 4 -022 027 Fail 238750 12340 4 3 28570L 2213900 - 1 333 Fail - - 70L - - 20037

Totgem 36224 2416 gkg 1-level 227 (175) 10 210211 (36L44L 70L) 10 9Totstd= 55669 4003 5-level 184 (151) 3

64RESULTS Mean = 2102106 gkg

Repeatability variance S2r = 117627Repeatability std Sr = 108456 --gt 516 r = 30368Between lab variance S2L = 176699Reproducibility var S2R = 294326Reproducibility std SR = 171559 --gt 816 R = 48037Remarks 3 Labs rejected (36L44L 70L)

000 050 100 150 200 250 300 350

k-values

44L

65L

45L

35L

32L

16L

9L

56L

19L

34L

36L

66L

70L

Mandels k statistics(Soil 5 - TOC)

-500 00 500 1000 1500 2000 2500

Deviation from Mean

44L

65L

45L

35L

32L

16L

9L

56L

19L

34L

36L

66L

70L

Labo

rato

ries

Soil 5 - TOC -- Mean PARM = 2102 [gkg]

-100 000 100 200 300 400

h-values

44L

65L

45L

35L

32L

16L

9L

56L

19L

34L

36L

66L

70L

Labo

rato

ries

Mandels h statistics(Soil 5 - TOC)

Soil 5-TOC

17

Annex 4

Raw data submitted

Sample Compost 1 Sample Compost 2 Sample Sewage Sludge 1Element TOC [gkg] Element TOC [gkg] Element TOC [gkg]

LAB PARM LAB PARM LAB PARM30L 2600 19L 1691 19L 286730L 2580 19L 1634 19L 281430L 2560 19L 1619 19L 276934L 2969 19L 1604 19L 272034L 2936 19L 1499 19L 268834L 2958 19L 1414 19L 266234L 2994 34L 1527 34L 315234L 3199 34L 1622 34L 314934L 3024 34L 1519 34L 343035L 2306 34L 1753 34L 336535L 2300 34L 1636 34L 304235L 2298 34L 1874 34L 298335L 2296 35L 1506 35L 270735L 2291 35L 1312 35L 270335L 2259 35L 1294 35L 268836L 2546 35L 1279 35L 267436L 2527 35L 1191 35L 263136L 2470 35L 1177 35L 262644L 2583 36L 1418 36L 271344L 2581 36L 1408 36L 266544L 2578 36L 1320 36L 261444L 2539 44L 1719 44L 292044L 2528 44L 1664 44L 291644L 2525 44L 1654 44L 291245L 2658 44L 1637 44L 290045L 2600 44L 1624 44L 289645L 2546 44L 1620 44L 289345L 2461 45L 1428 45L 297645L 2409 45L 1325 45L 295245L 2350 45L 1323 45L 288546L 2460 45L 1321 45L 286646L 2400 45L 1309 45L 284046L 2370 45L 1253 45L 278746L 2350 46L 1580 46L 233056L 2436 46L 1550 46L 233056L 2435 46L 1170 46L 230056L 2405 46L 1120 46L 229056L 2397 56L 1642 56L 270256L 2375 56L 1626 56L 270156L 2358 56L 1622 56L 269465L 2587 56L 1571 56L 269365L 2542 56L 1561 56L 268465L 2483 56L 1545 56L 268066L 2454 65L 1933 65L 264166L 2429 65L 1838 65L 260966L 2365 65L 1693 65L 260766L 2262 65L 1562 65L 260569L 2730 66L 1561 66L 270169L 2250 66L 1545 66L 267469L 1440 66L 1420 66L 261969L 1420 66L 1417 66L 251470L 2435 69L 2700 69L 2639L 2594 69L 2660 69L 2409L 2570 69L 2170 69L 2199L 2565 69L 2130 69L 2109L 2563 70L 1414 70L 28159L 2562 9L 1644 9L 28579L 2555 9L 1641 9L 2856

32L 2290 9L 1602 9L 285532L 2390 9L 1589 9L 285532L 2510 9L 1526 9L 285332L 2470 9L 1492 9L 284616L 2380 32L 1470 32L 265016L 2530 32L 1520 32L 271016L 2400 32L 1540 32L 271016L 2500 32L 1600 32L 280016L 2420 16L 1400 16L 284016L 2410 16L 1440 16L 2840

16L 1470 16L 286016L 1510 16L 287016L 1360 16L 287016L 1390 16L 2880

Sample Sewage Sludge 2 Sample Soil 4 Sample Soil 5Element TOC [gkg] Element TOC [gkg] Element TOC [gkg]

LAB PARM LAB PARM LAB PARM19L 2308 19L 1720 19L 225019L 2303 19L 1700 19L 223019L 2239 19L 1690 19L 221019L 2204 19L 1670 19L 211019L 2192 19L 1640 19L 210019L 2096 19L 1580 19L 206034L 2631 30L 1790 34L 244334L 2471 30L 1770 34L 233434L 2977 30L 1700 34L 231534L 2785 34L 1740 34L 222134L 2780 34L 1692 34L 217634L 2668 34L 1727 34L 207335L 2179 34L 1767 35L 233035L 2160 34L 1777 35L 208035L 2158 34L 1783 35L 201035L 2132 35L 1700 35L 198035L 2119 35L 1650 35L 193035L 2094 35L 1650 35L 178036L 2096 35L 1640 36L 254036L 2069 35L 1630 36L 253436L 2052 35L 1630 36L 179044L 2325 36L 1500 44L 302144L 2309 36L 1497 44L 298244L 2307 36L 1417 44L 295644L 2305 44L 1594 44L 30744L 2287 44L 1587 44L 30044L 2283 44L 1584 44L 29745L 2331 44L 1574 45L 214945L 2327 44L 1573 45L 209245L 2308 44L 1562 45L 203345L 2287 45L 1827 45L 197145L 2234 45L 1709 45L 193345L 2113 45L 1666 45L 184146L 190 45L 1665 56L 223746L 180 45L 1664 56L 222246L 180 45L 1600 56L 220346L 180 46L 2300 56L 206956L 2204 46L 2300 56L 206856L 2197 46L 2300 56L 204456L 2193 46L 2200 65L 192056L 2185 56L 1668 65L 182056L 2183 56L 1654 65L 179056L 2167 56L 1653 65L 172065L 2136 56L 1643 66L 254365L 2091 56L 1639 66L 242465L 2065 56L 1638 66L 232165L 2047 65L 1630 66L 226266L 2105 65L 1560 70L 2213966L 2022 65L 1530 9L 218066L 2009 65L 1490 9L 214066L 1983 66L 2179 9L 213070L 2272 66L 1900 9L 21109L 2385 66L 1762 9L 20709L 2377 66L 1734 9L 20709L 2375 70L 10404 32L 20509L 2359 9L 1640 32L 21009L 2356 9L 1640 32L 20209L 2354 9L 1610 32L 1960

32L 2240 9L 1590 16L 210032L 2260 9L 1590 16L 220032L 2200 9L 1560 16L 220032L 2270 32L 1640 16L 206016L 2300 32L 1600 16L 197016L 2310 32L 1560 16L 201016L 2350 32L 157016L 2260 16L 170016L 2290 16L 180016L 2240 16L 1700

16L 180016L 170016L 1700

European Commission EUR 23012 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on total organic carbon Author(s) E Sobiecka H van der Sloot K Andersen B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 50 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07412-7 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 total organic carbon (TOC) in soils sludge and treated bio-waste 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

-23012-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

16

Annex 3

Statistical calculations

Unit gkg

Mandels k statistics(Compost 1 - TOC)Mandels h statistics(Compost 1 - TOC)

Sample Compost 1 Compost 1 - TOC -- Mean PARM = 2463 [gkg]

Element TOC

General calcparmT1= 142643E+04T2= 351264E+06T3= 58T4= 292T5= 16501E+03

n= variabelp= 13

N-table= 5

Mandels statistics End ResultLAB 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

69L 1960000 64265 4 -235 352 Fail - - 69L - - -502735L 2291667 1674 6 -081 009 2291667 16741 6 5 -171066L 2377425 8552 4 -041 047 2377425 85518 4 3 -85346L 2395000 4796 4 -033 026 2395000 47958 4 3 -67756L 2401227 3133 6 -030 017 2401227 31330 6 5 -61432L 2415000 9713 4 -024 053 2415000 97125 4 3 -47770L 2435100 - 1 -014 2435100 - 1 -27616L 2440000 6033 6 -012 033 2440000 60332 6 5 -22745L 2503800 11759 6 018 064 2503800 117589 6 5 41136L 2514416 3994 3 023 022 2514416 39937 3 2 51765L 2537333 5216 3 033 029 2537333 52157 3 2 74744L 2555667 2783 6 042 015 2555667 27826 6 5 9309L 2568167 1356 6 048 007 2568167 13556 6 5 105530L 2580000 2000 3 053 011 2580000 20000 3 2 117334L 3013269 9580 6 255 053 Fail - - 34L - - 5506

Totgem 246587 9632 gkg 1-level 232 (176) 13 2462677 (34L 69L) 13 12Totstd= 21507 16070 5-level 186 (152) 2

68RESULTS Mean = 24626770 gkg

Repeatability variance S2r = 3666797Repeatability std Sr = 605541 --gt 246 r = 169551Between lab variance S2L = 7715586Reproducibility var S2R = 11382383Reproducibility std SR = 1066882 --gt 433 R = 298727Remarks 2 Labs rejected (34L 69L)

000 050 100 150 200 250 300 350 400

k-values

69L

35L

66L

46L

56L

32L

70L

16L

45L

36L

65L

44L

9L

30L

34L

Mandels k statistics(Compost 1 - TOC)

-600 -400 -200 00 200 400 600

Deviation from Mean

69L

35L

66L

46L

56L

32L

70L

16L

45L

36L

65L

44L

9L

30L

34L

Labo

rato

ries

Compost 1 - TOC -- Mean PARM = 2463 [gkg]

-300 -200 -100 000 100 200 300

h-values

69L

66L

56L

70L

45L

65L

9L

34L

Labo

rato

ries

Mandels h statistics(Compost 1 - TOC)

Compost 1-TOC

Unit gkg

Mandels k statistics(Compost 2 - TOC)Mandels h statistics(Compost 2 - TOC)

Sample Compost 2 Compost 2 - TOC -- Mean PARM = 1542 [gkg]

Element TOC

General calcparmT1= 994897E+03T2= 155556E+06T3= 64T4= 346T5= 41738E+03

n= variabelp= 13

N-table= 5

Mandels statistics End ResultLAB 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

45L 1326733 5665 6 -100 042 Fail 1326733 56646 6 5 -215046L 1355000 24365 4 -089 181 Fail - - 46L - - -186736L 1381949 5407 3 -078 040 Fail 1381949 54070 3 2 -159870L 1414120 - 1 -066 Fail 1414120 - 1 -127616L 1428333 5565 6 -061 041 1428333 55648 6 5 -113466L 1485550 7805 4 -039 058 1485550 78047 4 3 -56232L 1532500 5377 4 -021 040 1532500 53774 4 3 -09219L 1576833 10138 6 -004 075 1576833 101381 6 5 3519L 1582333 6166 6 -002 046 1582333 61659 6 5 40656L 1594432 4046 6 003 030 1594432 40463 6 5 52744L 1653000 3651 6 025 027 1653000 36508 6 5 111334L 1655127 13717 6 026 102 1655127 137168 6 5 113434L 1655127 13717 6 026 102 1655127 137168 6 5 113465L 1756500 16295 4 065 121 Fail 1756500 162949 4 3 214869L 2415000 30687 4 316 228 Fail - - 69L - - 8733

Totgem 158750 10900 gkg 1-level 232 (176) 13 1541734 (46L 69L) 13 12Totstd= 26187 8164 5-level 186 (152) 2

72RESULTS Mean = 15417337 gkg

Repeatability variance S2r = 8183950Repeatability std Sr = 904652 --gt 587 r = 253303Between lab variance S2L = 13631046Reproducibility var S2R = 21814995Reproducibility std SR = 1476990 --gt 958 R = 413557Remarks 2 Labs rejected (46L 69L)

000 050 100 150 200 250

k-values

45L

46L

36L

70L

16L

66L

32L

19L

9L

56L

44L

34L

34L

65L

69L

Mandels k statistics(Compost 2 - TOC)

-400 -200 00 200 400 600 800 1000

Deviation from Mean

45L

46L

36L

70L

16L

66L

32L

19L

9L

56L

44L

34L

34L

65L

69L

Labo

rato

ries

Compost 2 - TOC -- Mean PARM = 1542 [gkg]

-100 000 100 200 300 400

h-values

45L

36L

16L

32L

9L

44L

34L

69L

Labo

rato

ries

Mandels h statistics(Compost 2 - TOC)

Compost 2-TOC

Unit gkg

Mandels k statistics(Sludge 1 - TOC)Mandels h statistics(Sludge 1 - TOC)

Sample Sludge 1 Sludge 1 - TOC -- Mean PARM = 2721 [gkg]

Element TOC

General calcparmT1= 169626E+04T2= 465445E+06T3= 62T4= 326T5= 10312E+03

n= variabelp= 13

N-table= 5

Mandels statistics End ResultLAB 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

69L 233000 2362 4 -347 037 Fail - - 69L - - -2488046L 2312500 2062 4 -040 032 Fail 2312500 20616 4 3 -408565L 2615500 1708 4 004 026 2615500 17078 4 3 -105566L 2627200 8268 4 006 128 2627200 82678 4 3 -93836L 2664041 4976 3 011 077 2664041 49758 3 2 -56935L 2671500 3533 6 013 055 2671500 35331 6 5 -49556L 2692298 0874 6 016 014 Fail 2692298 08738 6 5 -28732L 2717500 6185 4 019 096 Fail 2717500 61847 4 3 -03519L 2753333 7819 6 025 121 Fail 2753333 78189 6 5 32470L 2814600 - 1 034 Fail 2814600 - 1 9369L 2853667 0398 6 039 006 Fail 2853667 03983 6 5 132716L 2860000 1673 6 040 026 Fail 2860000 16733 6 5 139045L 2884433 7033 6 044 109 Fail 2884433 70331 6 5 163544L 2906167 1129 6 047 017 Fail 2906167 11286 6 5 185234L 3186874 17674 6 089 274 Fail - - 34L - - 4659

Totgem 258617 4692 gkg 1-level 232 (176) 13 2720980 (34L 69L) 13 12Totstd= 67800 4610 5-level 186 (152) 2

72RESULTS Mean = 27209799 gkg

Repeatability variance S2r = 2104538Repeatability std Sr = 458752 --gt 169 r = 128451Between lab variance S2L = 23618387Reproducibility var S2R = 25722925Reproducibility std SR = 1603837 --gt 589 R = 449074Remarks 2 Labs rejected (34L 69L)

000 050 100 150 200 250 300

k-values

69L

46L

65L

66L

36L

35L

56L

32L

19L

70L

9L

16L

45L

44L

34L

Mandels k statistics(Sludge 1 - TOC)

-2500 -2000 -1500 -1000 -500 00 500

Deviation from Mean

69L

46L

65L

66L

36L

35L

56L

32L

19L

70L

9L

16L

45L

44L

34L

Labo

rato

ries

Sludge 1 - TOC -- Mean PARM = 2721 [gkg]

-400 -300 -200 -100 000 100

h-values

69L

65L

36L

56L

19L

9L

45L

34L

Labo

rato

ries

Mandels h statistics(Sludge 1 - TOC)

Sludge 1-TOC

68 Unit gkg

Mandels k statistics(Sludge 2 - TOC)Mandels h statistics(Sludge 2 - TOC)

Sample Sludge 2 Sludge 2 - TOC -- Mean PARM = 2207 [gkg]

Element TOC

General calcparmT1= 128601E+04T2= 285689E+06T3= 58T4= 310T5= 97826E+02

n= variabelp= 12

N-table= 5

Mandels statistics End ResultLAB 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

46L 182500 0500 4 -333 008 Fail - - 46L - - -2024466L 2029475 5267 4 -012 084 2029475 52674 4 3 -177436L 2072609 2222 3 -005 035 2072609 22222 3 2 -134365L 2084750 3865 4 -002 062 2084750 38647 4 3 -122135L 2140333 3119 6 007 050 2140333 31194 6 5 -66556L 2188021 1282 6 015 020 2188021 12822 6 5 -18819L 2223667 7916 6 022 126 Fail 2223667 79157 6 5 16832L 2242500 3096 4 025 049 Fail 2242500 30957 4 3 35645L 2266600 8322 6 029 132 Fail 2266600 83216 6 5 59770L 2272460 - 1 030 Fail 2272460 - 1 65616L 2291667 3869 6 033 062 Fail 2291667 38687 6 5 84844L 2302667 1546 6 035 025 Fail 2302667 15462 6 5 9589L 2367667 1296 6 047 021 Fail 2367667 12956 6 5 160834L 2718591 17124 6 108 273 Fail - - 34L - - 5117

Totgem 209882 4571 gkg 1-level 230 (176) 12 2206868 (34L 46L) 12 11Totstd= 57628 4485 5-level 185 (151) 2

68RESULTS Mean = 22068679 gkg

Repeatability variance S2r = 2126659Repeatability std Sr = 461157 --gt 209 r = 129124Between lab variance S2L = 9960432Reproducibility var S2R = 12087091Reproducibility std SR = 1099413 --gt 498 R = 307836Remarks 2 Labs rejected (34L 46L)

000 050 100 150 200 250 300

k-values

46L

66L

36L

65L

35L

56L

19L

32L

45L

70L

16L

44L

9L

34L

Mandels k statistics(Sludge 2 - TOC)

-2500 -2000 -1500 -1000 -500 00 500 1000

Deviation from Mean

46L

66L

36L

65L

35L

56L

19L

32L

45L

70L

16L

44L

9L

34L

Labo

rato

ries

Sludge 2 - TOC -- Mean PARM = 2207 [gkg]

-400 -300 -200 -100 000 100 200

h-values

46L

66L

36L

65L

35L

56L

19L

32L

45L

70L

16L

44L

9L

34L

Labo

rato

ries

Mandels h statistics(Sludge 2 - TOC)

Sludge 2-TOC

Unit gkg

Mandels k statistics(Soil 4 - TOC)Mandels h statistics(Soil 4 - TOC)

Sample Soil 4 Soil 4 - TOC -- Mean PARM = 1641 [gkg]

Element TOC

General calcparmT1= 102171E+03T2= 168700E+04T3= 62T4= 338T5= 94040E+00

n= variabelp= 12

N-table= 5

Mandels statistics End ResultLAB 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

36L 147161 0470 3 -036 068 Fail 147161 04702 3 2 -16965L 155250 0591 4 -032 085 Fail 155250 05909 4 3 -08844L 157900 0115 6 -031 017 Fail 157900 01152 6 5 -06232L 159250 0359 4 -031 052 Fail 159250 03594 4 3 -0489L 160500 0315 6 -030 045 Fail 160500 03146 6 5 -03656L 164927 0113 6 -028 016 Fail 164927 01127 6 5 00835L 165000 0261 6 -028 038 Fail 165000 02608 6 5 00919L 166667 0505 6 -027 073 Fail 166667 05046 6 5 02645L 168850 0763 6 -026 110 Fail 168850 07628 6 5 04816L 173333 0516 6 -024 074 Fail 173333 05164 6 5 09334L 174761 0346 6 -024 050 Fail 174761 03462 6 5 10730L 175333 0473 3 -024 068 Fail 175333 04726 3 2 11366L 189375 2035 4 -017 294 Fail - - 66L - - 25346L 227500 0500 4 000 072 - - 46L - - 63470L 1040400 - 1 360 Fail - - 70L - - 8763

Totgem 22841 0526 gkg 1-level 232 (176) 12 164078 (46L 66L70L) 12 11Totstd= 22541 0469 5-level 186 (152) 3

71RESULTS Mean = 1640777 gkg

Repeatability variance S2r = 018808Repeatability std Sr = 043368 --gt 264 r = 12143Between lab variance S2L = 054747Reproducibility var S2R = 073555Reproducibility std SR = 085764 --gt 523 R = 24014Remarks 3 Labs rejected (46L 66L70L)

000 050 100 150 200 250 300

k-values

36L

65L

44L

32L

9L

56L

35L

19L

45L

16L

34L

30L

66L

46L

70L

Mandels k statistics(Soil 4 - TOC)

-100 00 100 200 300 400 500 600 700 800 900

Deviation from Mean

36L

65L

44L

32L

9L

56L

35L

19L

45L

16L

34L

30L

66L

46L

70L

Labo

rato

ries

Soil 4 - TOC -- Mean PARM = 1641 [gkg]

-100 000 100 200 300 400

h-values

36L

44L

9L

35L

45L

34L

66L

70L

Labo

rato

ries

Mandels h statistics(Soil 4 - TOC)

Soil 4-TOC

Unit gkg

Mandels k statistics(Soil 5 - TOC)Mandels h statistics(Soil 5 - TOC)

Sample Soil 5 Soil 5 - TOC -- Mean PARM = 2102 [gkg]

Element TOC

General calcparmT1= 113661E+03T2= 240201E+04T3= 54T4= 300T5= 51756E+01

n= variabelp= 10

N-table= 5

Mandels statistics End ResultLAB 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

44L 164383 14708 6 -036 325 Fail - - 44L - - -45865L 181250 0830 4 -033 018 Fail 181250 08302 4 3 -29045L 200317 1116 6 -029 025 Fail 200317 11163 6 5 -09935L 201833 1828 6 -029 040 Fail 201833 18280 6 5 -08432L 203250 0585 4 -029 013 Fail 203250 05852 4 3 -07016L 209000 0959 6 -028 021 Fail 209000 09592 6 5 -0129L 211667 0427 6 -027 009 Fail 211667 04274 6 5 01556L 214030 0887 6 -027 020 Fail 214030 08868 6 5 03819L 216000 0795 6 -026 018 Fail 216000 07950 6 5 05834L 226009 1308 6 -024 029 Fail 226009 13076 6 5 15836L 228783 4310 3 -024 095 Fail - - 36L - - 18666L 238750 1234 4 -022 027 Fail 238750 12340 4 3 28570L 2213900 - 1 333 Fail - - 70L - - 20037

Totgem 36224 2416 gkg 1-level 227 (175) 10 210211 (36L44L 70L) 10 9Totstd= 55669 4003 5-level 184 (151) 3

64RESULTS Mean = 2102106 gkg

Repeatability variance S2r = 117627Repeatability std Sr = 108456 --gt 516 r = 30368Between lab variance S2L = 176699Reproducibility var S2R = 294326Reproducibility std SR = 171559 --gt 816 R = 48037Remarks 3 Labs rejected (36L44L 70L)

000 050 100 150 200 250 300 350

k-values

44L

65L

45L

35L

32L

16L

9L

56L

19L

34L

36L

66L

70L

Mandels k statistics(Soil 5 - TOC)

-500 00 500 1000 1500 2000 2500

Deviation from Mean

44L

65L

45L

35L

32L

16L

9L

56L

19L

34L

36L

66L

70L

Labo

rato

ries

Soil 5 - TOC -- Mean PARM = 2102 [gkg]

-100 000 100 200 300 400

h-values

44L

65L

45L

35L

32L

16L

9L

56L

19L

34L

36L

66L

70L

Labo

rato

ries

Mandels h statistics(Soil 5 - TOC)

Soil 5-TOC

17

Annex 4

Raw data submitted

Sample Compost 1 Sample Compost 2 Sample Sewage Sludge 1Element TOC [gkg] Element TOC [gkg] Element TOC [gkg]

LAB PARM LAB PARM LAB PARM30L 2600 19L 1691 19L 286730L 2580 19L 1634 19L 281430L 2560 19L 1619 19L 276934L 2969 19L 1604 19L 272034L 2936 19L 1499 19L 268834L 2958 19L 1414 19L 266234L 2994 34L 1527 34L 315234L 3199 34L 1622 34L 314934L 3024 34L 1519 34L 343035L 2306 34L 1753 34L 336535L 2300 34L 1636 34L 304235L 2298 34L 1874 34L 298335L 2296 35L 1506 35L 270735L 2291 35L 1312 35L 270335L 2259 35L 1294 35L 268836L 2546 35L 1279 35L 267436L 2527 35L 1191 35L 263136L 2470 35L 1177 35L 262644L 2583 36L 1418 36L 271344L 2581 36L 1408 36L 266544L 2578 36L 1320 36L 261444L 2539 44L 1719 44L 292044L 2528 44L 1664 44L 291644L 2525 44L 1654 44L 291245L 2658 44L 1637 44L 290045L 2600 44L 1624 44L 289645L 2546 44L 1620 44L 289345L 2461 45L 1428 45L 297645L 2409 45L 1325 45L 295245L 2350 45L 1323 45L 288546L 2460 45L 1321 45L 286646L 2400 45L 1309 45L 284046L 2370 45L 1253 45L 278746L 2350 46L 1580 46L 233056L 2436 46L 1550 46L 233056L 2435 46L 1170 46L 230056L 2405 46L 1120 46L 229056L 2397 56L 1642 56L 270256L 2375 56L 1626 56L 270156L 2358 56L 1622 56L 269465L 2587 56L 1571 56L 269365L 2542 56L 1561 56L 268465L 2483 56L 1545 56L 268066L 2454 65L 1933 65L 264166L 2429 65L 1838 65L 260966L 2365 65L 1693 65L 260766L 2262 65L 1562 65L 260569L 2730 66L 1561 66L 270169L 2250 66L 1545 66L 267469L 1440 66L 1420 66L 261969L 1420 66L 1417 66L 251470L 2435 69L 2700 69L 2639L 2594 69L 2660 69L 2409L 2570 69L 2170 69L 2199L 2565 69L 2130 69L 2109L 2563 70L 1414 70L 28159L 2562 9L 1644 9L 28579L 2555 9L 1641 9L 2856

32L 2290 9L 1602 9L 285532L 2390 9L 1589 9L 285532L 2510 9L 1526 9L 285332L 2470 9L 1492 9L 284616L 2380 32L 1470 32L 265016L 2530 32L 1520 32L 271016L 2400 32L 1540 32L 271016L 2500 32L 1600 32L 280016L 2420 16L 1400 16L 284016L 2410 16L 1440 16L 2840

16L 1470 16L 286016L 1510 16L 287016L 1360 16L 287016L 1390 16L 2880

Sample Sewage Sludge 2 Sample Soil 4 Sample Soil 5Element TOC [gkg] Element TOC [gkg] Element TOC [gkg]

LAB PARM LAB PARM LAB PARM19L 2308 19L 1720 19L 225019L 2303 19L 1700 19L 223019L 2239 19L 1690 19L 221019L 2204 19L 1670 19L 211019L 2192 19L 1640 19L 210019L 2096 19L 1580 19L 206034L 2631 30L 1790 34L 244334L 2471 30L 1770 34L 233434L 2977 30L 1700 34L 231534L 2785 34L 1740 34L 222134L 2780 34L 1692 34L 217634L 2668 34L 1727 34L 207335L 2179 34L 1767 35L 233035L 2160 34L 1777 35L 208035L 2158 34L 1783 35L 201035L 2132 35L 1700 35L 198035L 2119 35L 1650 35L 193035L 2094 35L 1650 35L 178036L 2096 35L 1640 36L 254036L 2069 35L 1630 36L 253436L 2052 35L 1630 36L 179044L 2325 36L 1500 44L 302144L 2309 36L 1497 44L 298244L 2307 36L 1417 44L 295644L 2305 44L 1594 44L 30744L 2287 44L 1587 44L 30044L 2283 44L 1584 44L 29745L 2331 44L 1574 45L 214945L 2327 44L 1573 45L 209245L 2308 44L 1562 45L 203345L 2287 45L 1827 45L 197145L 2234 45L 1709 45L 193345L 2113 45L 1666 45L 184146L 190 45L 1665 56L 223746L 180 45L 1664 56L 222246L 180 45L 1600 56L 220346L 180 46L 2300 56L 206956L 2204 46L 2300 56L 206856L 2197 46L 2300 56L 204456L 2193 46L 2200 65L 192056L 2185 56L 1668 65L 182056L 2183 56L 1654 65L 179056L 2167 56L 1653 65L 172065L 2136 56L 1643 66L 254365L 2091 56L 1639 66L 242465L 2065 56L 1638 66L 232165L 2047 65L 1630 66L 226266L 2105 65L 1560 70L 2213966L 2022 65L 1530 9L 218066L 2009 65L 1490 9L 214066L 1983 66L 2179 9L 213070L 2272 66L 1900 9L 21109L 2385 66L 1762 9L 20709L 2377 66L 1734 9L 20709L 2375 70L 10404 32L 20509L 2359 9L 1640 32L 21009L 2356 9L 1640 32L 20209L 2354 9L 1610 32L 1960

32L 2240 9L 1590 16L 210032L 2260 9L 1590 16L 220032L 2200 9L 1560 16L 220032L 2270 32L 1640 16L 206016L 2300 32L 1600 16L 197016L 2310 32L 1560 16L 201016L 2350 32L 157016L 2260 16L 170016L 2290 16L 180016L 2240 16L 1700

16L 180016L 170016L 1700

European Commission EUR 23012 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on total organic carbon Author(s) E Sobiecka H van der Sloot K Andersen B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 50 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07412-7 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 total organic carbon (TOC) in soils sludge and treated bio-waste 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

-23012-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

16

Annex 3

Statistical calculations

Unit gkg

Mandels k statistics(Compost 1 - TOC)Mandels h statistics(Compost 1 - TOC)

Sample Compost 1 Compost 1 - TOC -- Mean PARM = 2463 [gkg]

Element TOC

General calcparmT1= 142643E+04T2= 351264E+06T3= 58T4= 292T5= 16501E+03

n= variabelp= 13

N-table= 5

Mandels statistics End ResultLAB 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

69L 1960000 64265 4 -235 352 Fail - - 69L - - -502735L 2291667 1674 6 -081 009 2291667 16741 6 5 -171066L 2377425 8552 4 -041 047 2377425 85518 4 3 -85346L 2395000 4796 4 -033 026 2395000 47958 4 3 -67756L 2401227 3133 6 -030 017 2401227 31330 6 5 -61432L 2415000 9713 4 -024 053 2415000 97125 4 3 -47770L 2435100 - 1 -014 2435100 - 1 -27616L 2440000 6033 6 -012 033 2440000 60332 6 5 -22745L 2503800 11759 6 018 064 2503800 117589 6 5 41136L 2514416 3994 3 023 022 2514416 39937 3 2 51765L 2537333 5216 3 033 029 2537333 52157 3 2 74744L 2555667 2783 6 042 015 2555667 27826 6 5 9309L 2568167 1356 6 048 007 2568167 13556 6 5 105530L 2580000 2000 3 053 011 2580000 20000 3 2 117334L 3013269 9580 6 255 053 Fail - - 34L - - 5506

Totgem 246587 9632 gkg 1-level 232 (176) 13 2462677 (34L 69L) 13 12Totstd= 21507 16070 5-level 186 (152) 2

68RESULTS Mean = 24626770 gkg

Repeatability variance S2r = 3666797Repeatability std Sr = 605541 --gt 246 r = 169551Between lab variance S2L = 7715586Reproducibility var S2R = 11382383Reproducibility std SR = 1066882 --gt 433 R = 298727Remarks 2 Labs rejected (34L 69L)

000 050 100 150 200 250 300 350 400

k-values

69L

35L

66L

46L

56L

32L

70L

16L

45L

36L

65L

44L

9L

30L

34L

Mandels k statistics(Compost 1 - TOC)

-600 -400 -200 00 200 400 600

Deviation from Mean

69L

35L

66L

46L

56L

32L

70L

16L

45L

36L

65L

44L

9L

30L

34L

Labo

rato

ries

Compost 1 - TOC -- Mean PARM = 2463 [gkg]

-300 -200 -100 000 100 200 300

h-values

69L

66L

56L

70L

45L

65L

9L

34L

Labo

rato

ries

Mandels h statistics(Compost 1 - TOC)

Compost 1-TOC

Unit gkg

Mandels k statistics(Compost 2 - TOC)Mandels h statistics(Compost 2 - TOC)

Sample Compost 2 Compost 2 - TOC -- Mean PARM = 1542 [gkg]

Element TOC

General calcparmT1= 994897E+03T2= 155556E+06T3= 64T4= 346T5= 41738E+03

n= variabelp= 13

N-table= 5

Mandels statistics End ResultLAB 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

45L 1326733 5665 6 -100 042 Fail 1326733 56646 6 5 -215046L 1355000 24365 4 -089 181 Fail - - 46L - - -186736L 1381949 5407 3 -078 040 Fail 1381949 54070 3 2 -159870L 1414120 - 1 -066 Fail 1414120 - 1 -127616L 1428333 5565 6 -061 041 1428333 55648 6 5 -113466L 1485550 7805 4 -039 058 1485550 78047 4 3 -56232L 1532500 5377 4 -021 040 1532500 53774 4 3 -09219L 1576833 10138 6 -004 075 1576833 101381 6 5 3519L 1582333 6166 6 -002 046 1582333 61659 6 5 40656L 1594432 4046 6 003 030 1594432 40463 6 5 52744L 1653000 3651 6 025 027 1653000 36508 6 5 111334L 1655127 13717 6 026 102 1655127 137168 6 5 113434L 1655127 13717 6 026 102 1655127 137168 6 5 113465L 1756500 16295 4 065 121 Fail 1756500 162949 4 3 214869L 2415000 30687 4 316 228 Fail - - 69L - - 8733

