Analytical Proficiency Tests relating to measurements of … · 2011. 12. 23. · ISO 13528 : statistical methods used in aptitude tests by inter-laboratory comparisons – December

REPORT 23/12/2011

N° DRC-11-119507-08855B

Analytical Proficiency Tests relating to measurements of hydrochloric acid, hydrofluoric acid, ammonia, sulphur dioxide, mercury, and metals (and metalloids) in samples coming from stationary source emissions.

FINAL REPORT

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ANALYTICAL INTER-LABORATORY COMPARISONS ORGANIZED FOR THE LABORATORIES INVOLVED IN REGULATORY EMISSIONS CHECKS.

2011 Campaign :

“ HCl, HF, NH3, SO2, total Hg, Heavy metals ”

FINAL REPORT

D R C - 1 1 - 1 1 9 5 0 7 - 0 8 8 5 5 B

D E C E M B E R 2 3 , 2 0 1 1

Sylvain BAILLEUL

Characterization of the Environment Department Chronic Risks Division

List of persons having taken part in the study :

S. BAILLEUL, H. BIAUDET, F. DEL-GRATTA, J. POULLEAU, L. MEUNIER, B. DEFRENNE

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FOREWORD

This report was drawn up on the basis of the information provided to INERIS and the objective (scientific or technical) data available and applicable regulations.

INERIS cannot be held liable if the information received was incomplete or erroneous.

Any findings, recommendations, suggestions or equivalent that are recorded by INERIS as part of the services it is contracted to perform may assist with decision making. Given the tasks entrusted to INERIS on the basis of the decree founding the organization, INERIS cannot be involved in the decision making process itself. INERIS cannot therefore take responsibility in lieu and place of the decision maker.

The addressee shall use the results comprised in this report in whole or at least in an objective manner. Using this information in the form of excerpts or summary memos may take place only under the full and complete responsibility of the addressee. The same applies to any modification made to this report.

INERIS declines any liability for any use of this report outside of the scope of the service provided.

Drafting Checking Approval

Name Sylvain BAILLEUL Florence DEL-GRATTA Nicolas ALSAC

Quality

Coordinator of the Proficiency Test

« Analytical resources

unit »

Chronic Risks Division

Coordinator of the Proficiency Test

« Sources and Emissions

unit»


Head of Characterization of the Environment

Department


Signature

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TABLE OF CONTENTS 1 GLOSSARY .............................................................................................................................. 7

2 DEFINITIONS ............................................................................................................................ 8

3 REFERENCE DOCUMENTS .................................................................................................... 9

4 CLIENTS ................................................................................................................................. 10

5 ORGANIZATION OF THE INTER-LABORATORY COMPARISONS ................................... 10

6 PRESENTATION OF THE REPORT ...................................................................................... 10

7 INTRODUCTION ..................................................................................................................... 10

8 ILT PROGRAM ....................................................................................................................... 11

9 TEST PARTICIPANTS ........................................................................................................... 11

10 DESCRIPTION OF THE TEST MATERIALS ......................................................................... 12 10.1 DESCRIPTION AND INSTRUCTIONS ............................................................................................. 12

10.1.1 Total mercury in permanganate medium ........................................................................................................ 12 10.1.2 Total mercury in dichromate medium .............................................................................................................. 12 10.1.3 Hydrochloric acid ............................................................................................................................................ 13 10.1.4 Fluorhydric acid .............................................................................................................................................. 13 10.1.5 Metals (and metalloids) .................................................................................................................................. 14 10.1.6 Sulfur dioxide ................................................................................................................................................. 14 10.1.7 Ammonia ........................................................................................................................................................ 15

11 SHIPPING ............................................................................................................................... 15

12 HOMOGENEITY AND STABILITY OF THE SAMPLES ........................................................ 15 12.1 HOMOGENEITY OF THE MATERIALS ........................................................................................................ 15 12.2 STABILITY OF THE TEST MATERIALS........................................................................................................ 16

13 RESULTS OF THE INTER-LABORATORY COMPARISON ................................................. 17

13.1 EXPLOITATION OF THE DATA FROM THE TEST MATERIALS ..................................................... 17 13.1.1 General information ........................................................................................................................................ 17 13.1.2 Presentation of the results .............................................................................................................................. 17 13.1.3 Test material "11/119507_Hg_KMnO4" ........................................................................................................... 19 13.1.4 Test material "11/119507_Hg_K2Cr2O7" ......................................................................................................... 21 13.1.5 Test material "11_119507_HCl" ..................................................................................................................... 23 13.1.6 Test material "11_119507_HF_Solution" ........................................................................................................ 25 13.1.7 Test material "11_119507_HF_Poussière" ..................................................................................................... 27 13.1.8 Test material "11/119507_Metaux_solution" ................................................................................................... 29 13.1.9 Test material "11/119507_Metaux_Poussiére" free protocol ........................................................................... 41 13.1.10 Test material "11/119507_Métaux_Poussiére" imposed protocol.................................................................... 53 13.1.11 Test material "11_119507_SO2" ..................................................................................................................... 67 13.1.12 Test material "11_119507_NH3" ..................................................................................................................... 69