Totgem 158750 10900 gkg 1-level 232 (176) 13 1541734 (46L 69L) 13 12Totstd= 26187 8164 5-level 186 (152) 2

72RESULTS Mean = 15417337 gkg

Repeatability variance S2r = 8183950Repeatability std Sr = 904652 --gt 587 r = 253303Between lab variance S2L = 13631046Reproducibility var S2R = 21814995Reproducibility std SR = 1476990 --gt 958 R = 413557Remarks 2 Labs rejected (46L 69L)

000 050 100 150 200 250

k-values

45L

46L

36L

70L

16L

66L

32L

19L

9L

56L

44L

34L

34L

65L

69L

Mandels k statistics(Compost 2 - TOC)

-400 -200 00 200 400 600 800 1000

Deviation from Mean

45L

46L

36L

70L

16L

66L

32L

19L

9L

56L

44L

34L

34L

65L

69L

Labo

rato

ries

Compost 2 - TOC -- Mean PARM = 1542 [gkg]

-100 000 100 200 300 400

h-values

45L

36L

16L

32L

9L

44L

34L

69L

Labo

rato

ries

Mandels h statistics(Compost 2 - TOC)

Compost 2-TOC

Unit gkg

Mandels k statistics(Sludge 1 - TOC)Mandels h statistics(Sludge 1 - TOC)

Sample Sludge 1 Sludge 1 - TOC -- Mean PARM = 2721 [gkg]

Element TOC

General calcparmT1= 169626E+04T2= 465445E+06T3= 62T4= 326T5= 10312E+03

n= variabelp= 13

N-table= 5

Mandels statistics End ResultLAB 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

69L 233000 2362 4 -347 037 Fail - - 69L - - -2488046L 2312500 2062 4 -040 032 Fail 2312500 20616 4 3 -408565L 2615500 1708 4 004 026 2615500 17078 4 3 -105566L 2627200 8268 4 006 128 2627200 82678 4 3 -93836L 2664041 4976 3 011 077 2664041 49758 3 2 -56935L 2671500 3533 6 013 055 2671500 35331 6 5 -49556L 2692298 0874 6 016 014 Fail 2692298 08738 6 5 -28732L 2717500 6185 4 019 096 Fail 2717500 61847 4 3 -03519L 2753333 7819 6 025 121 Fail 2753333 78189 6 5 32470L 2814600 - 1 034 Fail 2814600 - 1 9369L 2853667 0398 6 039 006 Fail 2853667 03983 6 5 132716L 2860000 1673 6 040 026 Fail 2860000 16733 6 5 139045L 2884433 7033 6 044 109 Fail 2884433 70331 6 5 163544L 2906167 1129 6 047 017 Fail 2906167 11286 6 5 185234L 3186874 17674 6 089 274 Fail - - 34L - - 4659

Totgem 258617 4692 gkg 1-level 232 (176) 13 2720980 (34L 69L) 13 12Totstd= 67800 4610 5-level 186 (152) 2

72RESULTS Mean = 27209799 gkg

Repeatability variance S2r = 2104538Repeatability std Sr = 458752 --gt 169 r = 128451Between lab variance S2L = 23618387Reproducibility var S2R = 25722925Reproducibility std SR = 1603837 --gt 589 R = 449074Remarks 2 Labs rejected (34L 69L)

000 050 100 150 200 250 300

k-values

69L

46L

65L

66L

36L

35L

56L

32L

19L

70L

9L

16L

45L

44L

34L

Mandels k statistics(Sludge 1 - TOC)

-2500 -2000 -1500 -1000 -500 00 500

Deviation from Mean

69L

46L

65L

66L

36L

35L

56L

32L

19L

70L

9L

16L

45L

44L

34L

Labo

rato

ries

Sludge 1 - TOC -- Mean PARM = 2721 [gkg]

-400 -300 -200 -100 000 100

h-values

69L

65L

36L

56L

19L

9L

45L

34L

Labo

rato

ries

Mandels h statistics(Sludge 1 - TOC)

Sludge 1-TOC

68 Unit gkg

Mandels k statistics(Sludge 2 - TOC)Mandels h statistics(Sludge 2 - TOC)

Sample Sludge 2 Sludge 2 - TOC -- Mean PARM = 2207 [gkg]

Element TOC

General calcparmT1= 128601E+04T2= 285689E+06T3= 58T4= 310T5= 97826E+02

n= variabelp= 12

N-table= 5

Mandels statistics End ResultLAB 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

46L 182500 0500 4 -333 008 Fail - - 46L - - -2024466L 2029475 5267 4 -012 084 2029475 52674 4 3 -177436L 2072609 2222 3 -005 035 2072609 22222 3 2 -134365L 2084750 3865 4 -002 062 2084750 38647 4 3 -122135L 2140333 3119 6 007 050 2140333 31194 6 5 -66556L 2188021 1282 6 015 020 2188021 12822 6 5 -18819L 2223667 7916 6 022 126 Fail 2223667 79157 6 5 16832L 2242500 3096 4 025 049 Fail 2242500 30957 4 3 35645L 2266600 8322 6 029 132 Fail 2266600 83216 6 5 59770L 2272460 - 1 030 Fail 2272460 - 1 65616L 2291667 3869 6 033 062 Fail 2291667 38687 6 5 84844L 2302667 1546 6 035 025 Fail 2302667 15462 6 5 9589L 2367667 1296 6 047 021 Fail 2367667 12956 6 5 160834L 2718591 17124 6 108 273 Fail - - 34L - - 5117

Totgem 209882 4571 gkg 1-level 230 (176) 12 2206868 (34L 46L) 12 11Totstd= 57628 4485 5-level 185 (151) 2

68RESULTS Mean = 22068679 gkg

Repeatability variance S2r = 2126659Repeatability std Sr = 461157 --gt 209 r = 129124Between lab variance S2L = 9960432Reproducibility var S2R = 12087091Reproducibility std SR = 1099413 --gt 498 R = 307836Remarks 2 Labs rejected (34L 46L)

000 050 100 150 200 250 300

k-values

46L

66L

36L

65L

35L

56L

19L

32L

45L

70L

16L

44L

9L

34L

Mandels k statistics(Sludge 2 - TOC)

-2500 -2000 -1500 -1000 -500 00 500 1000

Deviation from Mean

46L

66L

36L

65L

35L

56L

19L

32L

45L

70L

16L

44L

9L

34L

Labo

rato

ries

Sludge 2 - TOC -- Mean PARM = 2207 [gkg]

-400 -300 -200 -100 000 100 200

h-values

46L

66L

36L

65L

35L

56L

19L

32L

45L

70L

16L

44L

9L

34L

Labo

rato

ries

Mandels h statistics(Sludge 2 - TOC)

Sludge 2-TOC

Unit gkg

Mandels k statistics(Soil 4 - TOC)Mandels h statistics(Soil 4 - TOC)

Sample Soil 4 Soil 4 - TOC -- Mean PARM = 1641 [gkg]

Element TOC

General calcparmT1= 102171E+03T2= 168700E+04T3= 62T4= 338T5= 94040E+00

n= variabelp= 12

N-table= 5

Mandels statistics End ResultLAB 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

36L 147161 0470 3 -036 068 Fail 147161 04702 3 2 -16965L 155250 0591 4 -032 085 Fail 155250 05909 4 3 -08844L 157900 0115 6 -031 017 Fail 157900 01152 6 5 -06232L 159250 0359 4 -031 052 Fail 159250 03594 4 3 -0489L 160500 0315 6 -030 045 Fail 160500 03146 6 5 -03656L 164927 0113 6 -028 016 Fail 164927 01127 6 5 00835L 165000 0261 6 -028 038 Fail 165000 02608 6 5 00919L 166667 0505 6 -027 073 Fail 166667 05046 6 5 02645L 168850 0763 6 -026 110 Fail 168850 07628 6 5 04816L 173333 0516 6 -024 074 Fail 173333 05164 6 5 09334L 174761 0346 6 -024 050 Fail 174761 03462 6 5 10730L 175333 0473 3 -024 068 Fail 175333 04726 3 2 11366L 189375 2035 4 -017 294 Fail - - 66L - - 25346L 227500 0500 4 000 072 - - 46L - - 63470L 1040400 - 1 360 Fail - - 70L - - 8763

Totgem 22841 0526 gkg 1-level 232 (176) 12 164078 (46L 66L70L) 12 11Totstd= 22541 0469 5-level 186 (152) 3

71RESULTS Mean = 1640777 gkg

Repeatability variance S2r = 018808Repeatability std Sr = 043368 --gt 264 r = 12143Between lab variance S2L = 054747Reproducibility var S2R = 073555Reproducibility std SR = 085764 --gt 523 R = 24014Remarks 3 Labs rejected (46L 66L70L)

000 050 100 150 200 250 300

k-values

36L

65L

44L

32L

9L

56L

35L

19L

45L

16L

34L

30L

66L

46L

70L

Mandels k statistics(Soil 4 - TOC)

-100 00 100 200 300 400 500 600 700 800 900

Deviation from Mean

36L

65L

44L

32L

9L

56L

35L

19L

45L

16L

34L

30L

66L

46L

70L

Labo

rato

ries

Soil 4 - TOC -- Mean PARM = 1641 [gkg]

-100 000 100 200 300 400

h-values

36L

44L

9L

35L

45L

34L

66L

70L

Labo

rato

ries

Mandels h statistics(Soil 4 - TOC)

Soil 4-TOC

Unit gkg

Mandels k statistics(Soil 5 - TOC)Mandels h statistics(Soil 5 - TOC)

Sample Soil 5 Soil 5 - TOC -- Mean PARM = 2102 [gkg]

Element TOC

General calcparmT1= 113661E+03T2= 240201E+04T3= 54T4= 300T5= 51756E+01

n= variabelp= 10

N-table= 5

Mandels statistics End ResultLAB 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

44L 164383 14708 6 -036 325 Fail - - 44L - - -45865L 181250 0830 4 -033 018 Fail 181250 08302 4 3 -29045L 200317 1116 6 -029 025 Fail 200317 11163 6 5 -09935L 201833 1828 6 -029 040 Fail 201833 18280 6 5 -08432L 203250 0585 4 -029 013 Fail 203250 05852 4 3 -07016L 209000 0959 6 -028 021 Fail 209000 09592 6 5 -0129L 211667 0427 6 -027 009 Fail 211667 04274 6 5 01556L 214030 0887 6 -027 020 Fail 214030 08868 6 5 03819L 216000 0795 6 -026 018 Fail 216000 07950 6 5 05834L 226009 1308 6 -024 029 Fail 226009 13076 6 5 15836L 228783 4310 3 -024 095 Fail - - 36L - - 18666L 238750 1234 4 -022 027 Fail 238750 12340 4 3 28570L 2213900 - 1 333 Fail - - 70L - - 20037

Totgem 36224 2416 gkg 1-level 227 (175) 10 210211 (36L44L 70L) 10 9Totstd= 55669 4003 5-level 184 (151) 3

64RESULTS Mean = 2102106 gkg

Repeatability variance S2r = 117627Repeatability std Sr = 108456 --gt 516 r = 30368Between lab variance S2L = 176699Reproducibility var S2R = 294326Reproducibility std SR = 171559 --gt 816 R = 48037Remarks 3 Labs rejected (36L44L 70L)

000 050 100 150 200 250 300 350

k-values

44L

65L

45L

35L

32L

16L

9L

56L

19L

34L

36L

66L

70L

Mandels k statistics(Soil 5 - TOC)

-500 00 500 1000 1500 2000 2500

Deviation from Mean

44L

65L

45L

35L

32L

16L

9L

56L

19L

34L

36L

66L

70L

Labo

rato

ries

Soil 5 - TOC -- Mean PARM = 2102 [gkg]

-100 000 100 200 300 400

h-values

44L

65L

45L

35L

32L

16L

9L

56L

19L

34L

36L

66L

70L

Labo

rato

ries

Mandels h statistics(Soil 5 - TOC)

Soil 5-TOC

17

Annex 4

Raw data submitted

Sample Compost 1 Sample Compost 2 Sample Sewage Sludge 1Element TOC [gkg] Element TOC [gkg] Element TOC [gkg]

LAB PARM LAB PARM LAB PARM30L 2600 19L 1691 19L 286730L 2580 19L 1634 19L 281430L 2560 19L 1619 19L 276934L 2969 19L 1604 19L 272034L 2936 19L 1499 19L 268834L 2958 19L 1414 19L 266234L 2994 34L 1527 34L 315234L 3199 34L 1622 34L 314934L 3024 34L 1519 34L 343035L 2306 34L 1753 34L 336535L 2300 34L 1636 34L 304235L 2298 34L 1874 34L 298335L 2296 35L 1506 35L 270735L 2291 35L 1312 35L 270335L 2259 35L 1294 35L 268836L 2546 35L 1279 35L 267436L 2527 35L 1191 35L 263136L 2470 35L 1177 35L 262644L 2583 36L 1418 36L 271344L 2581 36L 1408 36L 266544L 2578 36L 1320 36L 261444L 2539 44L 1719 44L 292044L 2528 44L 1664 44L 291644L 2525 44L 1654 44L 291245L 2658 44L 1637 44L 290045L 2600 44L 1624 44L 289645L 2546 44L 1620 44L 289345L 2461 45L 1428 45L 297645L 2409 45L 1325 45L 295245L 2350 45L 1323 45L 288546L 2460 45L 1321 45L 286646L 2400 45L 1309 45L 284046L 2370 45L 1253 45L 278746L 2350 46L 1580 46L 233056L 2436 46L 1550 46L 233056L 2435 46L 1170 46L 230056L 2405 46L 1120 46L 229056L 2397 56L 1642 56L 270256L 2375 56L 1626 56L 270156L 2358 56L 1622 56L 269465L 2587 56L 1571 56L 269365L 2542 56L 1561 56L 268465L 2483 56L 1545 56L 268066L 2454 65L 1933 65L 264166L 2429 65L 1838 65L 260966L 2365 65L 1693 65L 260766L 2262 65L 1562 65L 260569L 2730 66L 1561 66L 270169L 2250 66L 1545 66L 267469L 1440 66L 1420 66L 261969L 1420 66L 1417 66L 251470L 2435 69L 2700 69L 2639L 2594 69L 2660 69L 2409L 2570 69L 2170 69L 2199L 2565 69L 2130 69L 2109L 2563 70L 1414 70L 28159L 2562 9L 1644 9L 28579L 2555 9L 1641 9L 2856

32L 2290 9L 1602 9L 285532L 2390 9L 1589 9L 285532L 2510 9L 1526 9L 285332L 2470 9L 1492 9L 284616L 2380 32L 1470 32L 265016L 2530 32L 1520 32L 271016L 2400 32L 1540 32L 271016L 2500 32L 1600 32L 280016L 2420 16L 1400 16L 284016L 2410 16L 1440 16L 2840

16L 1470 16L 286016L 1510 16L 287016L 1360 16L 287016L 1390 16L 2880

Sample Sewage Sludge 2 Sample Soil 4 Sample Soil 5Element TOC [gkg] Element TOC [gkg] Element TOC [gkg]

LAB PARM LAB PARM LAB PARM19L 2308 19L 1720 19L 225019L 2303 19L 1700 19L 223019L 2239 19L 1690 19L 221019L 2204 19L 1670 19L 211019L 2192 19L 1640 19L 210019L 2096 19L 1580 19L 206034L 2631 30L 1790 34L 244334L 2471 30L 1770 34L 233434L 2977 30L 1700 34L 231534L 2785 34L 1740 34L 222134L 2780 34L 1692 34L 217634L 2668 34L 1727 34L 207335L 2179 34L 1767 35L 233035L 2160 34L 1777 35L 208035L 2158 34L 1783 35L 201035L 2132 35L 1700 35L 198035L 2119 35L 1650 35L 193035L 2094 35L 1650 35L 178036L 2096 35L 1640 36L 254036L 2069 35L 1630 36L 253436L 2052 35L 1630 36L 179044L 2325 36L 1500 44L 302144L 2309 36L 1497 44L 298244L 2307 36L 1417 44L 295644L 2305 44L 1594 44L 30744L 2287 44L 1587 44L 30044L 2283 44L 1584 44L 29745L 2331 44L 1574 45L 214945L 2327 44L 1573 45L 209245L 2308 44L 1562 45L 203345L 2287 45L 1827 45L 197145L 2234 45L 1709 45L 193345L 2113 45L 1666 45L 184146L 190 45L 1665 56L 223746L 180 45L 1664 56L 222246L 180 45L 1600 56L 220346L 180 46L 2300 56L 206956L 2204 46L 2300 56L 206856L 2197 46L 2300 56L 204456L 2193 46L 2200 65L 192056L 2185 56L 1668 65L 182056L 2183 56L 1654 65L 179056L 2167 56L 1653 65L 172065L 2136 56L 1643 66L 254365L 2091 56L 1639 66L 242465L 2065 56L 1638 66L 232165L 2047 65L 1630 66L 226266L 2105 65L 1560 70L 2213966L 2022 65L 1530 9L 218066L 2009 65L 1490 9L 214066L 1983 66L 2179 9L 213070L 2272 66L 1900 9L 21109L 2385 66L 1762 9L 20709L 2377 66L 1734 9L 20709L 2375 70L 10404 32L 20509L 2359 9L 1640 32L 21009L 2356 9L 1640 32L 20209L 2354 9L 1610 32L 1960

32L 2240 9L 1590 16L 210032L 2260 9L 1590 16L 220032L 2200 9L 1560 16L 220032L 2270 32L 1640 16L 206016L 2300 32L 1600 16L 197016L 2310 32L 1560 16L 201016L 2350 32L 157016L 2260 16L 170016L 2290 16L 180016L 2240 16L 1700

16L 180016L 170016L 1700

European Commission EUR 23012 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on total organic carbon Author(s) E Sobiecka H van der Sloot K Andersen B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 50 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07412-7 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 total organic carbon (TOC) in soils sludge and treated bio-waste 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

-23012-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

16

Annex 3

Statistical calculations

Unit gkg

Mandels k statistics(Compost 1 - TOC)Mandels h statistics(Compost 1 - TOC)

Sample Compost 1 Compost 1 - TOC -- Mean PARM = 2463 [gkg]

Element TOC

General calcparmT1= 142643E+04T2= 351264E+06T3= 58T4= 292T5= 16501E+03

n= variabelp= 13

N-table= 5

Mandels statistics End ResultLAB 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

69L 1960000 64265 4 -235 352 Fail - - 69L - - -502735L 2291667 1674 6 -081 009 2291667 16741 6 5 -171066L 2377425 8552 4 -041 047 2377425 85518 4 3 -85346L 2395000 4796 4 -033 026 2395000 47958 4 3 -67756L 2401227 3133 6 -030 017 2401227 31330 6 5 -61432L 2415000 9713 4 -024 053 2415000 97125 4 3 -47770L 2435100 - 1 -014 2435100 - 1 -27616L 2440000 6033 6 -012 033 2440000 60332 6 5 -22745L 2503800 11759 6 018 064 2503800 117589 6 5 41136L 2514416 3994 3 023 022 2514416 39937 3 2 51765L 2537333 5216 3 033 029 2537333 52157 3 2 74744L 2555667 2783 6 042 015 2555667 27826 6 5 9309L 2568167 1356 6 048 007 2568167 13556 6 5 105530L 2580000 2000 3 053 011 2580000 20000 3 2 117334L 3013269 9580 6 255 053 Fail - - 34L - - 5506

Totgem 246587 9632 gkg 1-level 232 (176) 13 2462677 (34L 69L) 13 12Totstd= 21507 16070 5-level 186 (152) 2

68RESULTS Mean = 24626770 gkg

Repeatability variance S2r = 3666797Repeatability std Sr = 605541 --gt 246 r = 169551Between lab variance S2L = 7715586Reproducibility var S2R = 11382383Reproducibility std SR = 1066882 --gt 433 R = 298727Remarks 2 Labs rejected (34L 69L)

000 050 100 150 200 250 300 350 400

k-values

69L

35L

66L

46L

56L

32L

70L

16L

45L

36L

65L

44L

9L

30L

34L

Mandels k statistics(Compost 1 - TOC)

-600 -400 -200 00 200 400 600

Deviation from Mean

69L

35L

66L

46L

56L

32L

70L

16L

45L

36L

65L

44L

9L

30L

34L

Labo

rato

ries

Compost 1 - TOC -- Mean PARM = 2463 [gkg]

-300 -200 -100 000 100 200 300

h-values

69L

66L

56L

70L

45L

65L

9L

34L

Labo

rato

ries

Mandels h statistics(Compost 1 - TOC)

Compost 1-TOC

Unit gkg

Mandels k statistics(Compost 2 - TOC)Mandels h statistics(Compost 2 - TOC)

Sample Compost 2 Compost 2 - TOC -- Mean PARM = 1542 [gkg]

Element TOC

General calcparmT1= 994897E+03T2= 155556E+06T3= 64T4= 346T5= 41738E+03

n= variabelp= 13

N-table= 5

Mandels statistics End ResultLAB 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

45L 1326733 5665 6 -100 042 Fail 1326733 56646 6 5 -215046L 1355000 24365 4 -089 181 Fail - - 46L - - -186736L 1381949 5407 3 -078 040 Fail 1381949 54070 3 2 -159870L 1414120 - 1 -066 Fail 1414120 - 1 -127616L 1428333 5565 6 -061 041 1428333 55648 6 5 -113466L 1485550 7805 4 -039 058 1485550 78047 4 3 -56232L 1532500 5377 4 -021 040 1532500 53774 4 3 -09219L 1576833 10138 6 -004 075 1576833 101381 6 5 3519L 1582333 6166 6 -002 046 1582333 61659 6 5 40656L 1594432 4046 6 003 030 1594432 40463 6 5 52744L 1653000 3651 6 025 027 1653000 36508 6 5 111334L 1655127 13717 6 026 102 1655127 137168 6 5 113434L 1655127 13717 6 026 102 1655127 137168 6 5 113465L 1756500 16295 4 065 121 Fail 1756500 162949 4 3 214869L 2415000 30687 4 316 228 Fail - - 69L - - 8733

Totgem 158750 10900 gkg 1-level 232 (176) 13 1541734 (46L 69L) 13 12Totstd= 26187 8164 5-level 186 (152) 2

72RESULTS Mean = 15417337 gkg

Repeatability variance S2r = 8183950Repeatability std Sr = 904652 --gt 587 r = 253303Between lab variance S2L = 13631046Reproducibility var S2R = 21814995Reproducibility std SR = 1476990 --gt 958 R = 413557Remarks 2 Labs rejected (46L 69L)

000 050 100 150 200 250

k-values

45L

46L

36L

70L

16L

66L

32L

19L

9L

56L

44L

34L

34L

65L

69L

Mandels k statistics(Compost 2 - TOC)

-400 -200 00 200 400 600 800 1000

Deviation from Mean

45L

46L

36L

70L

16L

66L

32L

19L

9L

56L

44L

34L

34L

65L

69L

Labo

rato

ries

Compost 2 - TOC -- Mean PARM = 1542 [gkg]

-100 000 100 200 300 400

h-values

45L

36L

16L

32L

9L

44L

34L

69L

Labo

rato

ries

Mandels h statistics(Compost 2 - TOC)

Compost 2-TOC

Unit gkg

Mandels k statistics(Sludge 1 - TOC)Mandels h statistics(Sludge 1 - TOC)

Sample Sludge 1 Sludge 1 - TOC -- Mean PARM = 2721 [gkg]

Element TOC

General calcparmT1= 169626E+04T2= 465445E+06T3= 62T4= 326T5= 10312E+03

n= variabelp= 13

N-table= 5

Mandels statistics End ResultLAB 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

69L 233000 2362 4 -347 037 Fail - - 69L - - -2488046L 2312500 2062 4 -040 032 Fail 2312500 20616 4 3 -408565L 2615500 1708 4 004 026 2615500 17078 4 3 -105566L 2627200 8268 4 006 128 2627200 82678 4 3 -93836L 2664041 4976 3 011 077 2664041 49758 3 2 -56935L 2671500 3533 6 013 055 2671500 35331 6 5 -49556L 2692298 0874 6 016 014 Fail 2692298 08738 6 5 -28732L 2717500 6185 4 019 096 Fail 2717500 61847 4 3 -03519L 2753333 7819 6 025 121 Fail 2753333 78189 6 5 32470L 2814600 - 1 034 Fail 2814600 - 1 9369L 2853667 0398 6 039 006 Fail 2853667 03983 6 5 132716L 2860000 1673 6 040 026 Fail 2860000 16733 6 5 139045L 2884433 7033 6 044 109 Fail 2884433 70331 6 5 163544L 2906167 1129 6 047 017 Fail 2906167 11286 6 5 185234L 3186874 17674 6 089 274 Fail - - 34L - - 4659

Totgem 258617 4692 gkg 1-level 232 (176) 13 2720980 (34L 69L) 13 12Totstd= 67800 4610 5-level 186 (152) 2

72RESULTS Mean = 27209799 gkg

Repeatability variance S2r = 2104538Repeatability std Sr = 458752 --gt 169 r = 128451Between lab variance S2L = 23618387Reproducibility var S2R = 25722925Reproducibility std SR = 1603837 --gt 589 R = 449074Remarks 2 Labs rejected (34L 69L)

000 050 100 150 200 250 300

k-values

69L

46L

65L

66L

36L

35L

56L

32L

19L

70L

9L

16L

45L

44L

34L

Mandels k statistics(Sludge 1 - TOC)

-2500 -2000 -1500 -1000 -500 00 500

Deviation from Mean

69L

46L

65L

66L

36L

35L

56L

32L

19L

70L

9L

16L

45L

44L

34L

Labo

rato

ries

Sludge 1 - TOC -- Mean PARM = 2721 [gkg]

-400 -300 -200 -100 000 100

h-values

69L

65L

36L

56L

19L

9L

45L

34L

Labo

rato

ries

Mandels h statistics(Sludge 1 - TOC)

Sludge 1-TOC

68 Unit gkg

Mandels k statistics(Sludge 2 - TOC)Mandels h statistics(Sludge 2 - TOC)

Sample Sludge 2 Sludge 2 - TOC -- Mean PARM = 2207 [gkg]

Element TOC

General calcparmT1= 128601E+04T2= 285689E+06T3= 58T4= 310T5= 97826E+02

n= variabelp= 12

N-table= 5

Mandels statistics End ResultLAB 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

46L 182500 0500 4 -333 008 Fail - - 46L - - -2024466L 2029475 5267 4 -012 084 2029475 52674 4 3 -177436L 2072609 2222 3 -005 035 2072609 22222 3 2 -134365L 2084750 3865 4 -002 062 2084750 38647 4 3 -122135L 2140333 3119 6 007 050 2140333 31194 6 5 -66556L 2188021 1282 6 015 020 2188021 12822 6 5 -18819L 2223667 7916 6 022 126 Fail 2223667 79157 6 5 16832L 2242500 3096 4 025 049 Fail 2242500 30957 4 3 35645L 2266600 8322 6 029 132 Fail 2266600 83216 6 5 59770L 2272460 - 1 030 Fail 2272460 - 1 65616L 2291667 3869 6 033 062 Fail 2291667 38687 6 5 84844L 2302667 1546 6 035 025 Fail 2302667 15462 6 5 9589L 2367667 1296 6 047 021 Fail 2367667 12956 6 5 160834L 2718591 17124 6 108 273 Fail - - 34L - - 5117

Totgem 209882 4571 gkg 1-level 230 (176) 12 2206868 (34L 46L) 12 11Totstd= 57628 4485 5-level 185 (151) 2

68RESULTS Mean = 22068679 gkg

Repeatability variance S2r = 2126659Repeatability std Sr = 461157 --gt 209 r = 129124Between lab variance S2L = 9960432Reproducibility var S2R = 12087091Reproducibility std SR = 1099413 --gt 498 R = 307836Remarks 2 Labs rejected (34L 46L)

000 050 100 150 200 250 300

k-values

46L

66L

36L

65L

35L

56L

19L

32L

45L

70L

16L

44L

9L

34L

Mandels k statistics(Sludge 2 - TOC)

-2500 -2000 -1500 -1000 -500 00 500 1000

Deviation from Mean

46L

66L

36L

65L

35L

56L

19L

32L

45L

70L

16L

44L

9L

34L

Labo

rato

ries

Sludge 2 - TOC -- Mean PARM = 2207 [gkg]

-400 -300 -200 -100 000 100 200

h-values

46L

66L

36L

65L

35L

56L

19L

32L

45L

70L

16L

44L

9L

34L

Labo

rato

ries

Mandels h statistics(Sludge 2 - TOC)

Sludge 2-TOC

Unit gkg

Mandels k statistics(Soil 4 - TOC)Mandels h statistics(Soil 4 - TOC)

Sample Soil 4 Soil 4 - TOC -- Mean PARM = 1641 [gkg]

Element TOC

General calcparmT1= 102171E+03T2= 168700E+04T3= 62T4= 338T5= 94040E+00

n= variabelp= 12

N-table= 5

Mandels statistics End ResultLAB 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

36L 147161 0470 3 -036 068 Fail 147161 04702 3 2 -16965L 155250 0591 4 -032 085 Fail 155250 05909 4 3 -08844L 157900 0115 6 -031 017 Fail 157900 01152 6 5 -06232L 159250 0359 4 -031 052 Fail 159250 03594 4 3 -0489L 160500 0315 6 -030 045 Fail 160500 03146 6 5 -03656L 164927 0113 6 -028 016 Fail 164927 01127 6 5 00835L 165000 0261 6 -028 038 Fail 165000 02608 6 5 00919L 166667 0505 6 -027 073 Fail 166667 05046 6 5 02645L 168850 0763 6 -026 110 Fail 168850 07628 6 5 04816L 173333 0516 6 -024 074 Fail 173333 05164 6 5 09334L 174761 0346 6 -024 050 Fail 174761 03462 6 5 10730L 175333 0473 3 -024 068 Fail 175333 04726 3 2 11366L 189375 2035 4 -017 294 Fail - - 66L - - 25346L 227500 0500 4 000 072 - - 46L - - 63470L 1040400 - 1 360 Fail - - 70L - - 8763

Totgem 22841 0526 gkg 1-level 232 (176) 12 164078 (46L 66L70L) 12 11Totstd= 22541 0469 5-level 186 (152) 3

71RESULTS Mean = 1640777 gkg

Repeatability variance S2r = 018808Repeatability std Sr = 043368 --gt 264 r = 12143Between lab variance S2L = 054747Reproducibility var S2R = 073555Reproducibility std SR = 085764 --gt 523 R = 24014Remarks 3 Labs rejected (46L 66L70L)

000 050 100 150 200 250 300

k-values

36L

65L

44L

32L

9L

56L

35L

19L

45L

16L

34L

30L

66L

46L

70L

Mandels k statistics(Soil 4 - TOC)

-100 00 100 200 300 400 500 600 700 800 900

Deviation from Mean

36L

65L

44L

32L

9L

56L

35L

19L

45L

16L

34L

30L

66L

46L

70L

Labo

rato

ries

Soil 4 - TOC -- Mean PARM = 1641 [gkg]

-100 000 100 200 300 400

h-values

36L

44L

9L

35L

45L

34L

66L

70L

Labo

rato

ries

Mandels h statistics(Soil 4 - TOC)

Soil 4-TOC

Unit gkg

Mandels k statistics(Soil 5 - TOC)Mandels h statistics(Soil 5 - TOC)

Sample Soil 5 Soil 5 - TOC -- Mean PARM = 2102 [gkg]

Element TOC

General calcparmT1= 113661E+03T2= 240201E+04T3= 54T4= 300T5= 51756E+01

n= variabelp= 10

N-table= 5

Mandels statistics End ResultLAB 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

44L 164383 14708 6 -036 325 Fail - - 44L - - -45865L 181250 0830 4 -033 018 Fail 181250 08302 4 3 -29045L 200317 1116 6 -029 025 Fail 200317 11163 6 5 -09935L 201833 1828 6 -029 040 Fail 201833 18280 6 5 -08432L 203250 0585 4 -029 013 Fail 203250 05852 4 3 -07016L 209000 0959 6 -028 021 Fail 209000 09592 6 5 -0129L 211667 0427 6 -027 009 Fail 211667 04274 6 5 01556L 214030 0887 6 -027 020 Fail 214030 08868 6 5 03819L 216000 0795 6 -026 018 Fail 216000 07950 6 5 05834L 226009 1308 6 -024 029 Fail 226009 13076 6 5 15836L 228783 4310 3 -024 095 Fail - - 36L - - 18666L 238750 1234 4 -022 027 Fail 238750 12340 4 3 28570L 2213900 - 1 333 Fail - - 70L - - 20037

Totgem 36224 2416 gkg 1-level 227 (175) 10 210211 (36L44L 70L) 10 9Totstd= 55669 4003 5-level 184 (151) 3

64RESULTS Mean = 2102106 gkg

Repeatability variance S2r = 117627Repeatability std Sr = 108456 --gt 516 r = 30368Between lab variance S2L = 176699Reproducibility var S2R = 294326Reproducibility std SR = 171559 --gt 816 R = 48037Remarks 3 Labs rejected (36L44L 70L)

000 050 100 150 200 250 300 350

k-values

44L

65L

45L

35L

32L

16L

9L

56L

19L

34L

36L

66L

70L

Mandels k statistics(Soil 5 - TOC)

-500 00 500 1000 1500 2000 2500

Deviation from Mean

44L

65L

45L

35L

32L

16L

9L

56L

19L

34L

36L

66L

70L

Labo

rato

ries

Soil 5 - TOC -- Mean PARM = 2102 [gkg]

-100 000 100 200 300 400

h-values

44L

65L

45L

35L

32L

16L

9L

56L

19L

34L

36L

66L

70L

Labo

rato

ries

Mandels h statistics(Soil 5 - TOC)

Soil 5-TOC

17

Annex 4

Raw data submitted

Sample Compost 1 Sample Compost 2 Sample Sewage Sludge 1Element TOC [gkg] Element TOC [gkg] Element TOC [gkg]

LAB PARM LAB PARM LAB PARM30L 2600 19L 1691 19L 286730L 2580 19L 1634 19L 281430L 2560 19L 1619 19L 276934L 2969 19L 1604 19L 272034L 2936 19L 1499 19L 268834L 2958 19L 1414 19L 266234L 2994 34L 1527 34L 315234L 3199 34L 1622 34L 314934L 3024 34L 1519 34L 343035L 2306 34L 1753 34L 336535L 2300 34L 1636 34L 304235L 2298 34L 1874 34L 298335L 2296 35L 1506 35L 270735L 2291 35L 1312 35L 270335L 2259 35L 1294 35L 268836L 2546 35L 1279 35L 267436L 2527 35L 1191 35L 263136L 2470 35L 1177 35L 262644L 2583 36L 1418 36L 271344L 2581 36L 1408 36L 266544L 2578 36L 1320 36L 261444L 2539 44L 1719 44L 292044L 2528 44L 1664 44L 291644L 2525 44L 1654 44L 291245L 2658 44L 1637 44L 290045L 2600 44L 1624 44L 289645L 2546 44L 1620 44L 289345L 2461 45L 1428 45L 297645L 2409 45L 1325 45L 295245L 2350 45L 1323 45L 288546L 2460 45L 1321 45L 286646L 2400 45L 1309 45L 284046L 2370 45L 1253 45L 278746L 2350 46L 1580 46L 233056L 2436 46L 1550 46L 233056L 2435 46L 1170 46L 230056L 2405 46L 1120 46L 229056L 2397 56L 1642 56L 270256L 2375 56L 1626 56L 270156L 2358 56L 1622 56L 269465L 2587 56L 1571 56L 269365L 2542 56L 1561 56L 268465L 2483 56L 1545 56L 268066L 2454 65L 1933 65L 264166L 2429 65L 1838 65L 260966L 2365 65L 1693 65L 260766L 2262 65L 1562 65L 260569L 2730 66L 1561 66L 270169L 2250 66L 1545 66L 267469L 1440 66L 1420 66L 261969L 1420 66L 1417 66L 251470L 2435 69L 2700 69L 2639L 2594 69L 2660 69L 2409L 2570 69L 2170 69L 2199L 2565 69L 2130 69L 2109L 2563 70L 1414 70L 28159L 2562 9L 1644 9L 28579L 2555 9L 1641 9L 2856

32L 2290 9L 1602 9L 285532L 2390 9L 1589 9L 285532L 2510 9L 1526 9L 285332L 2470 9L 1492 9L 284616L 2380 32L 1470 32L 265016L 2530 32L 1520 32L 271016L 2400 32L 1540 32L 271016L 2500 32L 1600 32L 280016L 2420 16L 1400 16L 284016L 2410 16L 1440 16L 2840

16L 1470 16L 286016L 1510 16L 287016L 1360 16L 287016L 1390 16L 2880

Sample Sewage Sludge 2 Sample Soil 4 Sample Soil 5Element TOC [gkg] Element TOC [gkg] Element TOC [gkg]

LAB PARM LAB PARM LAB PARM19L 2308 19L 1720 19L 225019L 2303 19L 1700 19L 223019L 2239 19L 1690 19L 221019L 2204 19L 1670 19L 211019L 2192 19L 1640 19L 210019L 2096 19L 1580 19L 206034L 2631 30L 1790 34L 244334L 2471 30L 1770 34L 233434L 2977 30L 1700 34L 231534L 2785 34L 1740 34L 222134L 2780 34L 1692 34L 217634L 2668 34L 1727 34L 207335L 2179 34L 1767 35L 233035L 2160 34L 1777 35L 208035L 2158 34L 1783 35L 201035L 2132 35L 1700 35L 198035L 2119 35L 1650 35L 193035L 2094 35L 1650 35L 178036L 2096 35L 1640 36L 254036L 2069 35L 1630 36L 253436L 2052 35L 1630 36L 179044L 2325 36L 1500 44L 302144L 2309 36L 1497 44L 298244L 2307 36L 1417 44L 295644L 2305 44L 1594 44L 30744L 2287 44L 1587 44L 30044L 2283 44L 1584 44L 29745L 2331 44L 1574 45L 214945L 2327 44L 1573 45L 209245L 2308 44L 1562 45L 203345L 2287 45L 1827 45L 197145L 2234 45L 1709 45L 193345L 2113 45L 1666 45L 184146L 190 45L 1665 56L 223746L 180 45L 1664 56L 222246L 180 45L 1600 56L 220346L 180 46L 2300 56L 206956L 2204 46L 2300 56L 206856L 2197 46L 2300 56L 204456L 2193 46L 2200 65L 192056L 2185 56L 1668 65L 182056L 2183 56L 1654 65L 179056L 2167 56L 1653 65L 172065L 2136 56L 1643 66L 254365L 2091 56L 1639 66L 242465L 2065 56L 1638 66L 232165L 2047 65L 1630 66L 226266L 2105 65L 1560 70L 2213966L 2022 65L 1530 9L 218066L 2009 65L 1490 9L 214066L 1983 66L 2179 9L 213070L 2272 66L 1900 9L 21109L 2385 66L 1762 9L 20709L 2377 66L 1734 9L 20709L 2375 70L 10404 32L 20509L 2359 9L 1640 32L 21009L 2356 9L 1640 32L 20209L 2354 9L 1610 32L 1960

32L 2240 9L 1590 16L 210032L 2260 9L 1590 16L 220032L 2200 9L 1560 16L 220032L 2270 32L 1640 16L 206016L 2300 32L 1600 16L 197016L 2310 32L 1560 16L 201016L 2350 32L 157016L 2260 16L 170016L 2290 16L 180016L 2240 16L 1700

16L 180016L 170016L 1700

European Commission EUR 23012 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on total organic carbon Author(s) E Sobiecka H van der Sloot K Andersen B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 50 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07412-7 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 total organic carbon (TOC) in soils sludge and treated bio-waste 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

-23012-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

16

Annex 3

Statistical calculations

Unit gkg

Mandels k statistics(Compost 1 - TOC)Mandels h statistics(Compost 1 - TOC)

Sample Compost 1 Compost 1 - TOC -- Mean PARM = 2463 [gkg]

Element TOC

General calcparmT1= 142643E+04T2= 351264E+06T3= 58T4= 292T5= 16501E+03

n= variabelp= 13

N-table= 5

Mandels statistics End ResultLAB 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

69L 1960000 64265 4 -235 352 Fail - - 69L - - -502735L 2291667 1674 6 -081 009 2291667 16741 6 5 -171066L 2377425 8552 4 -041 047 2377425 85518 4 3 -85346L 2395000 4796 4 -033 026 2395000 47958 4 3 -67756L 2401227 3133 6 -030 017 2401227 31330 6 5 -61432L 2415000 9713 4 -024 053 2415000 97125 4 3 -47770L 2435100 - 1 -014 2435100 - 1 -27616L 2440000 6033 6 -012 033 2440000 60332 6 5 -22745L 2503800 11759 6 018 064 2503800 117589 6 5 41136L 2514416 3994 3 023 022 2514416 39937 3 2 51765L 2537333 5216 3 033 029 2537333 52157 3 2 74744L 2555667 2783 6 042 015 2555667 27826 6 5 9309L 2568167 1356 6 048 007 2568167 13556 6 5 105530L 2580000 2000 3 053 011 2580000 20000 3 2 117334L 3013269 9580 6 255 053 Fail - - 34L - - 5506

Totgem 246587 9632 gkg 1-level 232 (176) 13 2462677 (34L 69L) 13 12Totstd= 21507 16070 5-level 186 (152) 2

68RESULTS Mean = 24626770 gkg

Repeatability variance S2r = 3666797Repeatability std Sr = 605541 --gt 246 r = 169551Between lab variance S2L = 7715586Reproducibility var S2R = 11382383Reproducibility std SR = 1066882 --gt 433 R = 298727Remarks 2 Labs rejected (34L 69L)

000 050 100 150 200 250 300 350 400

k-values

69L

35L

66L

46L

56L

32L

70L

16L

45L

36L

65L

44L

9L

30L

34L

Mandels k statistics(Compost 1 - TOC)

-600 -400 -200 00 200 400 600

Deviation from Mean

69L

35L

66L

46L

56L

32L

70L

16L

45L

36L

65L

44L

9L

30L

34L

Labo

rato

ries

Compost 1 - TOC -- Mean PARM = 2463 [gkg]

-300 -200 -100 000 100 200 300

h-values

69L

66L

56L

70L

45L

65L

9L

34L

Labo

rato

ries

Mandels h statistics(Compost 1 - TOC)

Compost 1-TOC

Unit gkg

Mandels k statistics(Compost 2 - TOC)Mandels h statistics(Compost 2 - TOC)

Sample Compost 2 Compost 2 - TOC -- Mean PARM = 1542 [gkg]

Element TOC

General calcparmT1= 994897E+03T2= 155556E+06T3= 64T4= 346T5= 41738E+03

n= variabelp= 13

N-table= 5

Mandels statistics End ResultLAB 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

45L 1326733 5665 6 -100 042 Fail 1326733 56646 6 5 -215046L 1355000 24365 4 -089 181 Fail - - 46L - - -186736L 1381949 5407 3 -078 040 Fail 1381949 54070 3 2 -159870L 1414120 - 1 -066 Fail 1414120 - 1 -127616L 1428333 5565 6 -061 041 1428333 55648 6 5 -113466L 1485550 7805 4 -039 058 1485550 78047 4 3 -56232L 1532500 5377 4 -021 040 1532500 53774 4 3 -09219L 1576833 10138 6 -004 075 1576833 101381 6 5 3519L 1582333 6166 6 -002 046 1582333 61659 6 5 40656L 1594432 4046 6 003 030 1594432 40463 6 5 52744L 1653000 3651 6 025 027 1653000 36508 6 5 111334L 1655127 13717 6 026 102 1655127 137168 6 5 113434L 1655127 13717 6 026 102 1655127 137168 6 5 113465L 1756500 16295 4 065 121 Fail 1756500 162949 4 3 214869L 2415000 30687 4 316 228 Fail - - 69L - - 8733

Totgem 158750 10900 gkg 1-level 232 (176) 13 1541734 (46L 69L) 13 12Totstd= 26187 8164 5-level 186 (152) 2

72RESULTS Mean = 15417337 gkg

Repeatability variance S2r = 8183950Repeatability std Sr = 904652 --gt 587 r = 253303Between lab variance S2L = 13631046Reproducibility var S2R = 21814995Reproducibility std SR = 1476990 --gt 958 R = 413557Remarks 2 Labs rejected (46L 69L)

000 050 100 150 200 250

k-values

45L

46L

36L

70L

16L

66L

32L

19L

9L

56L

44L

34L

34L

65L

69L

Mandels k statistics(Compost 2 - TOC)

-400 -200 00 200 400 600 800 1000

Deviation from Mean

45L

46L

36L

70L

16L

66L

32L

19L

9L

56L

44L

34L

34L

65L

69L

Labo

rato

ries

Compost 2 - TOC -- Mean PARM = 1542 [gkg]

-100 000 100 200 300 400

h-values

45L

36L

16L

32L

9L

44L

34L

69L

Labo

rato

ries

Mandels h statistics(Compost 2 - TOC)

Compost 2-TOC

Unit gkg

Mandels k statistics(Sludge 1 - TOC)Mandels h statistics(Sludge 1 - TOC)

Sample Sludge 1 Sludge 1 - TOC -- Mean PARM = 2721 [gkg]

Element TOC

General calcparmT1= 169626E+04T2= 465445E+06T3= 62T4= 326T5= 10312E+03

n= variabelp= 13

N-table= 5

Mandels statistics End ResultLAB 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

69L 233000 2362 4 -347 037 Fail - - 69L - - -2488046L 2312500 2062 4 -040 032 Fail 2312500 20616 4 3 -408565L 2615500 1708 4 004 026 2615500 17078 4 3 -105566L 2627200 8268 4 006 128 2627200 82678 4 3 -93836L 2664041 4976 3 011 077 2664041 49758 3 2 -56935L 2671500 3533 6 013 055 2671500 35331 6 5 -49556L 2692298 0874 6 016 014 Fail 2692298 08738 6 5 -28732L 2717500 6185 4 019 096 Fail 2717500 61847 4 3 -03519L 2753333 7819 6 025 121 Fail 2753333 78189 6 5 32470L 2814600 - 1 034 Fail 2814600 - 1 9369L 2853667 0398 6 039 006 Fail 2853667 03983 6 5 132716L 2860000 1673 6 040 026 Fail 2860000 16733 6 5 139045L 2884433 7033 6 044 109 Fail 2884433 70331 6 5 163544L 2906167 1129 6 047 017 Fail 2906167 11286 6 5 185234L 3186874 17674 6 089 274 Fail - - 34L - - 4659

Totgem 258617 4692 gkg 1-level 232 (176) 13 2720980 (34L 69L) 13 12Totstd= 67800 4610 5-level 186 (152) 2

72RESULTS Mean = 27209799 gkg

Repeatability variance S2r = 2104538Repeatability std Sr = 458752 --gt 169 r = 128451Between lab variance S2L = 23618387Reproducibility var S2R = 25722925Reproducibility std SR = 1603837 --gt 589 R = 449074Remarks 2 Labs rejected (34L 69L)

000 050 100 150 200 250 300

k-values

69L

46L

65L

66L

36L

35L

56L

32L

19L

70L

9L

16L

45L

44L

34L

Mandels k statistics(Sludge 1 - TOC)

-2500 -2000 -1500 -1000 -500 00 500

Deviation from Mean

69L

46L

65L

66L

36L

35L

56L

32L

19L

70L

9L

16L

45L

44L

34L

Labo

rato

ries

Sludge 1 - TOC -- Mean PARM = 2721 [gkg]

-400 -300 -200 -100 000 100

h-values

69L

65L

36L

56L

19L

9L

45L

34L

Labo

rato

ries

Mandels h statistics(Sludge 1 - TOC)

Sludge 1-TOC

68 Unit gkg

Mandels k statistics(Sludge 2 - TOC)Mandels h statistics(Sludge 2 - TOC)

Sample Sludge 2 Sludge 2 - TOC -- Mean PARM = 2207 [gkg]

Element TOC

General calcparmT1= 128601E+04T2= 285689E+06T3= 58T4= 310T5= 97826E+02

n= variabelp= 12

N-table= 5

Mandels statistics End ResultLAB 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

46L 182500 0500 4 -333 008 Fail - - 46L - - -2024466L 2029475 5267 4 -012 084 2029475 52674 4 3 -177436L 2072609 2222 3 -005 035 2072609 22222 3 2 -134365L 2084750 3865 4 -002 062 2084750 38647 4 3 -122135L 2140333 3119 6 007 050 2140333 31194 6 5 -66556L 2188021 1282 6 015 020 2188021 12822 6 5 -18819L 2223667 7916 6 022 126 Fail 2223667 79157 6 5 16832L 2242500 3096 4 025 049 Fail 2242500 30957 4 3 35645L 2266600 8322 6 029 132 Fail 2266600 83216 6 5 59770L 2272460 - 1 030 Fail 2272460 - 1 65616L 2291667 3869 6 033 062 Fail 2291667 38687 6 5 84844L 2302667 1546 6 035 025 Fail 2302667 15462 6 5 9589L 2367667 1296 6 047 021 Fail 2367667 12956 6 5 160834L 2718591 17124 6 108 273 Fail - - 34L - - 5117

Totgem 209882 4571 gkg 1-level 230 (176) 12 2206868 (34L 46L) 12 11Totstd= 57628 4485 5-level 185 (151) 2

68RESULTS Mean = 22068679 gkg

Repeatability variance S2r = 2126659Repeatability std Sr = 461157 --gt 209 r = 129124Between lab variance S2L = 9960432Reproducibility var S2R = 12087091Reproducibility std SR = 1099413 --gt 498 R = 307836Remarks 2 Labs rejected (34L 46L)

000 050 100 150 200 250 300

k-values

46L

66L

36L

65L

35L

56L

19L

32L

45L

70L

16L

44L

9L

34L

Mandels k statistics(Sludge 2 - TOC)

-2500 -2000 -1500 -1000 -500 00 500 1000

Deviation from Mean

46L

66L

36L

65L

35L

56L

19L

32L

45L

70L

16L

44L

9L

34L

Labo

rato

ries

Sludge 2 - TOC -- Mean PARM = 2207 [gkg]

-400 -300 -200 -100 000 100 200

h-values

46L

66L

36L

65L

35L

56L

19L

32L

45L

70L

16L

44L

9L

34L

Labo

rato

ries

Mandels h statistics(Sludge 2 - TOC)

Sludge 2-TOC

Unit gkg

Mandels k statistics(Soil 4 - TOC)Mandels h statistics(Soil 4 - TOC)

Sample Soil 4 Soil 4 - TOC -- Mean PARM = 1641 [gkg]

Element TOC

General calcparmT1= 102171E+03T2= 168700E+04T3= 62T4= 338T5= 94040E+00

n= variabelp= 12

N-table= 5

Mandels statistics End ResultLAB 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

36L 147161 0470 3 -036 068 Fail 147161 04702 3 2 -16965L 155250 0591 4 -032 085 Fail 155250 05909 4 3 -08844L 157900 0115 6 -031 017 Fail 157900 01152 6 5 -06232L 159250 0359 4 -031 052 Fail 159250 03594 4 3 -0489L 160500 0315 6 -030 045 Fail 160500 03146 6 5 -03656L 164927 0113 6 -028 016 Fail 164927 01127 6 5 00835L 165000 0261 6 -028 038 Fail 165000 02608 6 5 00919L 166667 0505 6 -027 073 Fail 166667 05046 6 5 02645L 168850 0763 6 -026 110 Fail 168850 07628 6 5 04816L 173333 0516 6 -024 074 Fail 173333 05164 6 5 09334L 174761 0346 6 -024 050 Fail 174761 03462 6 5 10730L 175333 0473 3 -024 068 Fail 175333 04726 3 2 11366L 189375 2035 4 -017 294 Fail - - 66L - - 25346L 227500 0500 4 000 072 - - 46L - - 63470L 1040400 - 1 360 Fail - - 70L - - 8763

Totgem 22841 0526 gkg 1-level 232 (176) 12 164078 (46L 66L70L) 12 11Totstd= 22541 0469 5-level 186 (152) 3

71RESULTS Mean = 1640777 gkg

Repeatability variance S2r = 018808Repeatability std Sr = 043368 --gt 264 r = 12143Between lab variance S2L = 054747Reproducibility var S2R = 073555Reproducibility std SR = 085764 --gt 523 R = 24014Remarks 3 Labs rejected (46L 66L70L)

000 050 100 150 200 250 300

k-values

36L

65L

44L

32L

9L

56L

35L

19L

45L

16L

34L

30L

66L

46L

70L

Mandels k statistics(Soil 4 - TOC)

-100 00 100 200 300 400 500 600 700 800 900

Deviation from Mean

36L

65L

44L

32L

9L

56L

35L

19L

45L

16L

34L

30L

66L

46L

70L

Labo

rato

ries

Soil 4 - TOC -- Mean PARM = 1641 [gkg]

-100 000 100 200 300 400

h-values

36L

44L

9L

35L

45L

34L

66L

70L

Labo

rato

ries

Mandels h statistics(Soil 4 - TOC)

Soil 4-TOC

Unit gkg

Mandels k statistics(Soil 5 - TOC)Mandels h statistics(Soil 5 - TOC)

Sample Soil 5 Soil 5 - TOC -- Mean PARM = 2102 [gkg]

Element TOC

General calcparmT1= 113661E+03T2= 240201E+04T3= 54T4= 300T5= 51756E+01

n= variabelp= 10

N-table= 5

Mandels statistics End ResultLAB 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

44L 164383 14708 6 -036 325 Fail - - 44L - - -45865L 181250 0830 4 -033 018 Fail 181250 08302 4 3 -29045L 200317 1116 6 -029 025 Fail 200317 11163 6 5 -09935L 201833 1828 6 -029 040 Fail 201833 18280 6 5 -08432L 203250 0585 4 -029 013 Fail 203250 05852 4 3 -07016L 209000 0959 6 -028 021 Fail 209000 09592 6 5 -0129L 211667 0427 6 -027 009 Fail 211667 04274 6 5 01556L 214030 0887 6 -027 020 Fail 214030 08868 6 5 03819L 216000 0795 6 -026 018 Fail 216000 07950 6 5 05834L 226009 1308 6 -024 029 Fail 226009 13076 6 5 15836L 228783 4310 3 -024 095 Fail - - 36L - - 18666L 238750 1234 4 -022 027 Fail 238750 12340 4 3 28570L 2213900 - 1 333 Fail - - 70L - - 20037

Totgem 36224 2416 gkg 1-level 227 (175) 10 210211 (36L44L 70L) 10 9Totstd= 55669 4003 5-level 184 (151) 3

64RESULTS Mean = 2102106 gkg

Repeatability variance S2r = 117627Repeatability std Sr = 108456 --gt 516 r = 30368Between lab variance S2L = 176699Reproducibility var S2R = 294326Reproducibility std SR = 171559 --gt 816 R = 48037Remarks 3 Labs rejected (36L44L 70L)

000 050 100 150 200 250 300 350

k-values

44L

65L

45L

35L

32L

16L

9L

56L

19L

34L

36L

66L

70L

Mandels k statistics(Soil 5 - TOC)

-500 00 500 1000 1500 2000 2500

Deviation from Mean

44L

65L

45L

35L

32L

16L

9L

56L

19L

34L

36L

66L

70L

Labo

rato

ries

Soil 5 - TOC -- Mean PARM = 2102 [gkg]

-100 000 100 200 300 400

h-values

44L

65L

45L

35L

32L

16L

9L

56L

19L

34L

36L

66L

70L

Labo

rato

ries

Mandels h statistics(Soil 5 - TOC)

Soil 5-TOC

17

Annex 4

Raw data submitted

Sample Compost 1 Sample Compost 2 Sample Sewage Sludge 1Element TOC [gkg] Element TOC [gkg] Element TOC [gkg]

LAB PARM LAB PARM LAB PARM30L 2600 19L 1691 19L 286730L 2580 19L 1634 19L 281430L 2560 19L 1619 19L 276934L 2969 19L 1604 19L 272034L 2936 19L 1499 19L 268834L 2958 19L 1414 19L 266234L 2994 34L 1527 34L 315234L 3199 34L 1622 34L 314934L 3024 34L 1519 34L 343035L 2306 34L 1753 34L 336535L 2300 34L 1636 34L 304235L 2298 34L 1874 34L 298335L 2296 35L 1506 35L 270735L 2291 35L 1312 35L 270335L 2259 35L 1294 35L 268836L 2546 35L 1279 35L 267436L 2527 35L 1191 35L 263136L 2470 35L 1177 35L 262644L 2583 36L 1418 36L 271344L 2581 36L 1408 36L 266544L 2578 36L 1320 36L 261444L 2539 44L 1719 44L 292044L 2528 44L 1664 44L 291644L 2525 44L 1654 44L 291245L 2658 44L 1637 44L 290045L 2600 44L 1624 44L 289645L 2546 44L 1620 44L 289345L 2461 45L 1428 45L 297645L 2409 45L 1325 45L 295245L 2350 45L 1323 45L 288546L 2460 45L 1321 45L 286646L 2400 45L 1309 45L 284046L 2370 45L 1253 45L 278746L 2350 46L 1580 46L 233056L 2436 46L 1550 46L 233056L 2435 46L 1170 46L 230056L 2405 46L 1120 46L 229056L 2397 56L 1642 56L 270256L 2375 56L 1626 56L 270156L 2358 56L 1622 56L 269465L 2587 56L 1571 56L 269365L 2542 56L 1561 56L 268465L 2483 56L 1545 56L 268066L 2454 65L 1933 65L 264166L 2429 65L 1838 65L 260966L 2365 65L 1693 65L 260766L 2262 65L 1562 65L 260569L 2730 66L 1561 66L 270169L 2250 66L 1545 66L 267469L 1440 66L 1420 66L 261969L 1420 66L 1417 66L 251470L 2435 69L 2700 69L 2639L 2594 69L 2660 69L 2409L 2570 69L 2170 69L 2199L 2565 69L 2130 69L 2109L 2563 70L 1414 70L 28159L 2562 9L 1644 9L 28579L 2555 9L 1641 9L 2856

32L 2290 9L 1602 9L 285532L 2390 9L 1589 9L 285532L 2510 9L 1526 9L 285332L 2470 9L 1492 9L 284616L 2380 32L 1470 32L 265016L 2530 32L 1520 32L 271016L 2400 32L 1540 32L 271016L 2500 32L 1600 32L 280016L 2420 16L 1400 16L 284016L 2410 16L 1440 16L 2840

16L 1470 16L 286016L 1510 16L 287016L 1360 16L 287016L 1390 16L 2880

Sample Sewage Sludge 2 Sample Soil 4 Sample Soil 5Element TOC [gkg] Element TOC [gkg] Element TOC [gkg]

LAB PARM LAB PARM LAB PARM19L 2308 19L 1720 19L 225019L 2303 19L 1700 19L 223019L 2239 19L 1690 19L 221019L 2204 19L 1670 19L 211019L 2192 19L 1640 19L 210019L 2096 19L 1580 19L 206034L 2631 30L 1790 34L 244334L 2471 30L 1770 34L 233434L 2977 30L 1700 34L 231534L 2785 34L 1740 34L 222134L 2780 34L 1692 34L 217634L 2668 34L 1727 34L 207335L 2179 34L 1767 35L 233035L 2160 34L 1777 35L 208035L 2158 34L 1783 35L 201035L 2132 35L 1700 35L 198035L 2119 35L 1650 35L 193035L 2094 35L 1650 35L 178036L 2096 35L 1640 36L 254036L 2069 35L 1630 36L 253436L 2052 35L 1630 36L 179044L 2325 36L 1500 44L 302144L 2309 36L 1497 44L 298244L 2307 36L 1417 44L 295644L 2305 44L 1594 44L 30744L 2287 44L 1587 44L 30044L 2283 44L 1584 44L 29745L 2331 44L 1574 45L 214945L 2327 44L 1573 45L 209245L 2308 44L 1562 45L 203345L 2287 45L 1827 45L 197145L 2234 45L 1709 45L 193345L 2113 45L 1666 45L 184146L 190 45L 1665 56L 223746L 180 45L 1664 56L 222246L 180 45L 1600 56L 220346L 180 46L 2300 56L 206956L 2204 46L 2300 56L 206856L 2197 46L 2300 56L 204456L 2193 46L 2200 65L 192056L 2185 56L 1668 65L 182056L 2183 56L 1654 65L 179056L 2167 56L 1653 65L 172065L 2136 56L 1643 66L 254365L 2091 56L 1639 66L 242465L 2065 56L 1638 66L 232165L 2047 65L 1630 66L 226266L 2105 65L 1560 70L 2213966L 2022 65L 1530 9L 218066L 2009 65L 1490 9L 214066L 1983 66L 2179 9L 213070L 2272 66L 1900 9L 21109L 2385 66L 1762 9L 20709L 2377 66L 1734 9L 20709L 2375 70L 10404 32L 20509L 2359 9L 1640 32L 21009L 2356 9L 1640 32L 20209L 2354 9L 1610 32L 1960

32L 2240 9L 1590 16L 210032L 2260 9L 1590 16L 220032L 2200 9L 1560 16L 220032L 2270 32L 1640 16L 206016L 2300 32L 1600 16L 197016L 2310 32L 1560 16L 201016L 2350 32L 157016L 2260 16L 170016L 2290 16L 180016L 2240 16L 1700

16L 180016L 170016L 1700

European Commission EUR 23012 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on total organic carbon Author(s) E Sobiecka H van der Sloot K Andersen B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 50 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07412-7 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 total organic carbon (TOC) in soils sludge and treated bio-waste 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

-23012-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

16

Annex 3

Statistical calculations

Unit gkg

Mandels k statistics(Compost 1 - TOC)Mandels h statistics(Compost 1 - TOC)

Sample Compost 1 Compost 1 - TOC -- Mean PARM = 2463 [gkg]

Element TOC

General calcparmT1= 142643E+04T2= 351264E+06T3= 58T4= 292T5= 16501E+03

n= variabelp= 13

N-table= 5

Mandels statistics End ResultLAB 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

69L 1960000 64265 4 -235 352 Fail - - 69L - - -502735L 2291667 1674 6 -081 009 2291667 16741 6 5 -171066L 2377425 8552 4 -041 047 2377425 85518 4 3 -85346L 2395000 4796 4 -033 026 2395000 47958 4 3 -67756L 2401227 3133 6 -030 017 2401227 31330 6 5 -61432L 2415000 9713 4 -024 053 2415000 97125 4 3 -47770L 2435100 - 1 -014 2435100 - 1 -27616L 2440000 6033 6 -012 033 2440000 60332 6 5 -22745L 2503800 11759 6 018 064 2503800 117589 6 5 41136L 2514416 3994 3 023 022 2514416 39937 3 2 51765L 2537333 5216 3 033 029 2537333 52157 3 2 74744L 2555667 2783 6 042 015 2555667 27826 6 5 9309L 2568167 1356 6 048 007 2568167 13556 6 5 105530L 2580000 2000 3 053 011 2580000 20000 3 2 117334L 3013269 9580 6 255 053 Fail - - 34L - - 5506

Totgem 246587 9632 gkg 1-level 232 (176) 13 2462677 (34L 69L) 13 12Totstd= 21507 16070 5-level 186 (152) 2

68RESULTS Mean = 24626770 gkg

Repeatability variance S2r = 3666797Repeatability std Sr = 605541 --gt 246 r = 169551Between lab variance S2L = 7715586Reproducibility var S2R = 11382383Reproducibility std SR = 1066882 --gt 433 R = 298727Remarks 2 Labs rejected (34L 69L)

000 050 100 150 200 250 300 350 400

k-values

69L

35L

66L

46L

56L

32L

70L

16L

45L

36L

65L

44L

9L

30L

34L

Mandels k statistics(Compost 1 - TOC)

-600 -400 -200 00 200 400 600

Deviation from Mean

69L

35L

66L

46L

56L

32L

70L

16L

45L

36L

65L

44L

9L

30L

34L

Labo

rato

ries

Compost 1 - TOC -- Mean PARM = 2463 [gkg]

-300 -200 -100 000 100 200 300

h-values

69L

66L

56L

70L

45L

65L

9L

34L

Labo

rato

ries

Mandels h statistics(Compost 1 - TOC)

Compost 1-TOC

Unit gkg

Mandels k statistics(Compost 2 - TOC)Mandels h statistics(Compost 2 - TOC)

Sample Compost 2 Compost 2 - TOC -- Mean PARM = 1542 [gkg]

Element TOC

General calcparmT1= 994897E+03T2= 155556E+06T3= 64T4= 346T5= 41738E+03

n= variabelp= 13

N-table= 5

Mandels statistics End ResultLAB 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

45L 1326733 5665 6 -100 042 Fail 1326733 56646 6 5 -215046L 1355000 24365 4 -089 181 Fail - - 46L - - -186736L 1381949 5407 3 -078 040 Fail 1381949 54070 3 2 -159870L 1414120 - 1 -066 Fail 1414120 - 1 -127616L 1428333 5565 6 -061 041 1428333 55648 6 5 -113466L 1485550 7805 4 -039 058 1485550 78047 4 3 -56232L 1532500 5377 4 -021 040 1532500 53774 4 3 -09219L 1576833 10138 6 -004 075 1576833 101381 6 5 3519L 1582333 6166 6 -002 046 1582333 61659 6 5 40656L 1594432 4046 6 003 030 1594432 40463 6 5 52744L 1653000 3651 6 025 027 1653000 36508 6 5 111334L 1655127 13717 6 026 102 1655127 137168 6 5 113434L 1655127 13717 6 026 102 1655127 137168 6 5 113465L 1756500 16295 4 065 121 Fail 1756500 162949 4 3 214869L 2415000 30687 4 316 228 Fail - - 69L - - 8733

Totgem 158750 10900 gkg 1-level 232 (176) 13 1541734 (46L 69L) 13 12Totstd= 26187 8164 5-level 186 (152) 2

72RESULTS Mean = 15417337 gkg

Repeatability variance S2r = 8183950Repeatability std Sr = 904652 --gt 587 r = 253303Between lab variance S2L = 13631046Reproducibility var S2R = 21814995Reproducibility std SR = 1476990 --gt 958 R = 413557Remarks 2 Labs rejected (46L 69L)

000 050 100 150 200 250

k-values

45L

46L

36L

70L

16L

66L

32L

19L

9L

56L

44L

34L

34L

65L

69L

Mandels k statistics(Compost 2 - TOC)

-400 -200 00 200 400 600 800 1000

Deviation from Mean

45L

46L

36L

70L

16L

66L

32L

19L

9L

56L

44L

34L

34L

65L

69L

Labo

rato

ries

Compost 2 - TOC -- Mean PARM = 1542 [gkg]

-100 000 100 200 300 400

h-values

45L

36L

16L

32L

9L

44L

34L

69L

Labo

rato

ries

Mandels h statistics(Compost 2 - TOC)

Compost 2-TOC

Unit gkg

Mandels k statistics(Sludge 1 - TOC)Mandels h statistics(Sludge 1 - TOC)

Sample Sludge 1 Sludge 1 - TOC -- Mean PARM = 2721 [gkg]

Element TOC

General calcparmT1= 169626E+04T2= 465445E+06T3= 62T4= 326T5= 10312E+03

n= variabelp= 13

N-table= 5

Mandels statistics End ResultLAB 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

69L 233000 2362 4 -347 037 Fail - - 69L - - -2488046L 2312500 2062 4 -040 032 Fail 2312500 20616 4 3 -408565L 2615500 1708 4 004 026 2615500 17078 4 3 -105566L 2627200 8268 4 006 128 2627200 82678 4 3 -93836L 2664041 4976 3 011 077 2664041 49758 3 2 -56935L 2671500 3533 6 013 055 2671500 35331 6 5 -49556L 2692298 0874 6 016 014 Fail 2692298 08738 6 5 -28732L 2717500 6185 4 019 096 Fail 2717500 61847 4 3 -03519L 2753333 7819 6 025 121 Fail 2753333 78189 6 5 32470L 2814600 - 1 034 Fail 2814600 - 1 9369L 2853667 0398 6 039 006 Fail 2853667 03983 6 5 132716L 2860000 1673 6 040 026 Fail 2860000 16733 6 5 139045L 2884433 7033 6 044 109 Fail 2884433 70331 6 5 163544L 2906167 1129 6 047 017 Fail 2906167 11286 6 5 185234L 3186874 17674 6 089 274 Fail - - 34L - - 4659

Totgem 258617 4692 gkg 1-level 232 (176) 13 2720980 (34L 69L) 13 12Totstd= 67800 4610 5-level 186 (152) 2

72RESULTS Mean = 27209799 gkg

Repeatability variance S2r = 2104538Repeatability std Sr = 458752 --gt 169 r = 128451Between lab variance S2L = 23618387Reproducibility var S2R = 25722925Reproducibility std SR = 1603837 --gt 589 R = 449074Remarks 2 Labs rejected (34L 69L)

000 050 100 150 200 250 300

k-values

69L

46L

65L

66L

36L

35L

56L

32L

19L

70L

9L

16L

45L

44L

34L

Mandels k statistics(Sludge 1 - TOC)

-2500 -2000 -1500 -1000 -500 00 500

Deviation from Mean

69L

46L

65L

66L

36L

35L

56L

32L

19L

70L

9L

16L

45L

44L

34L

Labo

rato

ries

Sludge 1 - TOC -- Mean PARM = 2721 [gkg]

-400 -300 -200 -100 000 100

h-values

69L

65L

36L

56L

19L

9L

45L

34L

Labo

rato

ries

Mandels h statistics(Sludge 1 - TOC)

Sludge 1-TOC

68 Unit gkg

Mandels k statistics(Sludge 2 - TOC)Mandels h statistics(Sludge 2 - TOC)

Sample Sludge 2 Sludge 2 - TOC -- Mean PARM = 2207 [gkg]

Element TOC

General calcparmT1= 128601E+04T2= 285689E+06T3= 58T4= 310T5= 97826E+02

n= variabelp= 12

N-table= 5

Mandels statistics End ResultLAB 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

46L 182500 0500 4 -333 008 Fail - - 46L - - -2024466L 2029475 5267 4 -012 084 2029475 52674 4 3 -177436L 2072609 2222 3 -005 035 2072609 22222 3 2 -134365L 2084750 3865 4 -002 062 2084750 38647 4 3 -122135L 2140333 3119 6 007 050 2140333 31194 6 5 -66556L 2188021 1282 6 015 020 2188021 12822 6 5 -18819L 2223667 7916 6 022 126 Fail 2223667 79157 6 5 16832L 2242500 3096 4 025 049 Fail 2242500 30957 4 3 35645L 2266600 8322 6 029 132 Fail 2266600 83216 6 5 59770L 2272460 - 1 030 Fail 2272460 - 1 65616L 2291667 3869 6 033 062 Fail 2291667 38687 6 5 84844L 2302667 1546 6 035 025 Fail 2302667 15462 6 5 9589L 2367667 1296 6 047 021 Fail 2367667 12956 6 5 160834L 2718591 17124 6 108 273 Fail - - 34L - - 5117

Totgem 209882 4571 gkg 1-level 230 (176) 12 2206868 (34L 46L) 12 11Totstd= 57628 4485 5-level 185 (151) 2

68RESULTS Mean = 22068679 gkg

Repeatability variance S2r = 2126659Repeatability std Sr = 461157 --gt 209 r = 129124Between lab variance S2L = 9960432Reproducibility var S2R = 12087091Reproducibility std SR = 1099413 --gt 498 R = 307836Remarks 2 Labs rejected (34L 46L)

000 050 100 150 200 250 300

k-values

46L

66L

36L

65L

35L

56L

19L

32L

45L

70L

16L

44L

9L

34L

Mandels k statistics(Sludge 2 - TOC)

-2500 -2000 -1500 -1000 -500 00 500 1000

Deviation from Mean

46L

66L

36L

65L

35L

56L

19L

32L

45L

70L

16L

44L

9L

34L

Labo

rato

ries

Sludge 2 - TOC -- Mean PARM = 2207 [gkg]

-400 -300 -200 -100 000 100 200

h-values

46L

66L

36L

65L

35L

56L

19L

32L

45L

70L

16L

44L

9L

34L

Labo

rato

ries

Mandels h statistics(Sludge 2 - TOC)

Sludge 2-TOC

Unit gkg

Mandels k statistics(Soil 4 - TOC)Mandels h statistics(Soil 4 - TOC)

Sample Soil 4 Soil 4 - TOC -- Mean PARM = 1641 [gkg]

Element TOC

General calcparmT1= 102171E+03T2= 168700E+04T3= 62T4= 338T5= 94040E+00

n= variabelp= 12

N-table= 5

Mandels statistics End ResultLAB 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

36L 147161 0470 3 -036 068 Fail 147161 04702 3 2 -16965L 155250 0591 4 -032 085 Fail 155250 05909 4 3 -08844L 157900 0115 6 -031 017 Fail 157900 01152 6 5 -06232L 159250 0359 4 -031 052 Fail 159250 03594 4 3 -0489L 160500 0315 6 -030 045 Fail 160500 03146 6 5 -03656L 164927 0113 6 -028 016 Fail 164927 01127 6 5 00835L 165000 0261 6 -028 038 Fail 165000 02608 6 5 00919L 166667 0505 6 -027 073 Fail 166667 05046 6 5 02645L 168850 0763 6 -026 110 Fail 168850 07628 6 5 04816L 173333 0516 6 -024 074 Fail 173333 05164 6 5 09334L 174761 0346 6 -024 050 Fail 174761 03462 6 5 10730L 175333 0473 3 -024 068 Fail 175333 04726 3 2 11366L 189375 2035 4 -017 294 Fail - - 66L - - 25346L 227500 0500 4 000 072 - - 46L - - 63470L 1040400 - 1 360 Fail - - 70L - - 8763

Totgem 22841 0526 gkg 1-level 232 (176) 12 164078 (46L 66L70L) 12 11Totstd= 22541 0469 5-level 186 (152) 3

71RESULTS Mean = 1640777 gkg

Repeatability variance S2r = 018808Repeatability std Sr = 043368 --gt 264 r = 12143Between lab variance S2L = 054747Reproducibility var S2R = 073555Reproducibility std SR = 085764 --gt 523 R = 24014Remarks 3 Labs rejected (46L 66L70L)

000 050 100 150 200 250 300

k-values

36L

65L

44L

32L

9L

56L

35L

19L

45L

16L

34L

30L

66L

46L

70L

Mandels k statistics(Soil 4 - TOC)

-100 00 100 200 300 400 500 600 700 800 900

Deviation from Mean

36L

65L

44L

32L

9L

56L

35L

19L

45L

16L

34L

30L

66L

46L

70L

Labo

rato

ries

Soil 4 - TOC -- Mean PARM = 1641 [gkg]

-100 000 100 200 300 400

h-values

36L

44L

9L

35L

45L

34L

66L

70L

Labo

rato

ries

Mandels h statistics(Soil 4 - TOC)

Soil 4-TOC

Unit gkg

Mandels k statistics(Soil 5 - TOC)Mandels h statistics(Soil 5 - TOC)

Sample Soil 5 Soil 5 - TOC -- Mean PARM = 2102 [gkg]

Element TOC

General calcparmT1= 113661E+03T2= 240201E+04T3= 54T4= 300T5= 51756E+01

n= variabelp= 10

N-table= 5

Mandels statistics End ResultLAB 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

44L 164383 14708 6 -036 325 Fail - - 44L - - -45865L 181250 0830 4 -033 018 Fail 181250 08302 4 3 -29045L 200317 1116 6 -029 025 Fail 200317 11163 6 5 -09935L 201833 1828 6 -029 040 Fail 201833 18280 6 5 -08432L 203250 0585 4 -029 013 Fail 203250 05852 4 3 -07016L 209000 0959 6 -028 021 Fail 209000 09592 6 5 -0129L 211667 0427 6 -027 009 Fail 211667 04274 6 5 01556L 214030 0887 6 -027 020 Fail 214030 08868 6 5 03819L 216000 0795 6 -026 018 Fail 216000 07950 6 5 05834L 226009 1308 6 -024 029 Fail 226009 13076 6 5 15836L 228783 4310 3 -024 095 Fail - - 36L - - 18666L 238750 1234 4 -022 027 Fail 238750 12340 4 3 28570L 2213900 - 1 333 Fail - - 70L - - 20037

Totgem 36224 2416 gkg 1-level 227 (175) 10 210211 (36L44L 70L) 10 9Totstd= 55669 4003 5-level 184 (151) 3

64RESULTS Mean = 2102106 gkg

Repeatability variance S2r = 117627Repeatability std Sr = 108456 --gt 516 r = 30368Between lab variance S2L = 176699Reproducibility var S2R = 294326Reproducibility std SR = 171559 --gt 816 R = 48037Remarks 3 Labs rejected (36L44L 70L)

000 050 100 150 200 250 300 350

k-values

44L

65L

45L

35L

32L

16L

9L

56L

19L

34L

36L

66L

70L

Mandels k statistics(Soil 5 - TOC)

-500 00 500 1000 1500 2000 2500

Deviation from Mean

44L

65L

45L

35L

32L

16L

9L

56L

19L

34L

36L

66L

70L

Labo

rato

ries

Soil 5 - TOC -- Mean PARM = 2102 [gkg]

-100 000 100 200 300 400

h-values

44L

65L

45L

35L

32L

16L

9L

56L

19L

34L

36L

66L

70L

Labo

rato

ries

Mandels h statistics(Soil 5 - TOC)

Soil 5-TOC

17

Annex 4

Raw data submitted

Sample Compost 1 Sample Compost 2 Sample Sewage Sludge 1Element TOC [gkg] Element TOC [gkg] Element TOC [gkg]

LAB PARM LAB PARM LAB PARM30L 2600 19L 1691 19L 286730L 2580 19L 1634 19L 281430L 2560 19L 1619 19L 276934L 2969 19L 1604 19L 272034L 2936 19L 1499 19L 268834L 2958 19L 1414 19L 266234L 2994 34L 1527 34L 315234L 3199 34L 1622 34L 314934L 3024 34L 1519 34L 343035L 2306 34L 1753 34L 336535L 2300 34L 1636 34L 304235L 2298 34L 1874 34L 298335L 2296 35L 1506 35L 270735L 2291 35L 1312 35L 270335L 2259 35L 1294 35L 268836L 2546 35L 1279 35L 267436L 2527 35L 1191 35L 263136L 2470 35L 1177 35L 262644L 2583 36L 1418 36L 271344L 2581 36L 1408 36L 266544L 2578 36L 1320 36L 261444L 2539 44L 1719 44L 292044L 2528 44L 1664 44L 291644L 2525 44L 1654 44L 291245L 2658 44L 1637 44L 290045L 2600 44L 1624 44L 289645L 2546 44L 1620 44L 289345L 2461 45L 1428 45L 297645L 2409 45L 1325 45L 295245L 2350 45L 1323 45L 288546L 2460 45L 1321 45L 286646L 2400 45L 1309 45L 284046L 2370 45L 1253 45L 278746L 2350 46L 1580 46L 233056L 2436 46L 1550 46L 233056L 2435 46L 1170 46L 230056L 2405 46L 1120 46L 229056L 2397 56L 1642 56L 270256L 2375 56L 1626 56L 270156L 2358 56L 1622 56L 269465L 2587 56L 1571 56L 269365L 2542 56L 1561 56L 268465L 2483 56L 1545 56L 268066L 2454 65L 1933 65L 264166L 2429 65L 1838 65L 260966L 2365 65L 1693 65L 260766L 2262 65L 1562 65L 260569L 2730 66L 1561 66L 270169L 2250 66L 1545 66L 267469L 1440 66L 1420 66L 261969L 1420 66L 1417 66L 251470L 2435 69L 2700 69L 2639L 2594 69L 2660 69L 2409L 2570 69L 2170 69L 2199L 2565 69L 2130 69L 2109L 2563 70L 1414 70L 28159L 2562 9L 1644 9L 28579L 2555 9L 1641 9L 2856

32L 2290 9L 1602 9L 285532L 2390 9L 1589 9L 285532L 2510 9L 1526 9L 285332L 2470 9L 1492 9L 284616L 2380 32L 1470 32L 265016L 2530 32L 1520 32L 271016L 2400 32L 1540 32L 271016L 2500 32L 1600 32L 280016L 2420 16L 1400 16L 284016L 2410 16L 1440 16L 2840

16L 1470 16L 286016L 1510 16L 287016L 1360 16L 287016L 1390 16L 2880

Sample Sewage Sludge 2 Sample Soil 4 Sample Soil 5Element TOC [gkg] Element TOC [gkg] Element TOC [gkg]

LAB PARM LAB PARM LAB PARM19L 2308 19L 1720 19L 225019L 2303 19L 1700 19L 223019L 2239 19L 1690 19L 221019L 2204 19L 1670 19L 211019L 2192 19L 1640 19L 210019L 2096 19L 1580 19L 206034L 2631 30L 1790 34L 244334L 2471 30L 1770 34L 233434L 2977 30L 1700 34L 231534L 2785 34L 1740 34L 222134L 2780 34L 1692 34L 217634L 2668 34L 1727 34L 207335L 2179 34L 1767 35L 233035L 2160 34L 1777 35L 208035L 2158 34L 1783 35L 201035L 2132 35L 1700 35L 198035L 2119 35L 1650 35L 193035L 2094 35L 1650 35L 178036L 2096 35L 1640 36L 254036L 2069 35L 1630 36L 253436L 2052 35L 1630 36L 179044L 2325 36L 1500 44L 302144L 2309 36L 1497 44L 298244L 2307 36L 1417 44L 295644L 2305 44L 1594 44L 30744L 2287 44L 1587 44L 30044L 2283 44L 1584 44L 29745L 2331 44L 1574 45L 214945L 2327 44L 1573 45L 209245L 2308 44L 1562 45L 203345L 2287 45L 1827 45L 197145L 2234 45L 1709 45L 193345L 2113 45L 1666 45L 184146L 190 45L 1665 56L 223746L 180 45L 1664 56L 222246L 180 45L 1600 56L 220346L 180 46L 2300 56L 206956L 2204 46L 2300 56L 206856L 2197 46L 2300 56L 204456L 2193 46L 2200 65L 192056L 2185 56L 1668 65L 182056L 2183 56L 1654 65L 179056L 2167 56L 1653 65L 172065L 2136 56L 1643 66L 254365L 2091 56L 1639 66L 242465L 2065 56L 1638 66L 232165L 2047 65L 1630 66L 226266L 2105 65L 1560 70L 2213966L 2022 65L 1530 9L 218066L 2009 65L 1490 9L 214066L 1983 66L 2179 9L 213070L 2272 66L 1900 9L 21109L 2385 66L 1762 9L 20709L 2377 66L 1734 9L 20709L 2375 70L 10404 32L 20509L 2359 9L 1640 32L 21009L 2356 9L 1640 32L 20209L 2354 9L 1610 32L 1960

32L 2240 9L 1590 16L 210032L 2260 9L 1590 16L 220032L 2200 9L 1560 16L 220032L 2270 32L 1640 16L 206016L 2300 32L 1600 16L 197016L 2310 32L 1560 16L 201016L 2350 32L 157016L 2260 16L 170016L 2290 16L 180016L 2240 16L 1700

16L 180016L 170016L 1700

European Commission EUR 23012 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on total organic carbon Author(s) E Sobiecka H van der Sloot K Andersen B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 50 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07412-7 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 total organic carbon (TOC) in soils sludge and treated bio-waste 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

-23012-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

16

Annex 3

Statistical calculations

Unit gkg

Mandels k statistics(Compost 1 - TOC)Mandels h statistics(Compost 1 - TOC)

Sample Compost 1 Compost 1 - TOC -- Mean PARM = 2463 [gkg]

Element TOC

General calcparmT1= 142643E+04T2= 351264E+06T3= 58T4= 292T5= 16501E+03

n= variabelp= 13

N-table= 5

Mandels statistics End ResultLAB 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

69L 1960000 64265 4 -235 352 Fail - - 69L - - -502735L 2291667 1674 6 -081 009 2291667 16741 6 5 -171066L 2377425 8552 4 -041 047 2377425 85518 4 3 -85346L 2395000 4796 4 -033 026 2395000 47958 4 3 -67756L 2401227 3133 6 -030 017 2401227 31330 6 5 -61432L 2415000 9713 4 -024 053 2415000 97125 4 3 -47770L 2435100 - 1 -014 2435100 - 1 -27616L 2440000 6033 6 -012 033 2440000 60332 6 5 -22745L 2503800 11759 6 018 064 2503800 117589 6 5 41136L 2514416 3994 3 023 022 2514416 39937 3 2 51765L 2537333 5216 3 033 029 2537333 52157 3 2 74744L 2555667 2783 6 042 015 2555667 27826 6 5 9309L 2568167 1356 6 048 007 2568167 13556 6 5 105530L 2580000 2000 3 053 011 2580000 20000 3 2 117334L 3013269 9580 6 255 053 Fail - - 34L - - 5506

Totgem 246587 9632 gkg 1-level 232 (176) 13 2462677 (34L 69L) 13 12Totstd= 21507 16070 5-level 186 (152) 2

68RESULTS Mean = 24626770 gkg

Repeatability variance S2r = 3666797Repeatability std Sr = 605541 --gt 246 r = 169551Between lab variance S2L = 7715586Reproducibility var S2R = 11382383Reproducibility std SR = 1066882 --gt 433 R = 298727Remarks 2 Labs rejected (34L 69L)

000 050 100 150 200 250 300 350 400

k-values

69L

35L

66L

46L

56L

32L

70L

16L

45L

36L

65L

44L

9L

30L

34L

Mandels k statistics(Compost 1 - TOC)

-600 -400 -200 00 200 400 600

Deviation from Mean

69L

35L

66L

46L

56L

32L

70L

16L

45L

36L

65L

44L

9L

30L

34L

Labo

rato

ries

Compost 1 - TOC -- Mean PARM = 2463 [gkg]

-300 -200 -100 000 100 200 300

h-values

69L

66L

56L

70L

45L

65L

9L

34L

Labo

rato

ries

Mandels h statistics(Compost 1 - TOC)

Compost 1-TOC

Unit gkg

Mandels k statistics(Compost 2 - TOC)Mandels h statistics(Compost 2 - TOC)

Sample Compost 2 Compost 2 - TOC -- Mean PARM = 1542 [gkg]

Element TOC

General calcparmT1= 994897E+03T2= 155556E+06T3= 64T4= 346T5= 41738E+03

n= variabelp= 13

N-table= 5

Mandels statistics End ResultLAB 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

45L 1326733 5665 6 -100 042 Fail 1326733 56646 6 5 -215046L 1355000 24365 4 -089 181 Fail - - 46L - - -186736L 1381949 5407 3 -078 040 Fail 1381949 54070 3 2 -159870L 1414120 - 1 -066 Fail 1414120 - 1 -127616L 1428333 5565 6 -061 041 1428333 55648 6 5 -113466L 1485550 7805 4 -039 058 1485550 78047 4 3 -56232L 1532500 5377 4 -021 040 1532500 53774 4 3 -09219L 1576833 10138 6 -004 075 1576833 101381 6 5 3519L 1582333 6166 6 -002 046 1582333 61659 6 5 40656L 1594432 4046 6 003 030 1594432 40463 6 5 52744L 1653000 3651 6 025 027 1653000 36508 6 5 111334L 1655127 13717 6 026 102 1655127 137168 6 5 113434L 1655127 13717 6 026 102 1655127 137168 6 5 113465L 1756500 16295 4 065 121 Fail 1756500 162949 4 3 214869L 2415000 30687 4 316 228 Fail - - 69L - - 8733

Totgem 158750 10900 gkg 1-level 232 (176) 13 1541734 (46L 69L) 13 12Totstd= 26187 8164 5-level 186 (152) 2

72RESULTS Mean = 15417337 gkg

Repeatability variance S2r = 8183950Repeatability std Sr = 904652 --gt 587 r = 253303Between lab variance S2L = 13631046Reproducibility var S2R = 21814995Reproducibility std SR = 1476990 --gt 958 R = 413557Remarks 2 Labs rejected (46L 69L)

000 050 100 150 200 250

k-values

45L

46L

36L

70L

16L

66L

32L

19L

9L

56L

44L

34L

34L

65L

69L

Mandels k statistics(Compost 2 - TOC)

-400 -200 00 200 400 600 800 1000

Deviation from Mean

45L

46L

36L

70L

16L

66L

32L

19L

9L

56L

44L

34L

34L

65L

69L

Labo

rato

ries

Compost 2 - TOC -- Mean PARM = 1542 [gkg]

-100 000 100 200 300 400

h-values

45L

36L

16L

32L

9L

44L

34L

69L

Labo

rato

ries

Mandels h statistics(Compost 2 - TOC)

Compost 2-TOC

Unit gkg

Mandels k statistics(Sludge 1 - TOC)Mandels h statistics(Sludge 1 - TOC)

Sample Sludge 1 Sludge 1 - TOC -- Mean PARM = 2721 [gkg]

Element TOC

General calcparmT1= 169626E+04T2= 465445E+06T3= 62T4= 326T5= 10312E+03

n= variabelp= 13

N-table= 5

Mandels statistics End ResultLAB 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

69L 233000 2362 4 -347 037 Fail - - 69L - - -2488046L 2312500 2062 4 -040 032 Fail 2312500 20616 4 3 -408565L 2615500 1708 4 004 026 2615500 17078 4 3 -105566L 2627200 8268 4 006 128 2627200 82678 4 3 -93836L 2664041 4976 3 011 077 2664041 49758 3 2 -56935L 2671500 3533 6 013 055 2671500 35331 6 5 -49556L 2692298 0874 6 016 014 Fail 2692298 08738 6 5 -28732L 2717500 6185 4 019 096 Fail 2717500 61847 4 3 -03519L 2753333 7819 6 025 121 Fail 2753333 78189 6 5 32470L 2814600 - 1 034 Fail 2814600 - 1 9369L 2853667 0398 6 039 006 Fail 2853667 03983 6 5 132716L 2860000 1673 6 040 026 Fail 2860000 16733 6 5 139045L 2884433 7033 6 044 109 Fail 2884433 70331 6 5 163544L 2906167 1129 6 047 017 Fail 2906167 11286 6 5 185234L 3186874 17674 6 089 274 Fail - - 34L - - 4659

Totgem 258617 4692 gkg 1-level 232 (176) 13 2720980 (34L 69L) 13 12Totstd= 67800 4610 5-level 186 (152) 2

72RESULTS Mean = 27209799 gkg

Repeatability variance S2r = 2104538Repeatability std Sr = 458752 --gt 169 r = 128451Between lab variance S2L = 23618387Reproducibility var S2R = 25722925Reproducibility std SR = 1603837 --gt 589 R = 449074Remarks 2 Labs rejected (34L 69L)

000 050 100 150 200 250 300

k-values

69L

46L

65L

66L

36L

35L

56L

32L

19L

70L

9L

16L

45L

44L

34L

Mandels k statistics(Sludge 1 - TOC)

-2500 -2000 -1500 -1000 -500 00 500

Deviation from Mean

69L

46L

65L

66L

36L

35L

56L

32L

19L

70L

9L

16L

45L

44L

34L

Labo

rato

ries

Sludge 1 - TOC -- Mean PARM = 2721 [gkg]

-400 -300 -200 -100 000 100

h-values

69L

65L

36L

56L

19L

9L

45L

34L

Labo

rato

ries

Mandels h statistics(Sludge 1 - TOC)

Sludge 1-TOC

68 Unit gkg

Mandels k statistics(Sludge 2 - TOC)Mandels h statistics(Sludge 2 - TOC)

Sample Sludge 2 Sludge 2 - TOC -- Mean PARM = 2207 [gkg]

Element TOC

General calcparmT1= 128601E+04T2= 285689E+06T3= 58T4= 310T5= 97826E+02

n= variabelp= 12

N-table= 5

Mandels statistics End ResultLAB 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

46L 182500 0500 4 -333 008 Fail - - 46L - - -2024466L 2029475 5267 4 -012 084 2029475 52674 4 3 -177436L 2072609 2222 3 -005 035 2072609 22222 3 2 -134365L 2084750 3865 4 -002 062 2084750 38647 4 3 -122135L 2140333 3119 6 007 050 2140333 31194 6 5 -66556L 2188021 1282 6 015 020 2188021 12822 6 5 -18819L 2223667 7916 6 022 126 Fail 2223667 79157 6 5 16832L 2242500 3096 4 025 049 Fail 2242500 30957 4 3 35645L 2266600 8322 6 029 132 Fail 2266600 83216 6 5 59770L 2272460 - 1 030 Fail 2272460 - 1 65616L 2291667 3869 6 033 062 Fail 2291667 38687 6 5 84844L 2302667 1546 6 035 025 Fail 2302667 15462 6 5 9589L 2367667 1296 6 047 021 Fail 2367667 12956 6 5 160834L 2718591 17124 6 108 273 Fail - - 34L - - 5117

Totgem 209882 4571 gkg 1-level 230 (176) 12 2206868 (34L 46L) 12 11Totstd= 57628 4485 5-level 185 (151) 2

68RESULTS Mean = 22068679 gkg

Repeatability variance S2r = 2126659Repeatability std Sr = 461157 --gt 209 r = 129124Between lab variance S2L = 9960432Reproducibility var S2R = 12087091Reproducibility std SR = 1099413 --gt 498 R = 307836Remarks 2 Labs rejected (34L 46L)

000 050 100 150 200 250 300

k-values

46L

66L

36L

65L

35L

56L

19L

32L

45L

70L

16L

44L

9L

34L

Mandels k statistics(Sludge 2 - TOC)

-2500 -2000 -1500 -1000 -500 00 500 1000

Deviation from Mean

46L

66L

36L

65L

35L

56L

19L

32L

45L

70L

16L

44L

9L

34L

Labo

rato

ries

Sludge 2 - TOC -- Mean PARM = 2207 [gkg]

-400 -300 -200 -100 000 100 200

h-values

46L

66L

36L

65L

35L

56L

19L

32L

45L

70L

16L

44L

9L

34L

Labo

rato

ries

Mandels h statistics(Sludge 2 - TOC)

Sludge 2-TOC

Unit gkg

Mandels k statistics(Soil 4 - TOC)Mandels h statistics(Soil 4 - TOC)

Sample Soil 4 Soil 4 - TOC -- Mean PARM = 1641 [gkg]

Element TOC

General calcparmT1= 102171E+03T2= 168700E+04T3= 62T4= 338T5= 94040E+00

n= variabelp= 12

N-table= 5

Mandels statistics End ResultLAB 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

36L 147161 0470 3 -036 068 Fail 147161 04702 3 2 -16965L 155250 0591 4 -032 085 Fail 155250 05909 4 3 -08844L 157900 0115 6 -031 017 Fail 157900 01152 6 5 -06232L 159250 0359 4 -031 052 Fail 159250 03594 4 3 -0489L 160500 0315 6 -030 045 Fail 160500 03146 6 5 -03656L 164927 0113 6 -028 016 Fail 164927 01127 6 5 00835L 165000 0261 6 -028 038 Fail 165000 02608 6 5 00919L 166667 0505 6 -027 073 Fail 166667 05046 6 5 02645L 168850 0763 6 -026 110 Fail 168850 07628 6 5 04816L 173333 0516 6 -024 074 Fail 173333 05164 6 5 09334L 174761 0346 6 -024 050 Fail 174761 03462 6 5 10730L 175333 0473 3 -024 068 Fail 175333 04726 3 2 11366L 189375 2035 4 -017 294 Fail - - 66L - - 25346L 227500 0500 4 000 072 - - 46L - - 63470L 1040400 - 1 360 Fail - - 70L - - 8763

Totgem 22841 0526 gkg 1-level 232 (176) 12 164078 (46L 66L70L) 12 11Totstd= 22541 0469 5-level 186 (152) 3

71RESULTS Mean = 1640777 gkg

Repeatability variance S2r = 018808Repeatability std Sr = 043368 --gt 264 r = 12143Between lab variance S2L = 054747Reproducibility var S2R = 073555Reproducibility std SR = 085764 --gt 523 R = 24014Remarks 3 Labs rejected (46L 66L70L)

000 050 100 150 200 250 300

k-values

36L

65L

44L

32L

9L

56L

35L

19L

45L

16L

34L

30L

66L

46L

70L

Mandels k statistics(Soil 4 - TOC)

-100 00 100 200 300 400 500 600 700 800 900

Deviation from Mean

36L

65L

44L

32L

9L

56L

35L

19L

45L

16L

34L

30L

66L

46L

70L

Labo

rato

ries

Soil 4 - TOC -- Mean PARM = 1641 [gkg]

-100 000 100 200 300 400

h-values

36L

44L

9L

35L

45L

34L

66L

70L

Labo

rato

ries

Mandels h statistics(Soil 4 - TOC)

Soil 4-TOC

Unit gkg

Mandels k statistics(Soil 5 - TOC)Mandels h statistics(Soil 5 - TOC)

Sample Soil 5 Soil 5 - TOC -- Mean PARM = 2102 [gkg]

Element TOC

General calcparmT1= 113661E+03T2= 240201E+04T3= 54T4= 300T5= 51756E+01

n= variabelp= 10

N-table= 5

Mandels statistics End ResultLAB 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

44L 164383 14708 6 -036 325 Fail - - 44L - - -45865L 181250 0830 4 -033 018 Fail 181250 08302 4 3 -29045L 200317 1116 6 -029 025 Fail 200317 11163 6 5 -09935L 201833 1828 6 -029 040 Fail 201833 18280 6 5 -08432L 203250 0585 4 -029 013 Fail 203250 05852 4 3 -07016L 209000 0959 6 -028 021 Fail 209000 09592 6 5 -0129L 211667 0427 6 -027 009 Fail 211667 04274 6 5 01556L 214030 0887 6 -027 020 Fail 214030 08868 6 5 03819L 216000 0795 6 -026 018 Fail 216000 07950 6 5 05834L 226009 1308 6 -024 029 Fail 226009 13076 6 5 15836L 228783 4310 3 -024 095 Fail - - 36L - - 18666L 238750 1234 4 -022 027 Fail 238750 12340 4 3 28570L 2213900 - 1 333 Fail - - 70L - - 20037

Totgem 36224 2416 gkg 1-level 227 (175) 10 210211 (36L44L 70L) 10 9Totstd= 55669 4003 5-level 184 (151) 3

64RESULTS Mean = 2102106 gkg

Repeatability variance S2r = 117627Repeatability std Sr = 108456 --gt 516 r = 30368Between lab variance S2L = 176699Reproducibility var S2R = 294326Reproducibility std SR = 171559 --gt 816 R = 48037Remarks 3 Labs rejected (36L44L 70L)

000 050 100 150 200 250 300 350

k-values

44L

65L

45L

35L

32L

16L

9L

56L

19L

34L

36L

66L

70L

Mandels k statistics(Soil 5 - TOC)

-500 00 500 1000 1500 2000 2500

Deviation from Mean

44L

65L

45L

35L

32L

16L

9L

56L

19L

34L

36L

66L

70L

Labo

rato

ries

Soil 5 - TOC -- Mean PARM = 2102 [gkg]

-100 000 100 200 300 400

h-values

44L

65L

45L

35L

32L

16L

9L

56L

19L

34L

36L

66L

70L

Labo

rato

ries

Mandels h statistics(Soil 5 - TOC)

Soil 5-TOC

17

Annex 4

Raw data submitted

Sample Compost 1 Sample Compost 2 Sample Sewage Sludge 1Element TOC [gkg] Element TOC [gkg] Element TOC [gkg]

LAB PARM LAB PARM LAB PARM30L 2600 19L 1691 19L 286730L 2580 19L 1634 19L 281430L 2560 19L 1619 19L 276934L 2969 19L 1604 19L 272034L 2936 19L 1499 19L 268834L 2958 19L 1414 19L 266234L 2994 34L 1527 34L 315234L 3199 34L 1622 34L 314934L 3024 34L 1519 34L 343035L 2306 34L 1753 34L 336535L 2300 34L 1636 34L 304235L 2298 34L 1874 34L 298335L 2296 35L 1506 35L 270735L 2291 35L 1312 35L 270335L 2259 35L 1294 35L 268836L 2546 35L 1279 35L 267436L 2527 35L 1191 35L 263136L 2470 35L 1177 35L 262644L 2583 36L 1418 36L 271344L 2581 36L 1408 36L 266544L 2578 36L 1320 36L 261444L 2539 44L 1719 44L 292044L 2528 44L 1664 44L 291644L 2525 44L 1654 44L 291245L 2658 44L 1637 44L 290045L 2600 44L 1624 44L 289645L 2546 44L 1620 44L 289345L 2461 45L 1428 45L 297645L 2409 45L 1325 45L 295245L 2350 45L 1323 45L 288546L 2460 45L 1321 45L 286646L 2400 45L 1309 45L 284046L 2370 45L 1253 45L 278746L 2350 46L 1580 46L 233056L 2436 46L 1550 46L 233056L 2435 46L 1170 46L 230056L 2405 46L 1120 46L 229056L 2397 56L 1642 56L 270256L 2375 56L 1626 56L 270156L 2358 56L 1622 56L 269465L 2587 56L 1571 56L 269365L 2542 56L 1561 56L 268465L 2483 56L 1545 56L 268066L 2454 65L 1933 65L 264166L 2429 65L 1838 65L 260966L 2365 65L 1693 65L 260766L 2262 65L 1562 65L 260569L 2730 66L 1561 66L 270169L 2250 66L 1545 66L 267469L 1440 66L 1420 66L 261969L 1420 66L 1417 66L 251470L 2435 69L 2700 69L 2639L 2594 69L 2660 69L 2409L 2570 69L 2170 69L 2199L 2565 69L 2130 69L 2109L 2563 70L 1414 70L 28159L 2562 9L 1644 9L 28579L 2555 9L 1641 9L 2856

32L 2290 9L 1602 9L 285532L 2390 9L 1589 9L 285532L 2510 9L 1526 9L 285332L 2470 9L 1492 9L 284616L 2380 32L 1470 32L 265016L 2530 32L 1520 32L 271016L 2400 32L 1540 32L 271016L 2500 32L 1600 32L 280016L 2420 16L 1400 16L 284016L 2410 16L 1440 16L 2840

16L 1470 16L 286016L 1510 16L 287016L 1360 16L 287016L 1390 16L 2880

Sample Sewage Sludge 2 Sample Soil 4 Sample Soil 5Element TOC [gkg] Element TOC [gkg] Element TOC [gkg]

LAB PARM LAB PARM LAB PARM19L 2308 19L 1720 19L 225019L 2303 19L 1700 19L 223019L 2239 19L 1690 19L 221019L 2204 19L 1670 19L 211019L 2192 19L 1640 19L 210019L 2096 19L 1580 19L 206034L 2631 30L 1790 34L 244334L 2471 30L 1770 34L 233434L 2977 30L 1700 34L 231534L 2785 34L 1740 34L 222134L 2780 34L 1692 34L 217634L 2668 34L 1727 34L 207335L 2179 34L 1767 35L 233035L 2160 34L 1777 35L 208035L 2158 34L 1783 35L 201035L 2132 35L 1700 35L 198035L 2119 35L 1650 35L 193035L 2094 35L 1650 35L 178036L 2096 35L 1640 36L 254036L 2069 35L 1630 36L 253436L 2052 35L 1630 36L 179044L 2325 36L 1500 44L 302144L 2309 36L 1497 44L 298244L 2307 36L 1417 44L 295644L 2305 44L 1594 44L 30744L 2287 44L 1587 44L 30044L 2283 44L 1584 44L 29745L 2331 44L 1574 45L 214945L 2327 44L 1573 45L 209245L 2308 44L 1562 45L 203345L 2287 45L 1827 45L 197145L 2234 45L 1709 45L 193345L 2113 45L 1666 45L 184146L 190 45L 1665 56L 223746L 180 45L 1664 56L 222246L 180 45L 1600 56L 220346L 180 46L 2300 56L 206956L 2204 46L 2300 56L 206856L 2197 46L 2300 56L 204456L 2193 46L 2200 65L 192056L 2185 56L 1668 65L 182056L 2183 56L 1654 65L 179056L 2167 56L 1653 65L 172065L 2136 56L 1643 66L 254365L 2091 56L 1639 66L 242465L 2065 56L 1638 66L 232165L 2047 65L 1630 66L 226266L 2105 65L 1560 70L 2213966L 2022 65L 1530 9L 218066L 2009 65L 1490 9L 214066L 1983 66L 2179 9L 213070L 2272 66L 1900 9L 21109L 2385 66L 1762 9L 20709L 2377 66L 1734 9L 20709L 2375 70L 10404 32L 20509L 2359 9L 1640 32L 21009L 2356 9L 1640 32L 20209L 2354 9L 1610 32L 1960

32L 2240 9L 1590 16L 210032L 2260 9L 1590 16L 220032L 2200 9L 1560 16L 220032L 2270 32L 1640 16L 206016L 2300 32L 1600 16L 197016L 2310 32L 1560 16L 201016L 2350 32L 157016L 2260 16L 170016L 2290 16L 180016L 2240 16L 1700

16L 180016L 170016L 1700

European Commission EUR 23012 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on total organic carbon Author(s) E Sobiecka H van der Sloot K Andersen B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 50 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07412-7 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 total organic carbon (TOC) in soils sludge and treated bio-waste 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

-23012-EN

-C

16

Annex 3

Statistical calculations

Unit gkg

Mandels k statistics(Compost 1 - TOC)Mandels h statistics(Compost 1 - TOC)

Sample Compost 1 Compost 1 - TOC -- Mean PARM = 2463 [gkg]

Element TOC

General calcparmT1= 142643E+04T2= 351264E+06T3= 58T4= 292T5= 16501E+03

n= variabelp= 13

N-table= 5

Mandels statistics End ResultLAB 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

69L 1960000 64265 4 -235 352 Fail - - 69L - - -502735L 2291667 1674 6 -081 009 2291667 16741 6 5 -171066L 2377425 8552 4 -041 047 2377425 85518 4 3 -85346L 2395000 4796 4 -033 026 2395000 47958 4 3 -67756L 2401227 3133 6 -030 017 2401227 31330 6 5 -61432L 2415000 9713 4 -024 053 2415000 97125 4 3 -47770L 2435100 - 1 -014 2435100 - 1 -27616L 2440000 6033 6 -012 033 2440000 60332 6 5 -22745L 2503800 11759 6 018 064 2503800 117589 6 5 41136L 2514416 3994 3 023 022 2514416 39937 3 2 51765L 2537333 5216 3 033 029 2537333 52157 3 2 74744L 2555667 2783 6 042 015 2555667 27826 6 5 9309L 2568167 1356 6 048 007 2568167 13556 6 5 105530L 2580000 2000 3 053 011 2580000 20000 3 2 117334L 3013269 9580 6 255 053 Fail - - 34L - - 5506

Totgem 246587 9632 gkg 1-level 232 (176) 13 2462677 (34L 69L) 13 12Totstd= 21507 16070 5-level 186 (152) 2

68RESULTS Mean = 24626770 gkg

Repeatability variance S2r = 3666797Repeatability std Sr = 605541 --gt 246 r = 169551Between lab variance S2L = 7715586Reproducibility var S2R = 11382383Reproducibility std SR = 1066882 --gt 433 R = 298727Remarks 2 Labs rejected (34L 69L)

000 050 100 150 200 250 300 350 400

k-values

69L

35L

66L

46L

56L

32L

70L

16L

45L

36L

65L

44L

9L

30L

34L

Mandels k statistics(Compost 1 - TOC)

-600 -400 -200 00 200 400 600

Deviation from Mean

69L

35L

66L

46L

56L

32L

70L

16L

45L

36L

65L

44L

9L

30L

34L

Labo

rato

ries

Compost 1 - TOC -- Mean PARM = 2463 [gkg]

-300 -200 -100 000 100 200 300

h-values

69L

66L

56L

70L

45L

65L

9L

34L

Labo

rato

ries

Mandels h statistics(Compost 1 - TOC)

Compost 1-TOC

Unit gkg

Mandels k statistics(Compost 2 - TOC)Mandels h statistics(Compost 2 - TOC)

Sample Compost 2 Compost 2 - TOC -- Mean PARM = 1542 [gkg]

Element TOC

General calcparmT1= 994897E+03T2= 155556E+06T3= 64T4= 346T5= 41738E+03

n= variabelp= 13

N-table= 5

Mandels statistics End ResultLAB 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

45L 1326733 5665 6 -100 042 Fail 1326733 56646 6 5 -215046L 1355000 24365 4 -089 181 Fail - - 46L - - -186736L 1381949 5407 3 -078 040 Fail 1381949 54070 3 2 -159870L 1414120 - 1 -066 Fail 1414120 - 1 -127616L 1428333 5565 6 -061 041 1428333 55648 6 5 -113466L 1485550 7805 4 -039 058 1485550 78047 4 3 -56232L 1532500 5377 4 -021 040 1532500 53774 4 3 -09219L 1576833 10138 6 -004 075 1576833 101381 6 5 3519L 1582333 6166 6 -002 046 1582333 61659 6 5 40656L 1594432 4046 6 003 030 1594432 40463 6 5 52744L 1653000 3651 6 025 027 1653000 36508 6 5 111334L 1655127 13717 6 026 102 1655127 137168 6 5 113434L 1655127 13717 6 026 102 1655127 137168 6 5 113465L 1756500 16295 4 065 121 Fail 1756500 162949 4 3 214869L 2415000 30687 4 316 228 Fail - - 69L - - 8733

Totgem 158750 10900 gkg 1-level 232 (176) 13 1541734 (46L 69L) 13 12Totstd= 26187 8164 5-level 186 (152) 2

72RESULTS Mean = 15417337 gkg

Repeatability variance S2r = 8183950Repeatability std Sr = 904652 --gt 587 r = 253303Between lab variance S2L = 13631046Reproducibility var S2R = 21814995Reproducibility std SR = 1476990 --gt 958 R = 413557Remarks 2 Labs rejected (46L 69L)

000 050 100 150 200 250

k-values

45L

46L

36L

70L

16L

66L

32L

19L

9L

56L

44L

34L

34L

65L

69L

Mandels k statistics(Compost 2 - TOC)

-400 -200 00 200 400 600 800 1000

Deviation from Mean

45L

46L

36L

70L

16L

66L

32L

19L

9L

56L

44L

34L

34L

65L

69L

Labo

rato

ries

Compost 2 - TOC -- Mean PARM = 1542 [gkg]

-100 000 100 200 300 400

h-values

45L

36L

16L

32L

9L

44L

34L

69L

Labo

rato

ries

Mandels h statistics(Compost 2 - TOC)

Compost 2-TOC

Unit gkg

Mandels k statistics(Sludge 1 - TOC)Mandels h statistics(Sludge 1 - TOC)

Sample Sludge 1 Sludge 1 - TOC -- Mean PARM = 2721 [gkg]

Element TOC

General calcparmT1= 169626E+04T2= 465445E+06T3= 62T4= 326T5= 10312E+03

n= variabelp= 13

N-table= 5

Mandels statistics End ResultLAB 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

69L 233000 2362 4 -347 037 Fail - - 69L - - -2488046L 2312500 2062 4 -040 032 Fail 2312500 20616 4 3 -408565L 2615500 1708 4 004 026 2615500 17078 4 3 -105566L 2627200 8268 4 006 128 2627200 82678 4 3 -93836L 2664041 4976 3 011 077 2664041 49758 3 2 -56935L 2671500 3533 6 013 055 2671500 35331 6 5 -49556L 2692298 0874 6 016 014 Fail 2692298 08738 6 5 -28732L 2717500 6185 4 019 096 Fail 2717500 61847 4 3 -03519L 2753333 7819 6 025 121 Fail 2753333 78189 6 5 32470L 2814600 - 1 034 Fail 2814600 - 1 9369L 2853667 0398 6 039 006 Fail 2853667 03983 6 5 132716L 2860000 1673 6 040 026 Fail 2860000 16733 6 5 139045L 2884433 7033 6 044 109 Fail 2884433 70331 6 5 163544L 2906167 1129 6 047 017 Fail 2906167 11286 6 5 185234L 3186874 17674 6 089 274 Fail - - 34L - - 4659

Totgem 258617 4692 gkg 1-level 232 (176) 13 2720980 (34L 69L) 13 12Totstd= 67800 4610 5-level 186 (152) 2

72RESULTS Mean = 27209799 gkg

Repeatability variance S2r = 2104538Repeatability std Sr = 458752 --gt 169 r = 128451Between lab variance S2L = 23618387Reproducibility var S2R = 25722925Reproducibility std SR = 1603837 --gt 589 R = 449074Remarks 2 Labs rejected (34L 69L)

000 050 100 150 200 250 300

k-values

69L

46L

65L

66L

36L

35L

56L

32L

19L

70L

9L

16L

45L

44L

34L

Mandels k statistics(Sludge 1 - TOC)

-2500 -2000 -1500 -1000 -500 00 500

Deviation from Mean

69L

46L

65L

66L

36L

35L

56L

32L

19L

70L

9L

16L

45L

44L

34L

Labo

rato

ries

Sludge 1 - TOC -- Mean PARM = 2721 [gkg]

-400 -300 -200 -100 000 100

h-values

69L

65L

36L

56L

19L

9L

45L

34L

Labo

rato

ries

Mandels h statistics(Sludge 1 - TOC)

Sludge 1-TOC

68 Unit gkg

Mandels k statistics(Sludge 2 - TOC)Mandels h statistics(Sludge 2 - TOC)

Sample Sludge 2 Sludge 2 - TOC -- Mean PARM = 2207 [gkg]

Element TOC

General calcparmT1= 128601E+04T2= 285689E+06T3= 58T4= 310T5= 97826E+02

n= variabelp= 12

N-table= 5

Mandels statistics End ResultLAB 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

46L 182500 0500 4 -333 008 Fail - - 46L - - -2024466L 2029475 5267 4 -012 084 2029475 52674 4 3 -177436L 2072609 2222 3 -005 035 2072609 22222 3 2 -134365L 2084750 3865 4 -002 062 2084750 38647 4 3 -122135L 2140333 3119 6 007 050 2140333 31194 6 5 -66556L 2188021 1282 6 015 020 2188021 12822 6 5 -18819L 2223667 7916 6 022 126 Fail 2223667 79157 6 5 16832L 2242500 3096 4 025 049 Fail 2242500 30957 4 3 35645L 2266600 8322 6 029 132 Fail 2266600 83216 6 5 59770L 2272460 - 1 030 Fail 2272460 - 1 65616L 2291667 3869 6 033 062 Fail 2291667 38687 6 5 84844L 2302667 1546 6 035 025 Fail 2302667 15462 6 5 9589L 2367667 1296 6 047 021 Fail 2367667 12956 6 5 160834L 2718591 17124 6 108 273 Fail - - 34L - - 5117

Totgem 209882 4571 gkg 1-level 230 (176) 12 2206868 (34L 46L) 12 11Totstd= 57628 4485 5-level 185 (151) 2

68RESULTS Mean = 22068679 gkg

Repeatability variance S2r = 2126659Repeatability std Sr = 461157 --gt 209 r = 129124Between lab variance S2L = 9960432Reproducibility var S2R = 12087091Reproducibility std SR = 1099413 --gt 498 R = 307836Remarks 2 Labs rejected (34L 46L)

000 050 100 150 200 250 300

k-values

46L

66L

36L

65L

35L

56L

19L

32L

45L

70L

16L

44L

9L

34L

Mandels k statistics(Sludge 2 - TOC)

-2500 -2000 -1500 -1000 -500 00 500 1000

Deviation from Mean

46L

66L

36L

65L

35L

56L

19L

32L

45L

70L

16L

44L

9L

34L

Labo

rato

ries

Sludge 2 - TOC -- Mean PARM = 2207 [gkg]

-400 -300 -200 -100 000 100 200

h-values

46L

66L

36L

65L

35L

56L

19L

32L

45L

70L

16L

44L

9L

34L

Labo

rato

ries

Mandels h statistics(Sludge 2 - TOC)

Sludge 2-TOC

Unit gkg

Mandels k statistics(Soil 4 - TOC)Mandels h statistics(Soil 4 - TOC)

Sample Soil 4 Soil 4 - TOC -- Mean PARM = 1641 [gkg]

Element TOC

General calcparmT1= 102171E+03T2= 168700E+04T3= 62T4= 338T5= 94040E+00

n= variabelp= 12

N-table= 5

Mandels statistics End ResultLAB 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

36L 147161 0470 3 -036 068 Fail 147161 04702 3 2 -16965L 155250 0591 4 -032 085 Fail 155250 05909 4 3 -08844L 157900 0115 6 -031 017 Fail 157900 01152 6 5 -06232L 159250 0359 4 -031 052 Fail 159250 03594 4 3 -0489L 160500 0315 6 -030 045 Fail 160500 03146 6 5 -03656L 164927 0113 6 -028 016 Fail 164927 01127 6 5 00835L 165000 0261 6 -028 038 Fail 165000 02608 6 5 00919L 166667 0505 6 -027 073 Fail 166667 05046 6 5 02645L 168850 0763 6 -026 110 Fail 168850 07628 6 5 04816L 173333 0516 6 -024 074 Fail 173333 05164 6 5 09334L 174761 0346 6 -024 050 Fail 174761 03462 6 5 10730L 175333 0473 3 -024 068 Fail 175333 04726 3 2 11366L 189375 2035 4 -017 294 Fail - - 66L - - 25346L 227500 0500 4 000 072 - - 46L - - 63470L 1040400 - 1 360 Fail - - 70L - - 8763

Totgem 22841 0526 gkg 1-level 232 (176) 12 164078 (46L 66L70L) 12 11Totstd= 22541 0469 5-level 186 (152) 3

71RESULTS Mean = 1640777 gkg

Repeatability variance S2r = 018808Repeatability std Sr = 043368 --gt 264 r = 12143Between lab variance S2L = 054747Reproducibility var S2R = 073555Reproducibility std SR = 085764 --gt 523 R = 24014Remarks 3 Labs rejected (46L 66L70L)

000 050 100 150 200 250 300

k-values

36L

65L

44L

32L

9L

56L

35L

19L

45L

16L

34L

30L

66L

46L

70L

Mandels k statistics(Soil 4 - TOC)

-100 00 100 200 300 400 500 600 700 800 900

Deviation from Mean

36L

65L

44L

32L

9L

56L

35L

19L

45L

16L

34L

30L

66L

46L

70L

Labo

rato

ries

Soil 4 - TOC -- Mean PARM = 1641 [gkg]

-100 000 100 200 300 400

h-values

36L

44L

9L

35L

45L

34L

66L

70L

Labo

rato

ries

Mandels h statistics(Soil 4 - TOC)

Soil 4-TOC

Unit gkg

Mandels k statistics(Soil 5 - TOC)Mandels h statistics(Soil 5 - TOC)

Sample Soil 5 Soil 5 - TOC -- Mean PARM = 2102 [gkg]

Element TOC

General calcparmT1= 113661E+03T2= 240201E+04T3= 54T4= 300T5= 51756E+01

n= variabelp= 10

N-table= 5

Mandels statistics End ResultLAB 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

44L 164383 14708 6 -036 325 Fail - - 44L - - -45865L 181250 0830 4 -033 018 Fail 181250 08302 4 3 -29045L 200317 1116 6 -029 025 Fail 200317 11163 6 5 -09935L 201833 1828 6 -029 040 Fail 201833 18280 6 5 -08432L 203250 0585 4 -029 013 Fail 203250 05852 4 3 -07016L 209000 0959 6 -028 021 Fail 209000 09592 6 5 -0129L 211667 0427 6 -027 009 Fail 211667 04274 6 5 01556L 214030 0887 6 -027 020 Fail 214030 08868 6 5 03819L 216000 0795 6 -026 018 Fail 216000 07950 6 5 05834L 226009 1308 6 -024 029 Fail 226009 13076 6 5 15836L 228783 4310 3 -024 095 Fail - - 36L - - 18666L 238750 1234 4 -022 027 Fail 238750 12340 4 3 28570L 2213900 - 1 333 Fail - - 70L - - 20037

Totgem 36224 2416 gkg 1-level 227 (175) 10 210211 (36L44L 70L) 10 9Totstd= 55669 4003 5-level 184 (151) 3

64RESULTS Mean = 2102106 gkg

Repeatability variance S2r = 117627Repeatability std Sr = 108456 --gt 516 r = 30368Between lab variance S2L = 176699Reproducibility var S2R = 294326Reproducibility std SR = 171559 --gt 816 R = 48037Remarks 3 Labs rejected (36L44L 70L)

000 050 100 150 200 250 300 350

k-values

44L

65L

45L

35L

32L

16L

9L

56L

19L

34L

36L

66L

70L

Mandels k statistics(Soil 5 - TOC)

-500 00 500 1000 1500 2000 2500

Deviation from Mean

44L

65L

45L

35L

32L

16L

9L

56L

19L

34L

36L

66L

70L

Labo

rato

ries

Soil 5 - TOC -- Mean PARM = 2102 [gkg]

-100 000 100 200 300 400

h-values

44L

65L

45L

35L

32L

16L

9L

56L

19L

34L

36L

66L

70L

Labo

rato

ries

Mandels h statistics(Soil 5 - TOC)

Soil 5-TOC

17

Annex 4

Raw data submitted

Sample Compost 1 Sample Compost 2 Sample Sewage Sludge 1Element TOC [gkg] Element TOC [gkg] Element TOC [gkg]

LAB PARM LAB PARM LAB PARM30L 2600 19L 1691 19L 286730L 2580 19L 1634 19L 281430L 2560 19L 1619 19L 276934L 2969 19L 1604 19L 272034L 2936 19L 1499 19L 268834L 2958 19L 1414 19L 266234L 2994 34L 1527 34L 315234L 3199 34L 1622 34L 314934L 3024 34L 1519 34L 343035L 2306 34L 1753 34L 336535L 2300 34L 1636 34L 304235L 2298 34L 1874 34L 298335L 2296 35L 1506 35L 270735L 2291 35L 1312 35L 270335L 2259 35L 1294 35L 268836L 2546 35L 1279 35L 267436L 2527 35L 1191 35L 263136L 2470 35L 1177 35L 262644L 2583 36L 1418 36L 271344L 2581 36L 1408 36L 266544L 2578 36L 1320 36L 261444L 2539 44L 1719 44L 292044L 2528 44L 1664 44L 291644L 2525 44L 1654 44L 291245L 2658 44L 1637 44L 290045L 2600 44L 1624 44L 289645L 2546 44L 1620 44L 289345L 2461 45L 1428 45L 297645L 2409 45L 1325 45L 295245L 2350 45L 1323 45L 288546L 2460 45L 1321 45L 286646L 2400 45L 1309 45L 284046L 2370 45L 1253 45L 278746L 2350 46L 1580 46L 233056L 2436 46L 1550 46L 233056L 2435 46L 1170 46L 230056L 2405 46L 1120 46L 229056L 2397 56L 1642 56L 270256L 2375 56L 1626 56L 270156L 2358 56L 1622 56L 269465L 2587 56L 1571 56L 269365L 2542 56L 1561 56L 268465L 2483 56L 1545 56L 268066L 2454 65L 1933 65L 264166L 2429 65L 1838 65L 260966L 2365 65L 1693 65L 260766L 2262 65L 1562 65L 260569L 2730 66L 1561 66L 270169L 2250 66L 1545 66L 267469L 1440 66L 1420 66L 261969L 1420 66L 1417 66L 251470L 2435 69L 2700 69L 2639L 2594 69L 2660 69L 2409L 2570 69L 2170 69L 2199L 2565 69L 2130 69L 2109L 2563 70L 1414 70L 28159L 2562 9L 1644 9L 28579L 2555 9L 1641 9L 2856

32L 2290 9L 1602 9L 285532L 2390 9L 1589 9L 285532L 2510 9L 1526 9L 285332L 2470 9L 1492 9L 284616L 2380 32L 1470 32L 265016L 2530 32L 1520 32L 271016L 2400 32L 1540 32L 271016L 2500 32L 1600 32L 280016L 2420 16L 1400 16L 284016L 2410 16L 1440 16L 2840

16L 1470 16L 286016L 1510 16L 287016L 1360 16L 287016L 1390 16L 2880

Sample Sewage Sludge 2 Sample Soil 4 Sample Soil 5Element TOC [gkg] Element TOC [gkg] Element TOC [gkg]

LAB PARM LAB PARM LAB PARM19L 2308 19L 1720 19L 225019L 2303 19L 1700 19L 223019L 2239 19L 1690 19L 221019L 2204 19L 1670 19L 211019L 2192 19L 1640 19L 210019L 2096 19L 1580 19L 206034L 2631 30L 1790 34L 244334L 2471 30L 1770 34L 233434L 2977 30L 1700 34L 231534L 2785 34L 1740 34L 222134L 2780 34L 1692 34L 217634L 2668 34L 1727 34L 207335L 2179 34L 1767 35L 233035L 2160 34L 1777 35L 208035L 2158 34L 1783 35L 201035L 2132 35L 1700 35L 198035L 2119 35L 1650 35L 193035L 2094 35L 1650 35L 178036L 2096 35L 1640 36L 254036L 2069 35L 1630 36L 253436L 2052 35L 1630 36L 179044L 2325 36L 1500 44L 302144L 2309 36L 1497 44L 298244L 2307 36L 1417 44L 295644L 2305 44L 1594 44L 30744L 2287 44L 1587 44L 30044L 2283 44L 1584 44L 29745L 2331 44L 1574 45L 214945L 2327 44L 1573 45L 209245L 2308 44L 1562 45L 203345L 2287 45L 1827 45L 197145L 2234 45L 1709 45L 193345L 2113 45L 1666 45L 184146L 190 45L 1665 56L 223746L 180 45L 1664 56L 222246L 180 45L 1600 56L 220346L 180 46L 2300 56L 206956L 2204 46L 2300 56L 206856L 2197 46L 2300 56L 204456L 2193 46L 2200 65L 192056L 2185 56L 1668 65L 182056L 2183 56L 1654 65L 179056L 2167 56L 1653 65L 172065L 2136 56L 1643 66L 254365L 2091 56L 1639 66L 242465L 2065 56L 1638 66L 232165L 2047 65L 1630 66L 226266L 2105 65L 1560 70L 2213966L 2022 65L 1530 9L 218066L 2009 65L 1490 9L 214066L 1983 66L 2179 9L 213070L 2272 66L 1900 9L 21109L 2385 66L 1762 9L 20709L 2377 66L 1734 9L 20709L 2375 70L 10404 32L 20509L 2359 9L 1640 32L 21009L 2356 9L 1640 32L 20209L 2354 9L 1610 32L 1960

32L 2240 9L 1590 16L 210032L 2260 9L 1590 16L 220032L 2200 9L 1560 16L 220032L 2270 32L 1640 16L 206016L 2300 32L 1600 16L 197016L 2310 32L 1560 16L 201016L 2350 32L 157016L 2260 16L 170016L 2290 16L 180016L 2240 16L 1700

16L 180016L 170016L 1700

European Commission EUR 23012 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on total organic carbon Author(s) E Sobiecka H van der Sloot K Andersen B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 50 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07412-7 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 total organic carbon (TOC) in soils sludge and treated bio-waste 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

-23012-EN

-C

Unit gkg

Mandels k statistics(Compost 1 - TOC)Mandels h statistics(Compost 1 - TOC)

Sample Compost 1 Compost 1 - TOC -- Mean PARM = 2463 [gkg]

Element TOC

General calcparmT1= 142643E+04T2= 351264E+06T3= 58T4= 292T5= 16501E+03

n= variabelp= 13

N-table= 5

Mandels statistics End ResultLAB 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

69L 1960000 64265 4 -235 352 Fail - - 69L - - -502735L 2291667 1674 6 -081 009 2291667 16741 6 5 -171066L 2377425 8552 4 -041 047 2377425 85518 4 3 -85346L 2395000 4796 4 -033 026 2395000 47958 4 3 -67756L 2401227 3133 6 -030 017 2401227 31330 6 5 -61432L 2415000 9713 4 -024 053 2415000 97125 4 3 -47770L 2435100 - 1 -014 2435100 - 1 -27616L 2440000 6033 6 -012 033 2440000 60332 6 5 -22745L 2503800 11759 6 018 064 2503800 117589 6 5 41136L 2514416 3994 3 023 022 2514416 39937 3 2 51765L 2537333 5216 3 033 029 2537333 52157 3 2 74744L 2555667 2783 6 042 015 2555667 27826 6 5 9309L 2568167 1356 6 048 007 2568167 13556 6 5 105530L 2580000 2000 3 053 011 2580000 20000 3 2 117334L 3013269 9580 6 255 053 Fail - - 34L - - 5506

Totgem 246587 9632 gkg 1-level 232 (176) 13 2462677 (34L 69L) 13 12Totstd= 21507 16070 5-level 186 (152) 2

68RESULTS Mean = 24626770 gkg

Repeatability variance S2r = 3666797Repeatability std Sr = 605541 --gt 246 r = 169551Between lab variance S2L = 7715586Reproducibility var S2R = 11382383Reproducibility std SR = 1066882 --gt 433 R = 298727Remarks 2 Labs rejected (34L 69L)

000 050 100 150 200 250 300 350 400

k-values

69L

35L

66L

46L

56L

32L

70L

16L

45L

36L

65L

44L

9L

30L

34L

Mandels k statistics(Compost 1 - TOC)

-600 -400 -200 00 200 400 600

Deviation from Mean

69L

35L

66L

46L

56L

32L

70L

16L

45L

36L

65L

44L

9L

30L

34L

Labo

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Compost 1 - TOC -- Mean PARM = 2463 [gkg]

-300 -200 -100 000 100 200 300

h-values

69L

66L

56L

70L

45L

65L

9L

34L

Labo

rato

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Mandels h statistics(Compost 1 - TOC)

Compost 1-TOC

Unit gkg

Mandels k statistics(Compost 2 - TOC)Mandels h statistics(Compost 2 - TOC)

Sample Compost 2 Compost 2 - TOC -- Mean PARM = 1542 [gkg]

Element TOC

General calcparmT1= 994897E+03T2= 155556E+06T3= 64T4= 346T5= 41738E+03

n= variabelp= 13

N-table= 5

Mandels statistics End ResultLAB 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

45L 1326733 5665 6 -100 042 Fail 1326733 56646 6 5 -215046L 1355000 24365 4 -089 181 Fail - - 46L - - -186736L 1381949 5407 3 -078 040 Fail 1381949 54070 3 2 -159870L 1414120 - 1 -066 Fail 1414120 - 1 -127616L 1428333 5565 6 -061 041 1428333 55648 6 5 -113466L 1485550 7805 4 -039 058 1485550 78047 4 3 -56232L 1532500 5377 4 -021 040 1532500 53774 4 3 -09219L 1576833 10138 6 -004 075 1576833 101381 6 5 3519L 1582333 6166 6 -002 046 1582333 61659 6 5 40656L 1594432 4046 6 003 030 1594432 40463 6 5 52744L 1653000 3651 6 025 027 1653000 36508 6 5 111334L 1655127 13717 6 026 102 1655127 137168 6 5 113434L 1655127 13717 6 026 102 1655127 137168 6 5 113465L 1756500 16295 4 065 121 Fail 1756500 162949 4 3 214869L 2415000 30687 4 316 228 Fail - - 69L - - 8733

Totgem 158750 10900 gkg 1-level 232 (176) 13 1541734 (46L 69L) 13 12Totstd= 26187 8164 5-level 186 (152) 2

72RESULTS Mean = 15417337 gkg

Repeatability variance S2r = 8183950Repeatability std Sr = 904652 --gt 587 r = 253303Between lab variance S2L = 13631046Reproducibility var S2R = 21814995Reproducibility std SR = 1476990 --gt 958 R = 413557Remarks 2 Labs rejected (46L 69L)

000 050 100 150 200 250

k-values

45L

46L

36L

70L

16L

66L

32L

19L

9L

56L

44L

34L

34L

65L

69L

Mandels k statistics(Compost 2 - TOC)

-400 -200 00 200 400 600 800 1000

Deviation from Mean

45L

46L

36L

70L

16L

66L

32L

19L

9L

56L

44L

34L

34L

65L

69L

Labo

rato

ries

Compost 2 - TOC -- Mean PARM = 1542 [gkg]

-100 000 100 200 300 400

h-values

45L

36L

16L

32L

9L

44L

34L

69L

Labo

rato

ries

Mandels h statistics(Compost 2 - TOC)

Compost 2-TOC

Unit gkg

Mandels k statistics(Sludge 1 - TOC)Mandels h statistics(Sludge 1 - TOC)

Sample Sludge 1 Sludge 1 - TOC -- Mean PARM = 2721 [gkg]

Element TOC

General calcparmT1= 169626E+04T2= 465445E+06T3= 62T4= 326T5= 10312E+03

n= variabelp= 13

N-table= 5

Mandels statistics End ResultLAB 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

69L 233000 2362 4 -347 037 Fail - - 69L - - -2488046L 2312500 2062 4 -040 032 Fail 2312500 20616 4 3 -408565L 2615500 1708 4 004 026 2615500 17078 4 3 -105566L 2627200 8268 4 006 128 2627200 82678 4 3 -93836L 2664041 4976 3 011 077 2664041 49758 3 2 -56935L 2671500 3533 6 013 055 2671500 35331 6 5 -49556L 2692298 0874 6 016 014 Fail 2692298 08738 6 5 -28732L 2717500 6185 4 019 096 Fail 2717500 61847 4 3 -03519L 2753333 7819 6 025 121 Fail 2753333 78189 6 5 32470L 2814600 - 1 034 Fail 2814600 - 1 9369L 2853667 0398 6 039 006 Fail 2853667 03983 6 5 132716L 2860000 1673 6 040 026 Fail 2860000 16733 6 5 139045L 2884433 7033 6 044 109 Fail 2884433 70331 6 5 163544L 2906167 1129 6 047 017 Fail 2906167 11286 6 5 185234L 3186874 17674 6 089 274 Fail - - 34L - - 4659

Totgem 258617 4692 gkg 1-level 232 (176) 13 2720980 (34L 69L) 13 12Totstd= 67800 4610 5-level 186 (152) 2

72RESULTS Mean = 27209799 gkg

Repeatability variance S2r = 2104538Repeatability std Sr = 458752 --gt 169 r = 128451Between lab variance S2L = 23618387Reproducibility var S2R = 25722925Reproducibility std SR = 1603837 --gt 589 R = 449074Remarks 2 Labs rejected (34L 69L)

000 050 100 150 200 250 300

k-values

69L

46L

65L

66L

36L

35L

56L

32L

19L

70L

9L

16L

45L

44L

34L

Mandels k statistics(Sludge 1 - TOC)

-2500 -2000 -1500 -1000 -500 00 500

Deviation from Mean

69L

46L

65L

66L

36L

35L

56L

32L

19L

70L

9L

16L

45L

44L

34L

Labo

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Sludge 1 - TOC -- Mean PARM = 2721 [gkg]

-400 -300 -200 -100 000 100

h-values

69L

65L

36L

56L

19L

9L

45L

34L

Labo

rato

ries

Mandels h statistics(Sludge 1 - TOC)

Sludge 1-TOC

68 Unit gkg

Mandels k statistics(Sludge 2 - TOC)Mandels h statistics(Sludge 2 - TOC)

Sample Sludge 2 Sludge 2 - TOC -- Mean PARM = 2207 [gkg]

Element TOC

General calcparmT1= 128601E+04T2= 285689E+06T3= 58T4= 310T5= 97826E+02

n= variabelp= 12

N-table= 5

Mandels statistics End ResultLAB 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

46L 182500 0500 4 -333 008 Fail - - 46L - - -2024466L 2029475 5267 4 -012 084 2029475 52674 4 3 -177436L 2072609 2222 3 -005 035 2072609 22222 3 2 -134365L 2084750 3865 4 -002 062 2084750 38647 4 3 -122135L 2140333 3119 6 007 050 2140333 31194 6 5 -66556L 2188021 1282 6 015 020 2188021 12822 6 5 -18819L 2223667 7916 6 022 126 Fail 2223667 79157 6 5 16832L 2242500 3096 4 025 049 Fail 2242500 30957 4 3 35645L 2266600 8322 6 029 132 Fail 2266600 83216 6 5 59770L 2272460 - 1 030 Fail 2272460 - 1 65616L 2291667 3869 6 033 062 Fail 2291667 38687 6 5 84844L 2302667 1546 6 035 025 Fail 2302667 15462 6 5 9589L 2367667 1296 6 047 021 Fail 2367667 12956 6 5 160834L 2718591 17124 6 108 273 Fail - - 34L - - 5117

Totgem 209882 4571 gkg 1-level 230 (176) 12 2206868 (34L 46L) 12 11Totstd= 57628 4485 5-level 185 (151) 2

68RESULTS Mean = 22068679 gkg

Repeatability variance S2r = 2126659Repeatability std Sr = 461157 --gt 209 r = 129124Between lab variance S2L = 9960432Reproducibility var S2R = 12087091Reproducibility std SR = 1099413 --gt 498 R = 307836Remarks 2 Labs rejected (34L 46L)

000 050 100 150 200 250 300

k-values

46L

66L

36L

65L

35L

56L

19L

32L

45L

70L

16L

44L

9L

34L

Mandels k statistics(Sludge 2 - TOC)

-2500 -2000 -1500 -1000 -500 00 500 1000

Deviation from Mean

46L

66L

36L

65L

35L

56L

19L

32L

45L

70L

16L

44L

9L

34L

Labo

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Sludge 2 - TOC -- Mean PARM = 2207 [gkg]

-400 -300 -200 -100 000 100 200

h-values

46L

66L

36L

65L

35L

56L

19L

32L

45L

70L

16L

44L

9L

34L

Labo

rato

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Mandels h statistics(Sludge 2 - TOC)

Sludge 2-TOC

Unit gkg

Mandels k statistics(Soil 4 - TOC)Mandels h statistics(Soil 4 - TOC)

Sample Soil 4 Soil 4 - TOC -- Mean PARM = 1641 [gkg]

Element TOC

General calcparmT1= 102171E+03T2= 168700E+04T3= 62T4= 338T5= 94040E+00

n= variabelp= 12

N-table= 5

Mandels statistics End ResultLAB 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

36L 147161 0470 3 -036 068 Fail 147161 04702 3 2 -16965L 155250 0591 4 -032 085 Fail 155250 05909 4 3 -08844L 157900 0115 6 -031 017 Fail 157900 01152 6 5 -06232L 159250 0359 4 -031 052 Fail 159250 03594 4 3 -0489L 160500 0315 6 -030 045 Fail 160500 03146 6 5 -03656L 164927 0113 6 -028 016 Fail 164927 01127 6 5 00835L 165000 0261 6 -028 038 Fail 165000 02608 6 5 00919L 166667 0505 6 -027 073 Fail 166667 05046 6 5 02645L 168850 0763 6 -026 110 Fail 168850 07628 6 5 04816L 173333 0516 6 -024 074 Fail 173333 05164 6 5 09334L 174761 0346 6 -024 050 Fail 174761 03462 6 5 10730L 175333 0473 3 -024 068 Fail 175333 04726 3 2 11366L 189375 2035 4 -017 294 Fail - - 66L - - 25346L 227500 0500 4 000 072 - - 46L - - 63470L 1040400 - 1 360 Fail - - 70L - - 8763

Totgem 22841 0526 gkg 1-level 232 (176) 12 164078 (46L 66L70L) 12 11Totstd= 22541 0469 5-level 186 (152) 3

71RESULTS Mean = 1640777 gkg

Repeatability variance S2r = 018808Repeatability std Sr = 043368 --gt 264 r = 12143Between lab variance S2L = 054747Reproducibility var S2R = 073555Reproducibility std SR = 085764 --gt 523 R = 24014Remarks 3 Labs rejected (46L 66L70L)

000 050 100 150 200 250 300

k-values

36L

65L

44L

32L

9L

56L

35L

19L

45L

16L

34L

30L

66L

46L

70L

Mandels k statistics(Soil 4 - TOC)

-100 00 100 200 300 400 500 600 700 800 900

Deviation from Mean

36L

65L

44L

32L

9L

56L

35L

19L

45L

16L

34L

30L

66L

46L

70L

Labo

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Soil 4 - TOC -- Mean PARM = 1641 [gkg]

-100 000 100 200 300 400

h-values

36L

44L

9L

35L

45L

34L

66L

70L

Labo

rato

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Mandels h statistics(Soil 4 - TOC)

Soil 4-TOC

Unit gkg

Mandels k statistics(Soil 5 - TOC)Mandels h statistics(Soil 5 - TOC)

Sample Soil 5 Soil 5 - TOC -- Mean PARM = 2102 [gkg]

Element TOC

General calcparmT1= 113661E+03T2= 240201E+04T3= 54T4= 300T5= 51756E+01

n= variabelp= 10

N-table= 5

Mandels statistics End ResultLAB 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

44L 164383 14708 6 -036 325 Fail - - 44L - - -45865L 181250 0830 4 -033 018 Fail 181250 08302 4 3 -29045L 200317 1116 6 -029 025 Fail 200317 11163 6 5 -09935L 201833 1828 6 -029 040 Fail 201833 18280 6 5 -08432L 203250 0585 4 -029 013 Fail 203250 05852 4 3 -07016L 209000 0959 6 -028 021 Fail 209000 09592 6 5 -0129L 211667 0427 6 -027 009 Fail 211667 04274 6 5 01556L 214030 0887 6 -027 020 Fail 214030 08868 6 5 03819L 216000 0795 6 -026 018 Fail 216000 07950 6 5 05834L 226009 1308 6 -024 029 Fail 226009 13076 6 5 15836L 228783 4310 3 -024 095 Fail - - 36L - - 18666L 238750 1234 4 -022 027 Fail 238750 12340 4 3 28570L 2213900 - 1 333 Fail - - 70L - - 20037

Totgem 36224 2416 gkg 1-level 227 (175) 10 210211 (36L44L 70L) 10 9Totstd= 55669 4003 5-level 184 (151) 3

64RESULTS Mean = 2102106 gkg

Repeatability variance S2r = 117627Repeatability std Sr = 108456 --gt 516 r = 30368Between lab variance S2L = 176699Reproducibility var S2R = 294326Reproducibility std SR = 171559 --gt 816 R = 48037Remarks 3 Labs rejected (36L44L 70L)

000 050 100 150 200 250 300 350

k-values

44L

65L

45L

35L

32L

16L

9L

56L

19L

34L

36L

66L

70L

Mandels k statistics(Soil 5 - TOC)

-500 00 500 1000 1500 2000 2500

Deviation from Mean

44L

65L

45L

35L

32L

16L

9L

56L

19L

34L

36L

66L

70L

Labo

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Soil 5 - TOC -- Mean PARM = 2102 [gkg]

-100 000 100 200 300 400

h-values

44L

65L

45L

35L

32L

16L

9L

56L

19L

34L

36L

66L

70L

Labo

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Mandels h statistics(Soil 5 - TOC)

Soil 5-TOC

17

Annex 4

Raw data submitted

Sample Compost 1 Sample Compost 2 Sample Sewage Sludge 1Element TOC [gkg] Element TOC [gkg] Element TOC [gkg]

LAB PARM LAB PARM LAB PARM30L 2600 19L 1691 19L 286730L 2580 19L 1634 19L 281430L 2560 19L 1619 19L 276934L 2969 19L 1604 19L 272034L 2936 19L 1499 19L 268834L 2958 19L 1414 19L 266234L 2994 34L 1527 34L 315234L 3199 34L 1622 34L 314934L 3024 34L 1519 34L 343035L 2306 34L 1753 34L 336535L 2300 34L 1636 34L 304235L 2298 34L 1874 34L 298335L 2296 35L 1506 35L 270735L 2291 35L 1312 35L 270335L 2259 35L 1294 35L 268836L 2546 35L 1279 35L 267436L 2527 35L 1191 35L 263136L 2470 35L 1177 35L 262644L 2583 36L 1418 36L 271344L 2581 36L 1408 36L 266544L 2578 36L 1320 36L 261444L 2539 44L 1719 44L 292044L 2528 44L 1664 44L 291644L 2525 44L 1654 44L 291245L 2658 44L 1637 44L 290045L 2600 44L 1624 44L 289645L 2546 44L 1620 44L 289345L 2461 45L 1428 45L 297645L 2409 45L 1325 45L 295245L 2350 45L 1323 45L 288546L 2460 45L 1321 45L 286646L 2400 45L 1309 45L 284046L 2370 45L 1253 45L 278746L 2350 46L 1580 46L 233056L 2436 46L 1550 46L 233056L 2435 46L 1170 46L 230056L 2405 46L 1120 46L 229056L 2397 56L 1642 56L 270256L 2375 56L 1626 56L 270156L 2358 56L 1622 56L 269465L 2587 56L 1571 56L 269365L 2542 56L 1561 56L 268465L 2483 56L 1545 56L 268066L 2454 65L 1933 65L 264166L 2429 65L 1838 65L 260966L 2365 65L 1693 65L 260766L 2262 65L 1562 65L 260569L 2730 66L 1561 66L 270169L 2250 66L 1545 66L 267469L 1440 66L 1420 66L 261969L 1420 66L 1417 66L 251470L 2435 69L 2700 69L 2639L 2594 69L 2660 69L 2409L 2570 69L 2170 69L 2199L 2565 69L 2130 69L 2109L 2563 70L 1414 70L 28159L 2562 9L 1644 9L 28579L 2555 9L 1641 9L 2856

32L 2290 9L 1602 9L 285532L 2390 9L 1589 9L 285532L 2510 9L 1526 9L 285332L 2470 9L 1492 9L 284616L 2380 32L 1470 32L 265016L 2530 32L 1520 32L 271016L 2400 32L 1540 32L 271016L 2500 32L 1600 32L 280016L 2420 16L 1400 16L 284016L 2410 16L 1440 16L 2840

16L 1470 16L 286016L 1510 16L 287016L 1360 16L 287016L 1390 16L 2880

Sample Sewage Sludge 2 Sample Soil 4 Sample Soil 5Element TOC [gkg] Element TOC [gkg] Element TOC [gkg]

LAB PARM LAB PARM LAB PARM19L 2308 19L 1720 19L 225019L 2303 19L 1700 19L 223019L 2239 19L 1690 19L 221019L 2204 19L 1670 19L 211019L 2192 19L 1640 19L 210019L 2096 19L 1580 19L 206034L 2631 30L 1790 34L 244334L 2471 30L 1770 34L 233434L 2977 30L 1700 34L 231534L 2785 34L 1740 34L 222134L 2780 34L 1692 34L 217634L 2668 34L 1727 34L 207335L 2179 34L 1767 35L 233035L 2160 34L 1777 35L 208035L 2158 34L 1783 35L 201035L 2132 35L 1700 35L 198035L 2119 35L 1650 35L 193035L 2094 35L 1650 35L 178036L 2096 35L 1640 36L 254036L 2069 35L 1630 36L 253436L 2052 35L 1630 36L 179044L 2325 36L 1500 44L 302144L 2309 36L 1497 44L 298244L 2307 36L 1417 44L 295644L 2305 44L 1594 44L 30744L 2287 44L 1587 44L 30044L 2283 44L 1584 44L 29745L 2331 44L 1574 45L 214945L 2327 44L 1573 45L 209245L 2308 44L 1562 45L 203345L 2287 45L 1827 45L 197145L 2234 45L 1709 45L 193345L 2113 45L 1666 45L 184146L 190 45L 1665 56L 223746L 180 45L 1664 56L 222246L 180 45L 1600 56L 220346L 180 46L 2300 56L 206956L 2204 46L 2300 56L 206856L 2197 46L 2300 56L 204456L 2193 46L 2200 65L 192056L 2185 56L 1668 65L 182056L 2183 56L 1654 65L 179056L 2167 56L 1653 65L 172065L 2136 56L 1643 66L 254365L 2091 56L 1639 66L 242465L 2065 56L 1638 66L 232165L 2047 65L 1630 66L 226266L 2105 65L 1560 70L 2213966L 2022 65L 1530 9L 218066L 2009 65L 1490 9L 214066L 1983 66L 2179 9L 213070L 2272 66L 1900 9L 21109L 2385 66L 1762 9L 20709L 2377 66L 1734 9L 20709L 2375 70L 10404 32L 20509L 2359 9L 1640 32L 21009L 2356 9L 1640 32L 20209L 2354 9L 1610 32L 1960

32L 2240 9L 1590 16L 210032L 2260 9L 1590 16L 220032L 2200 9L 1560 16L 220032L 2270 32L 1640 16L 206016L 2300 32L 1600 16L 197016L 2310 32L 1560 16L 201016L 2350 32L 157016L 2260 16L 170016L 2290 16L 180016L 2240 16L 1700

16L 180016L 170016L 1700

European Commission EUR 23012 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on total organic carbon Author(s) E Sobiecka H van der Sloot K Andersen B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 50 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07412-7 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 total organic carbon (TOC) in soils sludge and treated bio-waste 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

-23012-EN

-C

Unit gkg

Mandels k statistics(Compost 2 - TOC)Mandels h statistics(Compost 2 - TOC)

Sample Compost 2 Compost 2 - TOC -- Mean PARM = 1542 [gkg]

Element TOC

General calcparmT1= 994897E+03T2= 155556E+06T3= 64T4= 346T5= 41738E+03

n= variabelp= 13

N-table= 5

Mandels statistics End ResultLAB 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

45L 1326733 5665 6 -100 042 Fail 1326733 56646 6 5 -215046L 1355000 24365 4 -089 181 Fail - - 46L - - -186736L 1381949 5407 3 -078 040 Fail 1381949 54070 3 2 -159870L 1414120 - 1 -066 Fail 1414120 - 1 -127616L 1428333 5565 6 -061 041 1428333 55648 6 5 -113466L 1485550 7805 4 -039 058 1485550 78047 4 3 -56232L 1532500 5377 4 -021 040 1532500 53774 4 3 -09219L 1576833 10138 6 -004 075 1576833 101381 6 5 3519L 1582333 6166 6 -002 046 1582333 61659 6 5 40656L 1594432 4046 6 003 030 1594432 40463 6 5 52744L 1653000 3651 6 025 027 1653000 36508 6 5 111334L 1655127 13717 6 026 102 1655127 137168 6 5 113434L 1655127 13717 6 026 102 1655127 137168 6 5 113465L 1756500 16295 4 065 121 Fail 1756500 162949 4 3 214869L 2415000 30687 4 316 228 Fail - - 69L - - 8733

Totgem 158750 10900 gkg 1-level 232 (176) 13 1541734 (46L 69L) 13 12Totstd= 26187 8164 5-level 186 (152) 2

72RESULTS Mean = 15417337 gkg

Repeatability variance S2r = 8183950Repeatability std Sr = 904652 --gt 587 r = 253303Between lab variance S2L = 13631046Reproducibility var S2R = 21814995Reproducibility std SR = 1476990 --gt 958 R = 413557Remarks 2 Labs rejected (46L 69L)

000 050 100 150 200 250

k-values

45L

46L

36L

70L

16L

66L

32L

19L

9L

56L

44L

34L

34L

65L

69L

Mandels k statistics(Compost 2 - TOC)

-400 -200 00 200 400 600 800 1000

Deviation from Mean

45L

46L

36L

70L

16L

66L

32L

19L

9L

56L

44L

34L

34L

65L

69L

Labo

rato

ries

Compost 2 - TOC -- Mean PARM = 1542 [gkg]

-100 000 100 200 300 400

h-values

45L

36L

16L

32L

9L

44L

34L

69L

Labo

rato

ries

Mandels h statistics(Compost 2 - TOC)

Compost 2-TOC

Unit gkg

Mandels k statistics(Sludge 1 - TOC)Mandels h statistics(Sludge 1 - TOC)

Sample Sludge 1 Sludge 1 - TOC -- Mean PARM = 2721 [gkg]

Element TOC

General calcparmT1= 169626E+04T2= 465445E+06T3= 62T4= 326T5= 10312E+03

n= variabelp= 13

N-table= 5

Mandels statistics End ResultLAB 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

69L 233000 2362 4 -347 037 Fail - - 69L - - -2488046L 2312500 2062 4 -040 032 Fail 2312500 20616 4 3 -408565L 2615500 1708 4 004 026 2615500 17078 4 3 -105566L 2627200 8268 4 006 128 2627200 82678 4 3 -93836L 2664041 4976 3 011 077 2664041 49758 3 2 -56935L 2671500 3533 6 013 055 2671500 35331 6 5 -49556L 2692298 0874 6 016 014 Fail 2692298 08738 6 5 -28732L 2717500 6185 4 019 096 Fail 2717500 61847 4 3 -03519L 2753333 7819 6 025 121 Fail 2753333 78189 6 5 32470L 2814600 - 1 034 Fail 2814600 - 1 9369L 2853667 0398 6 039 006 Fail 2853667 03983 6 5 132716L 2860000 1673 6 040 026 Fail 2860000 16733 6 5 139045L 2884433 7033 6 044 109 Fail 2884433 70331 6 5 163544L 2906167 1129 6 047 017 Fail 2906167 11286 6 5 185234L 3186874 17674 6 089 274 Fail - - 34L - - 4659

Totgem 258617 4692 gkg 1-level 232 (176) 13 2720980 (34L 69L) 13 12Totstd= 67800 4610 5-level 186 (152) 2

72RESULTS Mean = 27209799 gkg

Repeatability variance S2r = 2104538Repeatability std Sr = 458752 --gt 169 r = 128451Between lab variance S2L = 23618387Reproducibility var S2R = 25722925Reproducibility std SR = 1603837 --gt 589 R = 449074Remarks 2 Labs rejected (34L 69L)

000 050 100 150 200 250 300

k-values

69L

46L

65L

66L

36L

35L

56L

32L

19L

70L

9L

16L

45L

44L

34L

Mandels k statistics(Sludge 1 - TOC)

-2500 -2000 -1500 -1000 -500 00 500

Deviation from Mean

69L

46L

65L

66L

36L

35L

56L

32L

19L

70L

9L

16L

45L

44L

34L

Labo

rato

ries

Sludge 1 - TOC -- Mean PARM = 2721 [gkg]

-400 -300 -200 -100 000 100

h-values

69L

65L

36L

56L

19L

9L

45L

34L

Labo

rato

ries

Mandels h statistics(Sludge 1 - TOC)

Sludge 1-TOC

68 Unit gkg

Mandels k statistics(Sludge 2 - TOC)Mandels h statistics(Sludge 2 - TOC)

Sample Sludge 2 Sludge 2 - TOC -- Mean PARM = 2207 [gkg]

Element TOC

General calcparmT1= 128601E+04T2= 285689E+06T3= 58T4= 310T5= 97826E+02

n= variabelp= 12

N-table= 5

Mandels statistics End ResultLAB 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

46L 182500 0500 4 -333 008 Fail - - 46L - - -2024466L 2029475 5267 4 -012 084 2029475 52674 4 3 -177436L 2072609 2222 3 -005 035 2072609 22222 3 2 -134365L 2084750 3865 4 -002 062 2084750 38647 4 3 -122135L 2140333 3119 6 007 050 2140333 31194 6 5 -66556L 2188021 1282 6 015 020 2188021 12822 6 5 -18819L 2223667 7916 6 022 126 Fail 2223667 79157 6 5 16832L 2242500 3096 4 025 049 Fail 2242500 30957 4 3 35645L 2266600 8322 6 029 132 Fail 2266600 83216 6 5 59770L 2272460 - 1 030 Fail 2272460 - 1 65616L 2291667 3869 6 033 062 Fail 2291667 38687 6 5 84844L 2302667 1546 6 035 025 Fail 2302667 15462 6 5 9589L 2367667 1296 6 047 021 Fail 2367667 12956 6 5 160834L 2718591 17124 6 108 273 Fail - - 34L - - 5117

Totgem 209882 4571 gkg 1-level 230 (176) 12 2206868 (34L 46L) 12 11Totstd= 57628 4485 5-level 185 (151) 2

68RESULTS Mean = 22068679 gkg

Repeatability variance S2r = 2126659Repeatability std Sr = 461157 --gt 209 r = 129124Between lab variance S2L = 9960432Reproducibility var S2R = 12087091Reproducibility std SR = 1099413 --gt 498 R = 307836Remarks 2 Labs rejected (34L 46L)

000 050 100 150 200 250 300

k-values

46L

66L

36L

65L

35L

56L

19L

32L

45L

70L

16L

44L

9L

34L

Mandels k statistics(Sludge 2 - TOC)

-2500 -2000 -1500 -1000 -500 00 500 1000

Deviation from Mean

46L

66L

36L

65L

35L

56L

19L

32L

45L

70L

16L

44L

9L

34L

Labo

rato

ries

Sludge 2 - TOC -- Mean PARM = 2207 [gkg]

-400 -300 -200 -100 000 100 200

h-values

46L

66L

36L

65L

35L

56L

19L

32L

45L

70L

16L

44L

9L

34L

Labo

rato

ries

Mandels h statistics(Sludge 2 - TOC)

Sludge 2-TOC

Unit gkg

Mandels k statistics(Soil 4 - TOC)Mandels h statistics(Soil 4 - TOC)

Sample Soil 4 Soil 4 - TOC -- Mean PARM = 1641 [gkg]

Element TOC

General calcparmT1= 102171E+03T2= 168700E+04T3= 62T4= 338T5= 94040E+00

n= variabelp= 12

N-table= 5

Mandels statistics End ResultLAB 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

36L 147161 0470 3 -036 068 Fail 147161 04702 3 2 -16965L 155250 0591 4 -032 085 Fail 155250 05909 4 3 -08844L 157900 0115 6 -031 017 Fail 157900 01152 6 5 -06232L 159250 0359 4 -031 052 Fail 159250 03594 4 3 -0489L 160500 0315 6 -030 045 Fail 160500 03146 6 5 -03656L 164927 0113 6 -028 016 Fail 164927 01127 6 5 00835L 165000 0261 6 -028 038 Fail 165000 02608 6 5 00919L 166667 0505 6 -027 073 Fail 166667 05046 6 5 02645L 168850 0763 6 -026 110 Fail 168850 07628 6 5 04816L 173333 0516 6 -024 074 Fail 173333 05164 6 5 09334L 174761 0346 6 -024 050 Fail 174761 03462 6 5 10730L 175333 0473 3 -024 068 Fail 175333 04726 3 2 11366L 189375 2035 4 -017 294 Fail - - 66L - - 25346L 227500 0500 4 000 072 - - 46L - - 63470L 1040400 - 1 360 Fail - - 70L - - 8763

Totgem 22841 0526 gkg 1-level 232 (176) 12 164078 (46L 66L70L) 12 11Totstd= 22541 0469 5-level 186 (152) 3

71RESULTS Mean = 1640777 gkg

Repeatability variance S2r = 018808Repeatability std Sr = 043368 --gt 264 r = 12143Between lab variance S2L = 054747Reproducibility var S2R = 073555Reproducibility std SR = 085764 --gt 523 R = 24014Remarks 3 Labs rejected (46L 66L70L)

000 050 100 150 200 250 300

k-values

36L

65L

44L

32L

9L

56L

35L

19L

45L

16L

34L

30L

66L

46L

70L

Mandels k statistics(Soil 4 - TOC)

-100 00 100 200 300 400 500 600 700 800 900

Deviation from Mean

36L

65L

44L

32L

9L

56L

35L

19L

45L

16L

34L

30L

66L

46L

70L

Labo

rato

ries

Soil 4 - TOC -- Mean PARM = 1641 [gkg]

-100 000 100 200 300 400

h-values

36L

44L

9L

35L

45L

34L

66L

70L

Labo

rato

ries

Mandels h statistics(Soil 4 - TOC)

Soil 4-TOC

Unit gkg

Mandels k statistics(Soil 5 - TOC)Mandels h statistics(Soil 5 - TOC)

Sample Soil 5 Soil 5 - TOC -- Mean PARM = 2102 [gkg]

Element TOC

General calcparmT1= 113661E+03T2= 240201E+04T3= 54T4= 300T5= 51756E+01

n= variabelp= 10

N-table= 5

Mandels statistics End ResultLAB 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

44L 164383 14708 6 -036 325 Fail - - 44L - - -45865L 181250 0830 4 -033 018 Fail 181250 08302 4 3 -29045L 200317 1116 6 -029 025 Fail 200317 11163 6 5 -09935L 201833 1828 6 -029 040 Fail 201833 18280 6 5 -08432L 203250 0585 4 -029 013 Fail 203250 05852 4 3 -07016L 209000 0959 6 -028 021 Fail 209000 09592 6 5 -0129L 211667 0427 6 -027 009 Fail 211667 04274 6 5 01556L 214030 0887 6 -027 020 Fail 214030 08868 6 5 03819L 216000 0795 6 -026 018 Fail 216000 07950 6 5 05834L 226009 1308 6 -024 029 Fail 226009 13076 6 5 15836L 228783 4310 3 -024 095 Fail - - 36L - - 18666L 238750 1234 4 -022 027 Fail 238750 12340 4 3 28570L 2213900 - 1 333 Fail - - 70L - - 20037

Totgem 36224 2416 gkg 1-level 227 (175) 10 210211 (36L44L 70L) 10 9Totstd= 55669 4003 5-level 184 (151) 3

64RESULTS Mean = 2102106 gkg

Repeatability variance S2r = 117627Repeatability std Sr = 108456 --gt 516 r = 30368Between lab variance S2L = 176699Reproducibility var S2R = 294326Reproducibility std SR = 171559 --gt 816 R = 48037Remarks 3 Labs rejected (36L44L 70L)

000 050 100 150 200 250 300 350

k-values

44L

65L

45L

35L

32L

16L

9L

56L

19L

34L

36L

66L

70L

Mandels k statistics(Soil 5 - TOC)

-500 00 500 1000 1500 2000 2500

Deviation from Mean

44L

65L

45L

35L

32L

16L

9L

56L

19L

34L

36L

66L

70L

Labo

rato

ries

Soil 5 - TOC -- Mean PARM = 2102 [gkg]

-100 000 100 200 300 400

h-values

44L

65L

45L

35L

32L

16L

9L

56L

19L

34L

36L

66L

70L

Labo

rato

ries

Mandels h statistics(Soil 5 - TOC)

Soil 5-TOC

17

Annex 4

Raw data submitted

Sample Compost 1 Sample Compost 2 Sample Sewage Sludge 1Element TOC [gkg] Element TOC [gkg] Element TOC [gkg]

LAB PARM LAB PARM LAB PARM30L 2600 19L 1691 19L 286730L 2580 19L 1634 19L 281430L 2560 19L 1619 19L 276934L 2969 19L 1604 19L 272034L 2936 19L 1499 19L 268834L 2958 19L 1414 19L 266234L 2994 34L 1527 34L 315234L 3199 34L 1622 34L 314934L 3024 34L 1519 34L 343035L 2306 34L 1753 34L 336535L 2300 34L 1636 34L 304235L 2298 34L 1874 34L 298335L 2296 35L 1506 35L 270735L 2291 35L 1312 35L 270335L 2259 35L 1294 35L 268836L 2546 35L 1279 35L 267436L 2527 35L 1191 35L 263136L 2470 35L 1177 35L 262644L 2583 36L 1418 36L 271344L 2581 36L 1408 36L 266544L 2578 36L 1320 36L 261444L 2539 44L 1719 44L 292044L 2528 44L 1664 44L 291644L 2525 44L 1654 44L 291245L 2658 44L 1637 44L 290045L 2600 44L 1624 44L 289645L 2546 44L 1620 44L 289345L 2461 45L 1428 45L 297645L 2409 45L 1325 45L 295245L 2350 45L 1323 45L 288546L 2460 45L 1321 45L 286646L 2400 45L 1309 45L 284046L 2370 45L 1253 45L 278746L 2350 46L 1580 46L 233056L 2436 46L 1550 46L 233056L 2435 46L 1170 46L 230056L 2405 46L 1120 46L 229056L 2397 56L 1642 56L 270256L 2375 56L 1626 56L 270156L 2358 56L 1622 56L 269465L 2587 56L 1571 56L 269365L 2542 56L 1561 56L 268465L 2483 56L 1545 56L 268066L 2454 65L 1933 65L 264166L 2429 65L 1838 65L 260966L 2365 65L 1693 65L 260766L 2262 65L 1562 65L 260569L 2730 66L 1561 66L 270169L 2250 66L 1545 66L 267469L 1440 66L 1420 66L 261969L 1420 66L 1417 66L 251470L 2435 69L 2700 69L 2639L 2594 69L 2660 69L 2409L 2570 69L 2170 69L 2199L 2565 69L 2130 69L 2109L 2563 70L 1414 70L 28159L 2562 9L 1644 9L 28579L 2555 9L 1641 9L 2856

32L 2290 9L 1602 9L 285532L 2390 9L 1589 9L 285532L 2510 9L 1526 9L 285332L 2470 9L 1492 9L 284616L 2380 32L 1470 32L 265016L 2530 32L 1520 32L 271016L 2400 32L 1540 32L 271016L 2500 32L 1600 32L 280016L 2420 16L 1400 16L 284016L 2410 16L 1440 16L 2840

16L 1470 16L 286016L 1510 16L 287016L 1360 16L 287016L 1390 16L 2880

Sample Sewage Sludge 2 Sample Soil 4 Sample Soil 5Element TOC [gkg] Element TOC [gkg] Element TOC [gkg]

LAB PARM LAB PARM LAB PARM19L 2308 19L 1720 19L 225019L 2303 19L 1700 19L 223019L 2239 19L 1690 19L 221019L 2204 19L 1670 19L 211019L 2192 19L 1640 19L 210019L 2096 19L 1580 19L 206034L 2631 30L 1790 34L 244334L 2471 30L 1770 34L 233434L 2977 30L 1700 34L 231534L 2785 34L 1740 34L 222134L 2780 34L 1692 34L 217634L 2668 34L 1727 34L 207335L 2179 34L 1767 35L 233035L 2160 34L 1777 35L 208035L 2158 34L 1783 35L 201035L 2132 35L 1700 35L 198035L 2119 35L 1650 35L 193035L 2094 35L 1650 35L 178036L 2096 35L 1640 36L 254036L 2069 35L 1630 36L 253436L 2052 35L 1630 36L 179044L 2325 36L 1500 44L 302144L 2309 36L 1497 44L 298244L 2307 36L 1417 44L 295644L 2305 44L 1594 44L 30744L 2287 44L 1587 44L 30044L 2283 44L 1584 44L 29745L 2331 44L 1574 45L 214945L 2327 44L 1573 45L 209245L 2308 44L 1562 45L 203345L 2287 45L 1827 45L 197145L 2234 45L 1709 45L 193345L 2113 45L 1666 45L 184146L 190 45L 1665 56L 223746L 180 45L 1664 56L 222246L 180 45L 1600 56L 220346L 180 46L 2300 56L 206956L 2204 46L 2300 56L 206856L 2197 46L 2300 56L 204456L 2193 46L 2200 65L 192056L 2185 56L 1668 65L 182056L 2183 56L 1654 65L 179056L 2167 56L 1653 65L 172065L 2136 56L 1643 66L 254365L 2091 56L 1639 66L 242465L 2065 56L 1638 66L 232165L 2047 65L 1630 66L 226266L 2105 65L 1560 70L 2213966L 2022 65L 1530 9L 218066L 2009 65L 1490 9L 214066L 1983 66L 2179 9L 213070L 2272 66L 1900 9L 21109L 2385 66L 1762 9L 20709L 2377 66L 1734 9L 20709L 2375 70L 10404 32L 20509L 2359 9L 1640 32L 21009L 2356 9L 1640 32L 20209L 2354 9L 1610 32L 1960

32L 2240 9L 1590 16L 210032L 2260 9L 1590 16L 220032L 2200 9L 1560 16L 220032L 2270 32L 1640 16L 206016L 2300 32L 1600 16L 197016L 2310 32L 1560 16L 201016L 2350 32L 157016L 2260 16L 170016L 2290 16L 180016L 2240 16L 1700

16L 180016L 170016L 1700

European Commission EUR 23012 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on total organic carbon Author(s) E Sobiecka H van der Sloot K Andersen B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 50 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07412-7 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 total organic carbon (TOC) in soils sludge and treated bio-waste 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

-23012-EN

-C

Unit gkg

Mandels k statistics(Sludge 1 - TOC)Mandels h statistics(Sludge 1 - TOC)

Sample Sludge 1 Sludge 1 - TOC -- Mean PARM = 2721 [gkg]

Element TOC

General calcparmT1= 169626E+04T2= 465445E+06T3= 62T4= 326T5= 10312E+03

n= variabelp= 13

N-table= 5

Mandels statistics End ResultLAB 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

69L 233000 2362 4 -347 037 Fail - - 69L - - -2488046L 2312500 2062 4 -040 032 Fail 2312500 20616 4 3 -408565L 2615500 1708 4 004 026 2615500 17078 4 3 -105566L 2627200 8268 4 006 128 2627200 82678 4 3 -93836L 2664041 4976 3 011 077 2664041 49758 3 2 -56935L 2671500 3533 6 013 055 2671500 35331 6 5 -49556L 2692298 0874 6 016 014 Fail 2692298 08738 6 5 -28732L 2717500 6185 4 019 096 Fail 2717500 61847 4 3 -03519L 2753333 7819 6 025 121 Fail 2753333 78189 6 5 32470L 2814600 - 1 034 Fail 2814600 - 1 9369L 2853667 0398 6 039 006 Fail 2853667 03983 6 5 132716L 2860000 1673 6 040 026 Fail 2860000 16733 6 5 139045L 2884433 7033 6 044 109 Fail 2884433 70331 6 5 163544L 2906167 1129 6 047 017 Fail 2906167 11286 6 5 185234L 3186874 17674 6 089 274 Fail - - 34L - - 4659

Totgem 258617 4692 gkg 1-level 232 (176) 13 2720980 (34L 69L) 13 12Totstd= 67800 4610 5-level 186 (152) 2

72RESULTS Mean = 27209799 gkg

Repeatability variance S2r = 2104538Repeatability std Sr = 458752 --gt 169 r = 128451Between lab variance S2L = 23618387Reproducibility var S2R = 25722925Reproducibility std SR = 1603837 --gt 589 R = 449074Remarks 2 Labs rejected (34L 69L)

000 050 100 150 200 250 300

k-values

69L

46L

65L

66L

36L

35L

56L

32L

19L

70L

9L

16L

45L

44L

34L

Mandels k statistics(Sludge 1 - TOC)

-2500 -2000 -1500 -1000 -500 00 500

Deviation from Mean

69L

46L

65L

66L

36L

35L

56L

32L

19L

70L

9L

16L

45L

44L

34L

Labo

rato

ries

Sludge 1 - TOC -- Mean PARM = 2721 [gkg]

-400 -300 -200 -100 000 100

h-values

69L

65L

36L

56L

19L

9L

45L

34L

Labo

rato

ries

Mandels h statistics(Sludge 1 - TOC)

Sludge 1-TOC

68 Unit gkg

Mandels k statistics(Sludge 2 - TOC)Mandels h statistics(Sludge 2 - TOC)

Sample Sludge 2 Sludge 2 - TOC -- Mean PARM = 2207 [gkg]

Element TOC

General calcparmT1= 128601E+04T2= 285689E+06T3= 58T4= 310T5= 97826E+02

n= variabelp= 12

N-table= 5

Mandels statistics End ResultLAB 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

46L 182500 0500 4 -333 008 Fail - - 46L - - -2024466L 2029475 5267 4 -012 084 2029475 52674 4 3 -177436L 2072609 2222 3 -005 035 2072609 22222 3 2 -134365L 2084750 3865 4 -002 062 2084750 38647 4 3 -122135L 2140333 3119 6 007 050 2140333 31194 6 5 -66556L 2188021 1282 6 015 020 2188021 12822 6 5 -18819L 2223667 7916 6 022 126 Fail 2223667 79157 6 5 16832L 2242500 3096 4 025 049 Fail 2242500 30957 4 3 35645L 2266600 8322 6 029 132 Fail 2266600 83216 6 5 59770L 2272460 - 1 030 Fail 2272460 - 1 65616L 2291667 3869 6 033 062 Fail 2291667 38687 6 5 84844L 2302667 1546 6 035 025 Fail 2302667 15462 6 5 9589L 2367667 1296 6 047 021 Fail 2367667 12956 6 5 160834L 2718591 17124 6 108 273 Fail - - 34L - - 5117

Totgem 209882 4571 gkg 1-level 230 (176) 12 2206868 (34L 46L) 12 11Totstd= 57628 4485 5-level 185 (151) 2

68RESULTS Mean = 22068679 gkg

Repeatability variance S2r = 2126659Repeatability std Sr = 461157 --gt 209 r = 129124Between lab variance S2L = 9960432Reproducibility var S2R = 12087091Reproducibility std SR = 1099413 --gt 498 R = 307836Remarks 2 Labs rejected (34L 46L)

000 050 100 150 200 250 300

k-values

46L

66L

36L

65L

35L

56L

19L

32L

45L

70L

16L

44L

9L

34L

Mandels k statistics(Sludge 2 - TOC)

-2500 -2000 -1500 -1000 -500 00 500 1000

Deviation from Mean

46L

66L

36L

65L

35L

56L

19L

32L

45L

70L

16L

44L

9L

34L

Labo

rato

ries

Sludge 2 - TOC -- Mean PARM = 2207 [gkg]

-400 -300 -200 -100 000 100 200

h-values

46L

66L

36L

65L

35L

56L

19L

32L

45L

70L

16L

44L

9L

34L

Labo

rato

ries

Mandels h statistics(Sludge 2 - TOC)

Sludge 2-TOC

Unit gkg

Mandels k statistics(Soil 4 - TOC)Mandels h statistics(Soil 4 - TOC)

Sample Soil 4 Soil 4 - TOC -- Mean PARM = 1641 [gkg]

Element TOC

General calcparmT1= 102171E+03T2= 168700E+04T3= 62T4= 338T5= 94040E+00

n= variabelp= 12

N-table= 5

Mandels statistics End ResultLAB 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

36L 147161 0470 3 -036 068 Fail 147161 04702 3 2 -16965L 155250 0591 4 -032 085 Fail 155250 05909 4 3 -08844L 157900 0115 6 -031 017 Fail 157900 01152 6 5 -06232L 159250 0359 4 -031 052 Fail 159250 03594 4 3 -0489L 160500 0315 6 -030 045 Fail 160500 03146 6 5 -03656L 164927 0113 6 -028 016 Fail 164927 01127 6 5 00835L 165000 0261 6 -028 038 Fail 165000 02608 6 5 00919L 166667 0505 6 -027 073 Fail 166667 05046 6 5 02645L 168850 0763 6 -026 110 Fail 168850 07628 6 5 04816L 173333 0516 6 -024 074 Fail 173333 05164 6 5 09334L 174761 0346 6 -024 050 Fail 174761 03462 6 5 10730L 175333 0473 3 -024 068 Fail 175333 04726 3 2 11366L 189375 2035 4 -017 294 Fail - - 66L - - 25346L 227500 0500 4 000 072 - - 46L - - 63470L 1040400 - 1 360 Fail - - 70L - - 8763

Totgem 22841 0526 gkg 1-level 232 (176) 12 164078 (46L 66L70L) 12 11Totstd= 22541 0469 5-level 186 (152) 3

71RESULTS Mean = 1640777 gkg

Repeatability variance S2r = 018808Repeatability std Sr = 043368 --gt 264 r = 12143Between lab variance S2L = 054747Reproducibility var S2R = 073555Reproducibility std SR = 085764 --gt 523 R = 24014Remarks 3 Labs rejected (46L 66L70L)

000 050 100 150 200 250 300

k-values

36L

65L

44L

32L

9L

56L

35L

19L

45L

16L

34L

30L

66L

46L

70L

Mandels k statistics(Soil 4 - TOC)

-100 00 100 200 300 400 500 600 700 800 900

Deviation from Mean

36L

65L

44L

32L

9L

56L

35L

19L

45L

16L

34L

30L

66L

46L

70L

Labo

rato

ries

Soil 4 - TOC -- Mean PARM = 1641 [gkg]

-100 000 100 200 300 400

h-values

36L

44L

9L

35L

45L

34L

66L

70L

Labo

rato

ries

Mandels h statistics(Soil 4 - TOC)

Soil 4-TOC

Unit gkg

Mandels k statistics(Soil 5 - TOC)Mandels h statistics(Soil 5 - TOC)

Sample Soil 5 Soil 5 - TOC -- Mean PARM = 2102 [gkg]

Element TOC

General calcparmT1= 113661E+03T2= 240201E+04T3= 54T4= 300T5= 51756E+01

n= variabelp= 10

N-table= 5

Mandels statistics End ResultLAB 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

44L 164383 14708 6 -036 325 Fail - - 44L - - -45865L 181250 0830 4 -033 018 Fail 181250 08302 4 3 -29045L 200317 1116 6 -029 025 Fail 200317 11163 6 5 -09935L 201833 1828 6 -029 040 Fail 201833 18280 6 5 -08432L 203250 0585 4 -029 013 Fail 203250 05852 4 3 -07016L 209000 0959 6 -028 021 Fail 209000 09592 6 5 -0129L 211667 0427 6 -027 009 Fail 211667 04274 6 5 01556L 214030 0887 6 -027 020 Fail 214030 08868 6 5 03819L 216000 0795 6 -026 018 Fail 216000 07950 6 5 05834L 226009 1308 6 -024 029 Fail 226009 13076 6 5 15836L 228783 4310 3 -024 095 Fail - - 36L - - 18666L 238750 1234 4 -022 027 Fail 238750 12340 4 3 28570L 2213900 - 1 333 Fail - - 70L - - 20037

Totgem 36224 2416 gkg 1-level 227 (175) 10 210211 (36L44L 70L) 10 9Totstd= 55669 4003 5-level 184 (151) 3

64RESULTS Mean = 2102106 gkg

Repeatability variance S2r = 117627Repeatability std Sr = 108456 --gt 516 r = 30368Between lab variance S2L = 176699Reproducibility var S2R = 294326Reproducibility std SR = 171559 --gt 816 R = 48037Remarks 3 Labs rejected (36L44L 70L)

000 050 100 150 200 250 300 350

k-values

44L

65L

45L

35L

32L

16L

9L

56L

19L

34L

36L

66L

70L

Mandels k statistics(Soil 5 - TOC)

-500 00 500 1000 1500 2000 2500

Deviation from Mean

44L

65L

45L

35L

32L

16L

9L

56L

19L

34L

36L

66L

70L

Labo

rato

ries

Soil 5 - TOC -- Mean PARM = 2102 [gkg]

-100 000 100 200 300 400

h-values

44L

65L

45L

35L

32L

16L

9L

56L

19L

34L

36L

66L

70L

Labo

rato

ries

Mandels h statistics(Soil 5 - TOC)

Soil 5-TOC

17

Annex 4

Raw data submitted

Sample Compost 1 Sample Compost 2 Sample Sewage Sludge 1Element TOC [gkg] Element TOC [gkg] Element TOC [gkg]

LAB PARM LAB PARM LAB PARM30L 2600 19L 1691 19L 286730L 2580 19L 1634 19L 281430L 2560 19L 1619 19L 276934L 2969 19L 1604 19L 272034L 2936 19L 1499 19L 268834L 2958 19L 1414 19L 266234L 2994 34L 1527 34L 315234L 3199 34L 1622 34L 314934L 3024 34L 1519 34L 343035L 2306 34L 1753 34L 336535L 2300 34L 1636 34L 304235L 2298 34L 1874 34L 298335L 2296 35L 1506 35L 270735L 2291 35L 1312 35L 270335L 2259 35L 1294 35L 268836L 2546 35L 1279 35L 267436L 2527 35L 1191 35L 263136L 2470 35L 1177 35L 262644L 2583 36L 1418 36L 271344L 2581 36L 1408 36L 266544L 2578 36L 1320 36L 261444L 2539 44L 1719 44L 292044L 2528 44L 1664 44L 291644L 2525 44L 1654 44L 291245L 2658 44L 1637 44L 290045L 2600 44L 1624 44L 289645L 2546 44L 1620 44L 289345L 2461 45L 1428 45L 297645L 2409 45L 1325 45L 295245L 2350 45L 1323 45L 288546L 2460 45L 1321 45L 286646L 2400 45L 1309 45L 284046L 2370 45L 1253 45L 278746L 2350 46L 1580 46L 233056L 2436 46L 1550 46L 233056L 2435 46L 1170 46L 230056L 2405 46L 1120 46L 229056L 2397 56L 1642 56L 270256L 2375 56L 1626 56L 270156L 2358 56L 1622 56L 269465L 2587 56L 1571 56L 269365L 2542 56L 1561 56L 268465L 2483 56L 1545 56L 268066L 2454 65L 1933 65L 264166L 2429 65L 1838 65L 260966L 2365 65L 1693 65L 260766L 2262 65L 1562 65L 260569L 2730 66L 1561 66L 270169L 2250 66L 1545 66L 267469L 1440 66L 1420 66L 261969L 1420 66L 1417 66L 251470L 2435 69L 2700 69L 2639L 2594 69L 2660 69L 2409L 2570 69L 2170 69L 2199L 2565 69L 2130 69L 2109L 2563 70L 1414 70L 28159L 2562 9L 1644 9L 28579L 2555 9L 1641 9L 2856

32L 2290 9L 1602 9L 285532L 2390 9L 1589 9L 285532L 2510 9L 1526 9L 285332L 2470 9L 1492 9L 284616L 2380 32L 1470 32L 265016L 2530 32L 1520 32L 271016L 2400 32L 1540 32L 271016L 2500 32L 1600 32L 280016L 2420 16L 1400 16L 284016L 2410 16L 1440 16L 2840

16L 1470 16L 286016L 1510 16L 287016L 1360 16L 287016L 1390 16L 2880

Sample Sewage Sludge 2 Sample Soil 4 Sample Soil 5Element TOC [gkg] Element TOC [gkg] Element TOC [gkg]

LAB PARM LAB PARM LAB PARM19L 2308 19L 1720 19L 225019L 2303 19L 1700 19L 223019L 2239 19L 1690 19L 221019L 2204 19L 1670 19L 211019L 2192 19L 1640 19L 210019L 2096 19L 1580 19L 206034L 2631 30L 1790 34L 244334L 2471 30L 1770 34L 233434L 2977 30L 1700 34L 231534L 2785 34L 1740 34L 222134L 2780 34L 1692 34L 217634L 2668 34L 1727 34L 207335L 2179 34L 1767 35L 233035L 2160 34L 1777 35L 208035L 2158 34L 1783 35L 201035L 2132 35L 1700 35L 198035L 2119 35L 1650 35L 193035L 2094 35L 1650 35L 178036L 2096 35L 1640 36L 254036L 2069 35L 1630 36L 253436L 2052 35L 1630 36L 179044L 2325 36L 1500 44L 302144L 2309 36L 1497 44L 298244L 2307 36L 1417 44L 295644L 2305 44L 1594 44L 30744L 2287 44L 1587 44L 30044L 2283 44L 1584 44L 29745L 2331 44L 1574 45L 214945L 2327 44L 1573 45L 209245L 2308 44L 1562 45L 203345L 2287 45L 1827 45L 197145L 2234 45L 1709 45L 193345L 2113 45L 1666 45L 184146L 190 45L 1665 56L 223746L 180 45L 1664 56L 222246L 180 45L 1600 56L 220346L 180 46L 2300 56L 206956L 2204 46L 2300 56L 206856L 2197 46L 2300 56L 204456L 2193 46L 2200 65L 192056L 2185 56L 1668 65L 182056L 2183 56L 1654 65L 179056L 2167 56L 1653 65L 172065L 2136 56L 1643 66L 254365L 2091 56L 1639 66L 242465L 2065 56L 1638 66L 232165L 2047 65L 1630 66L 226266L 2105 65L 1560 70L 2213966L 2022 65L 1530 9L 218066L 2009 65L 1490 9L 214066L 1983 66L 2179 9L 213070L 2272 66L 1900 9L 21109L 2385 66L 1762 9L 20709L 2377 66L 1734 9L 20709L 2375 70L 10404 32L 20509L 2359 9L 1640 32L 21009L 2356 9L 1640 32L 20209L 2354 9L 1610 32L 1960

32L 2240 9L 1590 16L 210032L 2260 9L 1590 16L 220032L 2200 9L 1560 16L 220032L 2270 32L 1640 16L 206016L 2300 32L 1600 16L 197016L 2310 32L 1560 16L 201016L 2350 32L 157016L 2260 16L 170016L 2290 16L 180016L 2240 16L 1700

16L 180016L 170016L 1700

European Commission EUR 23012 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on total organic carbon Author(s) E Sobiecka H van der Sloot K Andersen B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 50 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07412-7 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 total organic carbon (TOC) in soils sludge and treated bio-waste 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

-23012-EN

-C

68 Unit gkg

Mandels k statistics(Sludge 2 - TOC)Mandels h statistics(Sludge 2 - TOC)

Sample Sludge 2 Sludge 2 - TOC -- Mean PARM = 2207 [gkg]

Element TOC

General calcparmT1= 128601E+04T2= 285689E+06T3= 58T4= 310T5= 97826E+02

n= variabelp= 12

N-table= 5

Mandels statistics End ResultLAB 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

46L 182500 0500 4 -333 008 Fail - - 46L - - -2024466L 2029475 5267 4 -012 084 2029475 52674 4 3 -177436L 2072609 2222 3 -005 035 2072609 22222 3 2 -134365L 2084750 3865 4 -002 062 2084750 38647 4 3 -122135L 2140333 3119 6 007 050 2140333 31194 6 5 -66556L 2188021 1282 6 015 020 2188021 12822 6 5 -18819L 2223667 7916 6 022 126 Fail 2223667 79157 6 5 16832L 2242500 3096 4 025 049 Fail 2242500 30957 4 3 35645L 2266600 8322 6 029 132 Fail 2266600 83216 6 5 59770L 2272460 - 1 030 Fail 2272460 - 1 65616L 2291667 3869 6 033 062 Fail 2291667 38687 6 5 84844L 2302667 1546 6 035 025 Fail 2302667 15462 6 5 9589L 2367667 1296 6 047 021 Fail 2367667 12956 6 5 160834L 2718591 17124 6 108 273 Fail - - 34L - - 5117

Totgem 209882 4571 gkg 1-level 230 (176) 12 2206868 (34L 46L) 12 11Totstd= 57628 4485 5-level 185 (151) 2

68RESULTS Mean = 22068679 gkg

Repeatability variance S2r = 2126659Repeatability std Sr = 461157 --gt 209 r = 129124Between lab variance S2L = 9960432Reproducibility var S2R = 12087091Reproducibility std SR = 1099413 --gt 498 R = 307836Remarks 2 Labs rejected (34L 46L)

000 050 100 150 200 250 300

k-values

46L

66L

36L

65L

35L

56L

19L

32L

45L

70L

16L

44L

9L

34L

Mandels k statistics(Sludge 2 - TOC)

-2500 -2000 -1500 -1000 -500 00 500 1000

Deviation from Mean

46L

66L

36L

65L

35L

56L

19L

32L

45L

70L

16L

44L

9L

34L

Labo

rato

ries

Sludge 2 - TOC -- Mean PARM = 2207 [gkg]

-400 -300 -200 -100 000 100 200

h-values

46L

66L

36L

65L

35L

56L

19L

32L

45L

70L

16L

44L

9L

34L

Labo

rato

ries

Mandels h statistics(Sludge 2 - TOC)

Sludge 2-TOC

Unit gkg

Mandels k statistics(Soil 4 - TOC)Mandels h statistics(Soil 4 - TOC)

Sample Soil 4 Soil 4 - TOC -- Mean PARM = 1641 [gkg]

Element TOC

General calcparmT1= 102171E+03T2= 168700E+04T3= 62T4= 338T5= 94040E+00

n= variabelp= 12

N-table= 5

Mandels statistics End ResultLAB 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

36L 147161 0470 3 -036 068 Fail 147161 04702 3 2 -16965L 155250 0591 4 -032 085 Fail 155250 05909 4 3 -08844L 157900 0115 6 -031 017 Fail 157900 01152 6 5 -06232L 159250 0359 4 -031 052 Fail 159250 03594 4 3 -0489L 160500 0315 6 -030 045 Fail 160500 03146 6 5 -03656L 164927 0113 6 -028 016 Fail 164927 01127 6 5 00835L 165000 0261 6 -028 038 Fail 165000 02608 6 5 00919L 166667 0505 6 -027 073 Fail 166667 05046 6 5 02645L 168850 0763 6 -026 110 Fail 168850 07628 6 5 04816L 173333 0516 6 -024 074 Fail 173333 05164 6 5 09334L 174761 0346 6 -024 050 Fail 174761 03462 6 5 10730L 175333 0473 3 -024 068 Fail 175333 04726 3 2 11366L 189375 2035 4 -017 294 Fail - - 66L - - 25346L 227500 0500 4 000 072 - - 46L - - 63470L 1040400 - 1 360 Fail - - 70L - - 8763

Totgem 22841 0526 gkg 1-level 232 (176) 12 164078 (46L 66L70L) 12 11Totstd= 22541 0469 5-level 186 (152) 3

71RESULTS Mean = 1640777 gkg

Repeatability variance S2r = 018808Repeatability std Sr = 043368 --gt 264 r = 12143Between lab variance S2L = 054747Reproducibility var S2R = 073555Reproducibility std SR = 085764 --gt 523 R = 24014Remarks 3 Labs rejected (46L 66L70L)

000 050 100 150 200 250 300

k-values

36L

65L

44L

32L

9L

56L

35L

19L

45L

16L

34L

30L

66L

46L

70L

Mandels k statistics(Soil 4 - TOC)

-100 00 100 200 300 400 500 600 700 800 900

Deviation from Mean

36L

65L

44L

32L

9L

56L

35L

19L

45L

16L

34L

30L

66L

46L

70L

Labo

rato

ries

Soil 4 - TOC -- Mean PARM = 1641 [gkg]

-100 000 100 200 300 400

h-values

36L

44L

9L

35L

45L

34L

66L

70L

Labo

rato

ries

Mandels h statistics(Soil 4 - TOC)

Soil 4-TOC

Unit gkg

Mandels k statistics(Soil 5 - TOC)Mandels h statistics(Soil 5 - TOC)

Sample Soil 5 Soil 5 - TOC -- Mean PARM = 2102 [gkg]

Element TOC

General calcparmT1= 113661E+03T2= 240201E+04T3= 54T4= 300T5= 51756E+01

n= variabelp= 10

N-table= 5

Mandels statistics End ResultLAB 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

44L 164383 14708 6 -036 325 Fail - - 44L - - -45865L 181250 0830 4 -033 018 Fail 181250 08302 4 3 -29045L 200317 1116 6 -029 025 Fail 200317 11163 6 5 -09935L 201833 1828 6 -029 040 Fail 201833 18280 6 5 -08432L 203250 0585 4 -029 013 Fail 203250 05852 4 3 -07016L 209000 0959 6 -028 021 Fail 209000 09592 6 5 -0129L 211667 0427 6 -027 009 Fail 211667 04274 6 5 01556L 214030 0887 6 -027 020 Fail 214030 08868 6 5 03819L 216000 0795 6 -026 018 Fail 216000 07950 6 5 05834L 226009 1308 6 -024 029 Fail 226009 13076 6 5 15836L 228783 4310 3 -024 095 Fail - - 36L - - 18666L 238750 1234 4 -022 027 Fail 238750 12340 4 3 28570L 2213900 - 1 333 Fail - - 70L - - 20037

Totgem 36224 2416 gkg 1-level 227 (175) 10 210211 (36L44L 70L) 10 9Totstd= 55669 4003 5-level 184 (151) 3

64RESULTS Mean = 2102106 gkg

Repeatability variance S2r = 117627Repeatability std Sr = 108456 --gt 516 r = 30368Between lab variance S2L = 176699Reproducibility var S2R = 294326Reproducibility std SR = 171559 --gt 816 R = 48037Remarks 3 Labs rejected (36L44L 70L)

000 050 100 150 200 250 300 350

k-values

44L

65L

45L

35L

32L

16L

9L

56L

19L

34L

36L

66L

70L

Mandels k statistics(Soil 5 - TOC)

-500 00 500 1000 1500 2000 2500

Deviation from Mean

44L

65L

45L

35L

32L

16L

9L

56L

19L

34L

36L

66L

70L

Labo

rato

ries

Soil 5 - TOC -- Mean PARM = 2102 [gkg]

-100 000 100 200 300 400

h-values

44L

65L

45L

35L

32L

16L

9L

56L

19L

34L

36L

66L

70L

Labo

rato

ries

Mandels h statistics(Soil 5 - TOC)

Soil 5-TOC

17

Annex 4

Raw data submitted

Sample Compost 1 Sample Compost 2 Sample Sewage Sludge 1Element TOC [gkg] Element TOC [gkg] Element TOC [gkg]

LAB PARM LAB PARM LAB PARM30L 2600 19L 1691 19L 286730L 2580 19L 1634 19L 281430L 2560 19L 1619 19L 276934L 2969 19L 1604 19L 272034L 2936 19L 1499 19L 268834L 2958 19L 1414 19L 266234L 2994 34L 1527 34L 315234L 3199 34L 1622 34L 314934L 3024 34L 1519 34L 343035L 2306 34L 1753 34L 336535L 2300 34L 1636 34L 304235L 2298 34L 1874 34L 298335L 2296 35L 1506 35L 270735L 2291 35L 1312 35L 270335L 2259 35L 1294 35L 268836L 2546 35L 1279 35L 267436L 2527 35L 1191 35L 263136L 2470 35L 1177 35L 262644L 2583 36L 1418 36L 271344L 2581 36L 1408 36L 266544L 2578 36L 1320 36L 261444L 2539 44L 1719 44L 292044L 2528 44L 1664 44L 291644L 2525 44L 1654 44L 291245L 2658 44L 1637 44L 290045L 2600 44L 1624 44L 289645L 2546 44L 1620 44L 289345L 2461 45L 1428 45L 297645L 2409 45L 1325 45L 295245L 2350 45L 1323 45L 288546L 2460 45L 1321 45L 286646L 2400 45L 1309 45L 284046L 2370 45L 1253 45L 278746L 2350 46L 1580 46L 233056L 2436 46L 1550 46L 233056L 2435 46L 1170 46L 230056L 2405 46L 1120 46L 229056L 2397 56L 1642 56L 270256L 2375 56L 1626 56L 270156L 2358 56L 1622 56L 269465L 2587 56L 1571 56L 269365L 2542 56L 1561 56L 268465L 2483 56L 1545 56L 268066L 2454 65L 1933 65L 264166L 2429 65L 1838 65L 260966L 2365 65L 1693 65L 260766L 2262 65L 1562 65L 260569L 2730 66L 1561 66L 270169L 2250 66L 1545 66L 267469L 1440 66L 1420 66L 261969L 1420 66L 1417 66L 251470L 2435 69L 2700 69L 2639L 2594 69L 2660 69L 2409L 2570 69L 2170 69L 2199L 2565 69L 2130 69L 2109L 2563 70L 1414 70L 28159L 2562 9L 1644 9L 28579L 2555 9L 1641 9L 2856

32L 2290 9L 1602 9L 285532L 2390 9L 1589 9L 285532L 2510 9L 1526 9L 285332L 2470 9L 1492 9L 284616L 2380 32L 1470 32L 265016L 2530 32L 1520 32L 271016L 2400 32L 1540 32L 271016L 2500 32L 1600 32L 280016L 2420 16L 1400 16L 284016L 2410 16L 1440 16L 2840

16L 1470 16L 286016L 1510 16L 287016L 1360 16L 287016L 1390 16L 2880

Sample Sewage Sludge 2 Sample Soil 4 Sample Soil 5Element TOC [gkg] Element TOC [gkg] Element TOC [gkg]

LAB PARM LAB PARM LAB PARM19L 2308 19L 1720 19L 225019L 2303 19L 1700 19L 223019L 2239 19L 1690 19L 221019L 2204 19L 1670 19L 211019L 2192 19L 1640 19L 210019L 2096 19L 1580 19L 206034L 2631 30L 1790 34L 244334L 2471 30L 1770 34L 233434L 2977 30L 1700 34L 231534L 2785 34L 1740 34L 222134L 2780 34L 1692 34L 217634L 2668 34L 1727 34L 207335L 2179 34L 1767 35L 233035L 2160 34L 1777 35L 208035L 2158 34L 1783 35L 201035L 2132 35L 1700 35L 198035L 2119 35L 1650 35L 193035L 2094 35L 1650 35L 178036L 2096 35L 1640 36L 254036L 2069 35L 1630 36L 253436L 2052 35L 1630 36L 179044L 2325 36L 1500 44L 302144L 2309 36L 1497 44L 298244L 2307 36L 1417 44L 295644L 2305 44L 1594 44L 30744L 2287 44L 1587 44L 30044L 2283 44L 1584 44L 29745L 2331 44L 1574 45L 214945L 2327 44L 1573 45L 209245L 2308 44L 1562 45L 203345L 2287 45L 1827 45L 197145L 2234 45L 1709 45L 193345L 2113 45L 1666 45L 184146L 190 45L 1665 56L 223746L 180 45L 1664 56L 222246L 180 45L 1600 56L 220346L 180 46L 2300 56L 206956L 2204 46L 2300 56L 206856L 2197 46L 2300 56L 204456L 2193 46L 2200 65L 192056L 2185 56L 1668 65L 182056L 2183 56L 1654 65L 179056L 2167 56L 1653 65L 172065L 2136 56L 1643 66L 254365L 2091 56L 1639 66L 242465L 2065 56L 1638 66L 232165L 2047 65L 1630 66L 226266L 2105 65L 1560 70L 2213966L 2022 65L 1530 9L 218066L 2009 65L 1490 9L 214066L 1983 66L 2179 9L 213070L 2272 66L 1900 9L 21109L 2385 66L 1762 9L 20709L 2377 66L 1734 9L 20709L 2375 70L 10404 32L 20509L 2359 9L 1640 32L 21009L 2356 9L 1640 32L 20209L 2354 9L 1610 32L 1960

32L 2240 9L 1590 16L 210032L 2260 9L 1590 16L 220032L 2200 9L 1560 16L 220032L 2270 32L 1640 16L 206016L 2300 32L 1600 16L 197016L 2310 32L 1560 16L 201016L 2350 32L 157016L 2260 16L 170016L 2290 16L 180016L 2240 16L 1700

16L 180016L 170016L 1700

European Commission EUR 23012 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on total organic carbon Author(s) E Sobiecka H van der Sloot K Andersen B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 50 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07412-7 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 total organic carbon (TOC) in soils sludge and treated bio-waste 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

-23012-EN

-C

Unit gkg

Mandels k statistics(Soil 4 - TOC)Mandels h statistics(Soil 4 - TOC)

Sample Soil 4 Soil 4 - TOC -- Mean PARM = 1641 [gkg]

Element TOC

General calcparmT1= 102171E+03T2= 168700E+04T3= 62T4= 338T5= 94040E+00

n= variabelp= 12

N-table= 5

Mandels statistics End ResultLAB 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

36L 147161 0470 3 -036 068 Fail 147161 04702 3 2 -16965L 155250 0591 4 -032 085 Fail 155250 05909 4 3 -08844L 157900 0115 6 -031 017 Fail 157900 01152 6 5 -06232L 159250 0359 4 -031 052 Fail 159250 03594 4 3 -0489L 160500 0315 6 -030 045 Fail 160500 03146 6 5 -03656L 164927 0113 6 -028 016 Fail 164927 01127 6 5 00835L 165000 0261 6 -028 038 Fail 165000 02608 6 5 00919L 166667 0505 6 -027 073 Fail 166667 05046 6 5 02645L 168850 0763 6 -026 110 Fail 168850 07628 6 5 04816L 173333 0516 6 -024 074 Fail 173333 05164 6 5 09334L 174761 0346 6 -024 050 Fail 174761 03462 6 5 10730L 175333 0473 3 -024 068 Fail 175333 04726 3 2 11366L 189375 2035 4 -017 294 Fail - - 66L - - 25346L 227500 0500 4 000 072 - - 46L - - 63470L 1040400 - 1 360 Fail - - 70L - - 8763

Totgem 22841 0526 gkg 1-level 232 (176) 12 164078 (46L 66L70L) 12 11Totstd= 22541 0469 5-level 186 (152) 3

71RESULTS Mean = 1640777 gkg

Repeatability variance S2r = 018808Repeatability std Sr = 043368 --gt 264 r = 12143Between lab variance S2L = 054747Reproducibility var S2R = 073555Reproducibility std SR = 085764 --gt 523 R = 24014Remarks 3 Labs rejected (46L 66L70L)

000 050 100 150 200 250 300

k-values

36L

65L

44L

32L

9L

56L

35L

19L

45L

16L

34L

30L

66L

46L

70L

Mandels k statistics(Soil 4 - TOC)

-100 00 100 200 300 400 500 600 700 800 900

Deviation from Mean

36L

65L

44L

32L

9L

56L

35L

19L

45L

16L

34L

30L

66L

46L

70L

Labo

rato

ries

Soil 4 - TOC -- Mean PARM = 1641 [gkg]

-100 000 100 200 300 400

h-values

36L

44L

9L

35L

45L

34L

66L

70L

Labo

rato

ries

Mandels h statistics(Soil 4 - TOC)

Soil 4-TOC

Unit gkg

Mandels k statistics(Soil 5 - TOC)Mandels h statistics(Soil 5 - TOC)

Sample Soil 5 Soil 5 - TOC -- Mean PARM = 2102 [gkg]

Element TOC

General calcparmT1= 113661E+03T2= 240201E+04T3= 54T4= 300T5= 51756E+01

n= variabelp= 10

N-table= 5

Mandels statistics End ResultLAB 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

44L 164383 14708 6 -036 325 Fail - - 44L - - -45865L 181250 0830 4 -033 018 Fail 181250 08302 4 3 -29045L 200317 1116 6 -029 025 Fail 200317 11163 6 5 -09935L 201833 1828 6 -029 040 Fail 201833 18280 6 5 -08432L 203250 0585 4 -029 013 Fail 203250 05852 4 3 -07016L 209000 0959 6 -028 021 Fail 209000 09592 6 5 -0129L 211667 0427 6 -027 009 Fail 211667 04274 6 5 01556L 214030 0887 6 -027 020 Fail 214030 08868 6 5 03819L 216000 0795 6 -026 018 Fail 216000 07950 6 5 05834L 226009 1308 6 -024 029 Fail 226009 13076 6 5 15836L 228783 4310 3 -024 095 Fail - - 36L - - 18666L 238750 1234 4 -022 027 Fail 238750 12340 4 3 28570L 2213900 - 1 333 Fail - - 70L - - 20037

Totgem 36224 2416 gkg 1-level 227 (175) 10 210211 (36L44L 70L) 10 9Totstd= 55669 4003 5-level 184 (151) 3

64RESULTS Mean = 2102106 gkg

Repeatability variance S2r = 117627Repeatability std Sr = 108456 --gt 516 r = 30368Between lab variance S2L = 176699Reproducibility var S2R = 294326Reproducibility std SR = 171559 --gt 816 R = 48037Remarks 3 Labs rejected (36L44L 70L)

000 050 100 150 200 250 300 350

k-values

44L

65L

45L

35L

32L

16L

9L

56L

19L

34L

36L

66L

70L

Mandels k statistics(Soil 5 - TOC)

-500 00 500 1000 1500 2000 2500

Deviation from Mean

44L

65L

45L

35L

32L

16L

9L

56L

19L

34L

36L

66L

70L

Labo

rato

ries

Soil 5 - TOC -- Mean PARM = 2102 [gkg]

-100 000 100 200 300 400

h-values

44L

65L

45L

35L

32L

16L

9L

56L

19L

34L

36L

66L

70L

Labo

rato

ries

Mandels h statistics(Soil 5 - TOC)

Soil 5-TOC

17

Annex 4

Raw data submitted

Sample Compost 1 Sample Compost 2 Sample Sewage Sludge 1Element TOC [gkg] Element TOC [gkg] Element TOC [gkg]

LAB PARM LAB PARM LAB PARM30L 2600 19L 1691 19L 286730L 2580 19L 1634 19L 281430L 2560 19L 1619 19L 276934L 2969 19L 1604 19L 272034L 2936 19L 1499 19L 268834L 2958 19L 1414 19L 266234L 2994 34L 1527 34L 315234L 3199 34L 1622 34L 314934L 3024 34L 1519 34L 343035L 2306 34L 1753 34L 336535L 2300 34L 1636 34L 304235L 2298 34L 1874 34L 298335L 2296 35L 1506 35L 270735L 2291 35L 1312 35L 270335L 2259 35L 1294 35L 268836L 2546 35L 1279 35L 267436L 2527 35L 1191 35L 263136L 2470 35L 1177 35L 262644L 2583 36L 1418 36L 271344L 2581 36L 1408 36L 266544L 2578 36L 1320 36L 261444L 2539 44L 1719 44L 292044L 2528 44L 1664 44L 291644L 2525 44L 1654 44L 291245L 2658 44L 1637 44L 290045L 2600 44L 1624 44L 289645L 2546 44L 1620 44L 289345L 2461 45L 1428 45L 297645L 2409 45L 1325 45L 295245L 2350 45L 1323 45L 288546L 2460 45L 1321 45L 286646L 2400 45L 1309 45L 284046L 2370 45L 1253 45L 278746L 2350 46L 1580 46L 233056L 2436 46L 1550 46L 233056L 2435 46L 1170 46L 230056L 2405 46L 1120 46L 229056L 2397 56L 1642 56L 270256L 2375 56L 1626 56L 270156L 2358 56L 1622 56L 269465L 2587 56L 1571 56L 269365L 2542 56L 1561 56L 268465L 2483 56L 1545 56L 268066L 2454 65L 1933 65L 264166L 2429 65L 1838 65L 260966L 2365 65L 1693 65L 260766L 2262 65L 1562 65L 260569L 2730 66L 1561 66L 270169L 2250 66L 1545 66L 267469L 1440 66L 1420 66L 261969L 1420 66L 1417 66L 251470L 2435 69L 2700 69L 2639L 2594 69L 2660 69L 2409L 2570 69L 2170 69L 2199L 2565 69L 2130 69L 2109L 2563 70L 1414 70L 28159L 2562 9L 1644 9L 28579L 2555 9L 1641 9L 2856

32L 2290 9L 1602 9L 285532L 2390 9L 1589 9L 285532L 2510 9L 1526 9L 285332L 2470 9L 1492 9L 284616L 2380 32L 1470 32L 265016L 2530 32L 1520 32L 271016L 2400 32L 1540 32L 271016L 2500 32L 1600 32L 280016L 2420 16L 1400 16L 284016L 2410 16L 1440 16L 2840

16L 1470 16L 286016L 1510 16L 287016L 1360 16L 287016L 1390 16L 2880

Sample Sewage Sludge 2 Sample Soil 4 Sample Soil 5Element TOC [gkg] Element TOC [gkg] Element TOC [gkg]

LAB PARM LAB PARM LAB PARM19L 2308 19L 1720 19L 225019L 2303 19L 1700 19L 223019L 2239 19L 1690 19L 221019L 2204 19L 1670 19L 211019L 2192 19L 1640 19L 210019L 2096 19L 1580 19L 206034L 2631 30L 1790 34L 244334L 2471 30L 1770 34L 233434L 2977 30L 1700 34L 231534L 2785 34L 1740 34L 222134L 2780 34L 1692 34L 217634L 2668 34L 1727 34L 207335L 2179 34L 1767 35L 233035L 2160 34L 1777 35L 208035L 2158 34L 1783 35L 201035L 2132 35L 1700 35L 198035L 2119 35L 1650 35L 193035L 2094 35L 1650 35L 178036L 2096 35L 1640 36L 254036L 2069 35L 1630 36L 253436L 2052 35L 1630 36L 179044L 2325 36L 1500 44L 302144L 2309 36L 1497 44L 298244L 2307 36L 1417 44L 295644L 2305 44L 1594 44L 30744L 2287 44L 1587 44L 30044L 2283 44L 1584 44L 29745L 2331 44L 1574 45L 214945L 2327 44L 1573 45L 209245L 2308 44L 1562 45L 203345L 2287 45L 1827 45L 197145L 2234 45L 1709 45L 193345L 2113 45L 1666 45L 184146L 190 45L 1665 56L 223746L 180 45L 1664 56L 222246L 180 45L 1600 56L 220346L 180 46L 2300 56L 206956L 2204 46L 2300 56L 206856L 2197 46L 2300 56L 204456L 2193 46L 2200 65L 192056L 2185 56L 1668 65L 182056L 2183 56L 1654 65L 179056L 2167 56L 1653 65L 172065L 2136 56L 1643 66L 254365L 2091 56L 1639 66L 242465L 2065 56L 1638 66L 232165L 2047 65L 1630 66L 226266L 2105 65L 1560 70L 2213966L 2022 65L 1530 9L 218066L 2009 65L 1490 9L 214066L 1983 66L 2179 9L 213070L 2272 66L 1900 9L 21109L 2385 66L 1762 9L 20709L 2377 66L 1734 9L 20709L 2375 70L 10404 32L 20509L 2359 9L 1640 32L 21009L 2356 9L 1640 32L 20209L 2354 9L 1610 32L 1960

32L 2240 9L 1590 16L 210032L 2260 9L 1590 16L 220032L 2200 9L 1560 16L 220032L 2270 32L 1640 16L 206016L 2300 32L 1600 16L 197016L 2310 32L 1560 16L 201016L 2350 32L 157016L 2260 16L 170016L 2290 16L 180016L 2240 16L 1700

16L 180016L 170016L 1700

European Commission EUR 23012 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on total organic carbon Author(s) E Sobiecka H van der Sloot K Andersen B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 50 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07412-7 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 total organic carbon (TOC) in soils sludge and treated bio-waste 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

-23012-EN

-C

Unit gkg

Mandels k statistics(Soil 5 - TOC)Mandels h statistics(Soil 5 - TOC)

Sample Soil 5 Soil 5 - TOC -- Mean PARM = 2102 [gkg]

Element TOC

General calcparmT1= 113661E+03T2= 240201E+04T3= 54T4= 300T5= 51756E+01

n= variabelp= 10

N-table= 5

Mandels statistics End ResultLAB 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

44L 164383 14708 6 -036 325 Fail - - 44L - - -45865L 181250 0830 4 -033 018 Fail 181250 08302 4 3 -29045L 200317 1116 6 -029 025 Fail 200317 11163 6 5 -09935L 201833 1828 6 -029 040 Fail 201833 18280 6 5 -08432L 203250 0585 4 -029 013 Fail 203250 05852 4 3 -07016L 209000 0959 6 -028 021 Fail 209000 09592 6 5 -0129L 211667 0427 6 -027 009 Fail 211667 04274 6 5 01556L 214030 0887 6 -027 020 Fail 214030 08868 6 5 03819L 216000 0795 6 -026 018 Fail 216000 07950 6 5 05834L 226009 1308 6 -024 029 Fail 226009 13076 6 5 15836L 228783 4310 3 -024 095 Fail - - 36L - - 18666L 238750 1234 4 -022 027 Fail 238750 12340 4 3 28570L 2213900 - 1 333 Fail - - 70L - - 20037

Totgem 36224 2416 gkg 1-level 227 (175) 10 210211 (36L44L 70L) 10 9Totstd= 55669 4003 5-level 184 (151) 3

64RESULTS Mean = 2102106 gkg

Repeatability variance S2r = 117627Repeatability std Sr = 108456 --gt 516 r = 30368Between lab variance S2L = 176699Reproducibility var S2R = 294326Reproducibility std SR = 171559 --gt 816 R = 48037Remarks 3 Labs rejected (36L44L 70L)

000 050 100 150 200 250 300 350

k-values

44L

65L

45L

35L

32L

16L

9L

56L

19L

34L

36L

66L

70L

Mandels k statistics(Soil 5 - TOC)

-500 00 500 1000 1500 2000 2500

Deviation from Mean

44L

65L

45L

35L

32L

16L

9L

56L

19L

34L

36L

66L

70L

Labo

rato

ries

Soil 5 - TOC -- Mean PARM = 2102 [gkg]

-100 000 100 200 300 400

h-values

44L

65L

45L

35L

32L

16L

9L

56L

19L

34L

36L

66L

70L

Labo

rato

ries

Mandels h statistics(Soil 5 - TOC)

Soil 5-TOC

17

Annex 4

Raw data submitted

Sample Compost 1 Sample Compost 2 Sample Sewage Sludge 1Element TOC [gkg] Element TOC [gkg] Element TOC [gkg]

LAB PARM LAB PARM LAB PARM30L 2600 19L 1691 19L 286730L 2580 19L 1634 19L 281430L 2560 19L 1619 19L 276934L 2969 19L 1604 19L 272034L 2936 19L 1499 19L 268834L 2958 19L 1414 19L 266234L 2994 34L 1527 34L 315234L 3199 34L 1622 34L 314934L 3024 34L 1519 34L 343035L 2306 34L 1753 34L 336535L 2300 34L 1636 34L 304235L 2298 34L 1874 34L 298335L 2296 35L 1506 35L 270735L 2291 35L 1312 35L 270335L 2259 35L 1294 35L 268836L 2546 35L 1279 35L 267436L 2527 35L 1191 35L 263136L 2470 35L 1177 35L 262644L 2583 36L 1418 36L 271344L 2581 36L 1408 36L 266544L 2578 36L 1320 36L 261444L 2539 44L 1719 44L 292044L 2528 44L 1664 44L 291644L 2525 44L 1654 44L 291245L 2658 44L 1637 44L 290045L 2600 44L 1624 44L 289645L 2546 44L 1620 44L 289345L 2461 45L 1428 45L 297645L 2409 45L 1325 45L 295245L 2350 45L 1323 45L 288546L 2460 45L 1321 45L 286646L 2400 45L 1309 45L 284046L 2370 45L 1253 45L 278746L 2350 46L 1580 46L 233056L 2436 46L 1550 46L 233056L 2435 46L 1170 46L 230056L 2405 46L 1120 46L 229056L 2397 56L 1642 56L 270256L 2375 56L 1626 56L 270156L 2358 56L 1622 56L 269465L 2587 56L 1571 56L 269365L 2542 56L 1561 56L 268465L 2483 56L 1545 56L 268066L 2454 65L 1933 65L 264166L 2429 65L 1838 65L 260966L 2365 65L 1693 65L 260766L 2262 65L 1562 65L 260569L 2730 66L 1561 66L 270169L 2250 66L 1545 66L 267469L 1440 66L 1420 66L 261969L 1420 66L 1417 66L 251470L 2435 69L 2700 69L 2639L 2594 69L 2660 69L 2409L 2570 69L 2170 69L 2199L 2565 69L 2130 69L 2109L 2563 70L 1414 70L 28159L 2562 9L 1644 9L 28579L 2555 9L 1641 9L 2856

32L 2290 9L 1602 9L 285532L 2390 9L 1589 9L 285532L 2510 9L 1526 9L 285332L 2470 9L 1492 9L 284616L 2380 32L 1470 32L 265016L 2530 32L 1520 32L 271016L 2400 32L 1540 32L 271016L 2500 32L 1600 32L 280016L 2420 16L 1400 16L 284016L 2410 16L 1440 16L 2840

16L 1470 16L 286016L 1510 16L 287016L 1360 16L 287016L 1390 16L 2880

Sample Sewage Sludge 2 Sample Soil 4 Sample Soil 5Element TOC [gkg] Element TOC [gkg] Element TOC [gkg]

LAB PARM LAB PARM LAB PARM19L 2308 19L 1720 19L 225019L 2303 19L 1700 19L 223019L 2239 19L 1690 19L 221019L 2204 19L 1670 19L 211019L 2192 19L 1640 19L 210019L 2096 19L 1580 19L 206034L 2631 30L 1790 34L 244334L 2471 30L 1770 34L 233434L 2977 30L 1700 34L 231534L 2785 34L 1740 34L 222134L 2780 34L 1692 34L 217634L 2668 34L 1727 34L 207335L 2179 34L 1767 35L 233035L 2160 34L 1777 35L 208035L 2158 34L 1783 35L 201035L 2132 35L 1700 35L 198035L 2119 35L 1650 35L 193035L 2094 35L 1650 35L 178036L 2096 35L 1640 36L 254036L 2069 35L 1630 36L 253436L 2052 35L 1630 36L 179044L 2325 36L 1500 44L 302144L 2309 36L 1497 44L 298244L 2307 36L 1417 44L 295644L 2305 44L 1594 44L 30744L 2287 44L 1587 44L 30044L 2283 44L 1584 44L 29745L 2331 44L 1574 45L 214945L 2327 44L 1573 45L 209245L 2308 44L 1562 45L 203345L 2287 45L 1827 45L 197145L 2234 45L 1709 45L 193345L 2113 45L 1666 45L 184146L 190 45L 1665 56L 223746L 180 45L 1664 56L 222246L 180 45L 1600 56L 220346L 180 46L 2300 56L 206956L 2204 46L 2300 56L 206856L 2197 46L 2300 56L 204456L 2193 46L 2200 65L 192056L 2185 56L 1668 65L 182056L 2183 56L 1654 65L 179056L 2167 56L 1653 65L 172065L 2136 56L 1643 66L 254365L 2091 56L 1639 66L 242465L 2065 56L 1638 66L 232165L 2047 65L 1630 66L 226266L 2105 65L 1560 70L 2213966L 2022 65L 1530 9L 218066L 2009 65L 1490 9L 214066L 1983 66L 2179 9L 213070L 2272 66L 1900 9L 21109L 2385 66L 1762 9L 20709L 2377 66L 1734 9L 20709L 2375 70L 10404 32L 20509L 2359 9L 1640 32L 21009L 2356 9L 1640 32L 20209L 2354 9L 1610 32L 1960

32L 2240 9L 1590 16L 210032L 2260 9L 1590 16L 220032L 2200 9L 1560 16L 220032L 2270 32L 1640 16L 206016L 2300 32L 1600 16L 197016L 2310 32L 1560 16L 201016L 2350 32L 157016L 2260 16L 170016L 2290 16L 180016L 2240 16L 1700

16L 180016L 170016L 1700

European Commission EUR 23012 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on total organic carbon Author(s) E Sobiecka H van der Sloot K Andersen B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 50 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07412-7 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 total organic carbon (TOC) in soils sludge and treated bio-waste 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

-23012-EN

-C

17

Annex 4

Raw data submitted

Sample Compost 1 Sample Compost 2 Sample Sewage Sludge 1Element TOC [gkg] Element TOC [gkg] Element TOC [gkg]

LAB PARM LAB PARM LAB PARM30L 2600 19L 1691 19L 286730L 2580 19L 1634 19L 281430L 2560 19L 1619 19L 276934L 2969 19L 1604 19L 272034L 2936 19L 1499 19L 268834L 2958 19L 1414 19L 266234L 2994 34L 1527 34L 315234L 3199 34L 1622 34L 314934L 3024 34L 1519 34L 343035L 2306 34L 1753 34L 336535L 2300 34L 1636 34L 304235L 2298 34L 1874 34L 298335L 2296 35L 1506 35L 270735L 2291 35L 1312 35L 270335L 2259 35L 1294 35L 268836L 2546 35L 1279 35L 267436L 2527 35L 1191 35L 263136L 2470 35L 1177 35L 262644L 2583 36L 1418 36L 271344L 2581 36L 1408 36L 266544L 2578 36L 1320 36L 261444L 2539 44L 1719 44L 292044L 2528 44L 1664 44L 291644L 2525 44L 1654 44L 291245L 2658 44L 1637 44L 290045L 2600 44L 1624 44L 289645L 2546 44L 1620 44L 289345L 2461 45L 1428 45L 297645L 2409 45L 1325 45L 295245L 2350 45L 1323 45L 288546L 2460 45L 1321 45L 286646L 2400 45L 1309 45L 284046L 2370 45L 1253 45L 278746L 2350 46L 1580 46L 233056L 2436 46L 1550 46L 233056L 2435 46L 1170 46L 230056L 2405 46L 1120 46L 229056L 2397 56L 1642 56L 270256L 2375 56L 1626 56L 270156L 2358 56L 1622 56L 269465L 2587 56L 1571 56L 269365L 2542 56L 1561 56L 268465L 2483 56L 1545 56L 268066L 2454 65L 1933 65L 264166L 2429 65L 1838 65L 260966L 2365 65L 1693 65L 260766L 2262 65L 1562 65L 260569L 2730 66L 1561 66L 270169L 2250 66L 1545 66L 267469L 1440 66L 1420 66L 261969L 1420 66L 1417 66L 251470L 2435 69L 2700 69L 2639L 2594 69L 2660 69L 2409L 2570 69L 2170 69L 2199L 2565 69L 2130 69L 2109L 2563 70L 1414 70L 28159L 2562 9L 1644 9L 28579L 2555 9L 1641 9L 2856

32L 2290 9L 1602 9L 285532L 2390 9L 1589 9L 285532L 2510 9L 1526 9L 285332L 2470 9L 1492 9L 284616L 2380 32L 1470 32L 265016L 2530 32L 1520 32L 271016L 2400 32L 1540 32L 271016L 2500 32L 1600 32L 280016L 2420 16L 1400 16L 284016L 2410 16L 1440 16L 2840

16L 1470 16L 286016L 1510 16L 287016L 1360 16L 287016L 1390 16L 2880

Sample Sewage Sludge 2 Sample Soil 4 Sample Soil 5Element TOC [gkg] Element TOC [gkg] Element TOC [gkg]

LAB PARM LAB PARM LAB PARM19L 2308 19L 1720 19L 225019L 2303 19L 1700 19L 223019L 2239 19L 1690 19L 221019L 2204 19L 1670 19L 211019L 2192 19L 1640 19L 210019L 2096 19L 1580 19L 206034L 2631 30L 1790 34L 244334L 2471 30L 1770 34L 233434L 2977 30L 1700 34L 231534L 2785 34L 1740 34L 222134L 2780 34L 1692 34L 217634L 2668 34L 1727 34L 207335L 2179 34L 1767 35L 233035L 2160 34L 1777 35L 208035L 2158 34L 1783 35L 201035L 2132 35L 1700 35L 198035L 2119 35L 1650 35L 193035L 2094 35L 1650 35L 178036L 2096 35L 1640 36L 254036L 2069 35L 1630 36L 253436L 2052 35L 1630 36L 179044L 2325 36L 1500 44L 302144L 2309 36L 1497 44L 298244L 2307 36L 1417 44L 295644L 2305 44L 1594 44L 30744L 2287 44L 1587 44L 30044L 2283 44L 1584 44L 29745L 2331 44L 1574 45L 214945L 2327 44L 1573 45L 209245L 2308 44L 1562 45L 203345L 2287 45L 1827 45L 197145L 2234 45L 1709 45L 193345L 2113 45L 1666 45L 184146L 190 45L 1665 56L 223746L 180 45L 1664 56L 222246L 180 45L 1600 56L 220346L 180 46L 2300 56L 206956L 2204 46L 2300 56L 206856L 2197 46L 2300 56L 204456L 2193 46L 2200 65L 192056L 2185 56L 1668 65L 182056L 2183 56L 1654 65L 179056L 2167 56L 1653 65L 172065L 2136 56L 1643 66L 254365L 2091 56L 1639 66L 242465L 2065 56L 1638 66L 232165L 2047 65L 1630 66L 226266L 2105 65L 1560 70L 2213966L 2022 65L 1530 9L 218066L 2009 65L 1490 9L 214066L 1983 66L 2179 9L 213070L 2272 66L 1900 9L 21109L 2385 66L 1762 9L 20709L 2377 66L 1734 9L 20709L 2375 70L 10404 32L 20509L 2359 9L 1640 32L 21009L 2356 9L 1640 32L 20209L 2354 9L 1610 32L 1960

32L 2240 9L 1590 16L 210032L 2260 9L 1590 16L 220032L 2200 9L 1560 16L 220032L 2270 32L 1640 16L 206016L 2300 32L 1600 16L 197016L 2310 32L 1560 16L 201016L 2350 32L 157016L 2260 16L 170016L 2290 16L 180016L 2240 16L 1700

16L 180016L 170016L 1700

European Commission EUR 23012 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on total organic carbon Author(s) E Sobiecka H van der Sloot K Andersen B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 50 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07412-7 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 total organic carbon (TOC) in soils sludge and treated bio-waste 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

-23012-EN

-C

Sample Compost 1 Sample Compost 2 Sample Sewage Sludge 1Element TOC [gkg] Element TOC [gkg] Element TOC [gkg]

LAB PARM LAB PARM LAB PARM30L 2600 19L 1691 19L 286730L 2580 19L 1634 19L 281430L 2560 19L 1619 19L 276934L 2969 19L 1604 19L 272034L 2936 19L 1499 19L 268834L 2958 19L 1414 19L 266234L 2994 34L 1527 34L 315234L 3199 34L 1622 34L 314934L 3024 34L 1519 34L 343035L 2306 34L 1753 34L 336535L 2300 34L 1636 34L 304235L 2298 34L 1874 34L 298335L 2296 35L 1506 35L 270735L 2291 35L 1312 35L 270335L 2259 35L 1294 35L 268836L 2546 35L 1279 35L 267436L 2527 35L 1191 35L 263136L 2470 35L 1177 35L 262644L 2583 36L 1418 36L 271344L 2581 36L 1408 36L 266544L 2578 36L 1320 36L 261444L 2539 44L 1719 44L 292044L 2528 44L 1664 44L 291644L 2525 44L 1654 44L 291245L 2658 44L 1637 44L 290045L 2600 44L 1624 44L 289645L 2546 44L 1620 44L 289345L 2461 45L 1428 45L 297645L 2409 45L 1325 45L 295245L 2350 45L 1323 45L 288546L 2460 45L 1321 45L 286646L 2400 45L 1309 45L 284046L 2370 45L 1253 45L 278746L 2350 46L 1580 46L 233056L 2436 46L 1550 46L 233056L 2435 46L 1170 46L 230056L 2405 46L 1120 46L 229056L 2397 56L 1642 56L 270256L 2375 56L 1626 56L 270156L 2358 56L 1622 56L 269465L 2587 56L 1571 56L 269365L 2542 56L 1561 56L 268465L 2483 56L 1545 56L 268066L 2454 65L 1933 65L 264166L 2429 65L 1838 65L 260966L 2365 65L 1693 65L 260766L 2262 65L 1562 65L 260569L 2730 66L 1561 66L 270169L 2250 66L 1545 66L 267469L 1440 66L 1420 66L 261969L 1420 66L 1417 66L 251470L 2435 69L 2700 69L 2639L 2594 69L 2660 69L 2409L 2570 69L 2170 69L 2199L 2565 69L 2130 69L 2109L 2563 70L 1414 70L 28159L 2562 9L 1644 9L 28579L 2555 9L 1641 9L 2856

32L 2290 9L 1602 9L 285532L 2390 9L 1589 9L 285532L 2510 9L 1526 9L 285332L 2470 9L 1492 9L 284616L 2380 32L 1470 32L 265016L 2530 32L 1520 32L 271016L 2400 32L 1540 32L 271016L 2500 32L 1600 32L 280016L 2420 16L 1400 16L 284016L 2410 16L 1440 16L 2840

16L 1470 16L 286016L 1510 16L 287016L 1360 16L 287016L 1390 16L 2880

Sample Sewage Sludge 2 Sample Soil 4 Sample Soil 5Element TOC [gkg] Element TOC [gkg] Element TOC [gkg]

LAB PARM LAB PARM LAB PARM19L 2308 19L 1720 19L 225019L 2303 19L 1700 19L 223019L 2239 19L 1690 19L 221019L 2204 19L 1670 19L 211019L 2192 19L 1640 19L 210019L 2096 19L 1580 19L 206034L 2631 30L 1790 34L 244334L 2471 30L 1770 34L 233434L 2977 30L 1700 34L 231534L 2785 34L 1740 34L 222134L 2780 34L 1692 34L 217634L 2668 34L 1727 34L 207335L 2179 34L 1767 35L 233035L 2160 34L 1777 35L 208035L 2158 34L 1783 35L 201035L 2132 35L 1700 35L 198035L 2119 35L 1650 35L 193035L 2094 35L 1650 35L 178036L 2096 35L 1640 36L 254036L 2069 35L 1630 36L 253436L 2052 35L 1630 36L 179044L 2325 36L 1500 44L 302144L 2309 36L 1497 44L 298244L 2307 36L 1417 44L 295644L 2305 44L 1594 44L 30744L 2287 44L 1587 44L 30044L 2283 44L 1584 44L 29745L 2331 44L 1574 45L 214945L 2327 44L 1573 45L 209245L 2308 44L 1562 45L 203345L 2287 45L 1827 45L 197145L 2234 45L 1709 45L 193345L 2113 45L 1666 45L 184146L 190 45L 1665 56L 223746L 180 45L 1664 56L 222246L 180 45L 1600 56L 220346L 180 46L 2300 56L 206956L 2204 46L 2300 56L 206856L 2197 46L 2300 56L 204456L 2193 46L 2200 65L 192056L 2185 56L 1668 65L 182056L 2183 56L 1654 65L 179056L 2167 56L 1653 65L 172065L 2136 56L 1643 66L 254365L 2091 56L 1639 66L 242465L 2065 56L 1638 66L 232165L 2047 65L 1630 66L 226266L 2105 65L 1560 70L 2213966L 2022 65L 1530 9L 218066L 2009 65L 1490 9L 214066L 1983 66L 2179 9L 213070L 2272 66L 1900 9L 21109L 2385 66L 1762 9L 20709L 2377 66L 1734 9L 20709L 2375 70L 10404 32L 20509L 2359 9L 1640 32L 21009L 2356 9L 1640 32L 20209L 2354 9L 1610 32L 1960

32L 2240 9L 1590 16L 210032L 2260 9L 1590 16L 220032L 2200 9L 1560 16L 220032L 2270 32L 1640 16L 206016L 2300 32L 1600 16L 197016L 2310 32L 1560 16L 201016L 2350 32L 157016L 2260 16L 170016L 2290 16L 180016L 2240 16L 1700

16L 180016L 170016L 1700

European Commission EUR 23012 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on total organic carbon Author(s) E Sobiecka H van der Sloot K Andersen B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 50 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07412-7 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 total organic carbon (TOC) in soils sludge and treated bio-waste 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

-23012-EN

-C

Sample Sewage Sludge 2 Sample Soil 4 Sample Soil 5Element TOC [gkg] Element TOC [gkg] Element TOC [gkg]

LAB PARM LAB PARM LAB PARM19L 2308 19L 1720 19L 225019L 2303 19L 1700 19L 223019L 2239 19L 1690 19L 221019L 2204 19L 1670 19L 211019L 2192 19L 1640 19L 210019L 2096 19L 1580 19L 206034L 2631 30L 1790 34L 244334L 2471 30L 1770 34L 233434L 2977 30L 1700 34L 231534L 2785 34L 1740 34L 222134L 2780 34L 1692 34L 217634L 2668 34L 1727 34L 207335L 2179 34L 1767 35L 233035L 2160 34L 1777 35L 208035L 2158 34L 1783 35L 201035L 2132 35L 1700 35L 198035L 2119 35L 1650 35L 193035L 2094 35L 1650 35L 178036L 2096 35L 1640 36L 254036L 2069 35L 1630 36L 253436L 2052 35L 1630 36L 179044L 2325 36L 1500 44L 302144L 2309 36L 1497 44L 298244L 2307 36L 1417 44L 295644L 2305 44L 1594 44L 30744L 2287 44L 1587 44L 30044L 2283 44L 1584 44L 29745L 2331 44L 1574 45L 214945L 2327 44L 1573 45L 209245L 2308 44L 1562 45L 203345L 2287 45L 1827 45L 197145L 2234 45L 1709 45L 193345L 2113 45L 1666 45L 184146L 190 45L 1665 56L 223746L 180 45L 1664 56L 222246L 180 45L 1600 56L 220346L 180 46L 2300 56L 206956L 2204 46L 2300 56L 206856L 2197 46L 2300 56L 204456L 2193 46L 2200 65L 192056L 2185 56L 1668 65L 182056L 2183 56L 1654 65L 179056L 2167 56L 1653 65L 172065L 2136 56L 1643 66L 254365L 2091 56L 1639 66L 242465L 2065 56L 1638 66L 232165L 2047 65L 1630 66L 226266L 2105 65L 1560 70L 2213966L 2022 65L 1530 9L 218066L 2009 65L 1490 9L 214066L 1983 66L 2179 9L 213070L 2272 66L 1900 9L 21109L 2385 66L 1762 9L 20709L 2377 66L 1734 9L 20709L 2375 70L 10404 32L 20509L 2359 9L 1640 32L 21009L 2356 9L 1640 32L 20209L 2354 9L 1610 32L 1960

32L 2240 9L 1590 16L 210032L 2260 9L 1590 16L 220032L 2200 9L 1560 16L 220032L 2270 32L 1640 16L 206016L 2300 32L 1600 16L 197016L 2310 32L 1560 16L 201016L 2350 32L 157016L 2260 16L 170016L 2290 16L 180016L 2240 16L 1700

16L 180016L 170016L 1700

European Commission EUR 23012 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on total organic carbon Author(s) E Sobiecka H van der Sloot K Andersen B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 50 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07412-7 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 total organic carbon (TOC) in soils sludge and treated bio-waste 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

-23012-EN

-C

European Commission EUR 23012 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on total organic carbon Author(s) E Sobiecka H van der Sloot K Andersen B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 50 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07412-7 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 total organic carbon (TOC) in soils sludge and treated bio-waste 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

-23012-EN

-C

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

-23012-EN

-C