14 LIST OF ANNEXES ................................................................................................................ 71 ANNEX 1 GENERAL ORGANIZATION, DESCRIPTION OF TESTS AND ALGORITHMS .............................................. 72

General organization of the test ................................................................................................................................... 73 Prior checking of the data before launching statistical calculations ............................................................................... 75 Materials prepared by the INERIS : .............................................................................................................................. 77 Statistical performance tests ........................................................................................................................................ 79

ANNEX 2 DATA RECEIVED, AVERAGES AND REPEATABILITY STANDARD DEVIATIONS FOR THE LABORATORIES AND VALUES DISMISSED BY EXPERT OPINION ...................................................................................... 81

Table 1 - 11 119507 HCl – Water – Hydrochloric acid – Raw data in mg/liter ............................................................... 82 Table 2 - 11 119507 HF – Sodium hydroxide (NaOH) – Fluorhydric Acid - Raw data in mg/liter ................................... 83 Table 3 - 11 119507 HF – Dust – Fluorhydric Acid – Raw data in mg/g ........................................................................ 84 Table 4 - 11 119507 NH3 – Sulfuric acid - Ammonia – Raw data in mg/liter ................................................................. 85 Table 5 - 11 119507 SO2 – Hydroperoxide – Sulfur dioxide – Raw data in mg/liter ...................................................... 86 Table 6 - 11 119507 Hg_ K2Cr2O7 – Nitric acid - Dichromate (HNO3-K2Cr2O7) - Mercury – Raw data in µg/liter ...... 87 Table 7 - 11 119507 Hg_KMnO4 – Sulfuric acid - Permanganate (H2SO4-KMnO4) - Mercury – Raw Data in µg/liter .. 88 Tables 8 to 18 - 11 119507 Metals_solution – Raw data in µg/liter ............................................................................... 89

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Tables 19 to 29 - 11 119507 Metals – Dust – Free protocol – Raw Data in µg/g ........................................................ 100 Table 30 à 40 - 11 119507 Metals – Dust – Imposed protocol- Raw Data in µg/g ....................................................... 111

ANNEX 3 STATISTICAL DISTRIBUTION CURVES ............................................................................................. 122 11 119507 HF – Acide Fluorhydrique ......................................................................................................................... 124 11 119507 HF – Poussière - Acide Fluorhydrique ...................................................................................................... 125 11 119507 NH3 – Ammoniac ..................................................................................................................................... 126 11 119507 SO2 – Dioxyde de soufre ......................................................................................................................... 127 11 119507 Hg – K2Cr2O7 - Mercure .......................................................................................................................... 128 11 119507 Hg_KMnO4 - Mercure .............................................................................................................................. 129 11 119507 Métaux_solution – (11 figures) ................................................................................................................. 130 11 119507 Métaux – Poussière – Protocole libre – (11 figures) .................................................................................. 141 11 119507 Métaux – Poussière – Protocole imposé – (11 figures) ............................................................................. 152

ANNEX 4 GENERAL ORGANIZATION, DESCRIPTION OF TESTS AND ALGORITHMS ............................................ 163 Figure 1 : 11/119507_Métaux solution (part 1 to 3) .................................................................................................... 164 Figure 2: 11/119507_Métaux poussière Free Protocol (part 1 to 3) ..................................................................... 167 Figure 3: 11/119507_Métaux poussière Imposed Protocole (part 1 to 2) .................................................................... 170

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1 GLOSSARY

ILC An Inter-Laboratory Comparison is defined and implemented to allow the laboratories to assess and demonstrate their performance in particular test, calibration or measuring sectors,

ILT An Inter-Laboratory Test is a technical operation that consists of determining the concentration of a sample, according to a specific operating mode, using comparisons between different laboratories; it makes it possible to assess laboratories’ performance,

NOTE: Three terms may be used: “inter-laboratory tests” or “inter-comparison tests” or “aptitude tests,”

Extract Obtained either from extracted water, or from a solvent spiked by all of the sought substances,

QL Quantification limit,

Test material Matrix of interest containing the element subject to the inter-laboratory comparison, potentially added using a spiking solution. The test matrices are also called, in the referential, LAB-CIL REF 02, comparison substrate,

Matrix Natural element, physical element as well as all of its components other than the species to be analyzed in which the substance subject to the inter-laboratory test is placed,

CRM Certified reference material,

ILCA Inter-laboratory comparison analyzer,

Spiking solution Concentration solution with known substance(s) dissolved in a solvent,

Assigned value Value assigned to a particular and recognized size, sometimes by convention, as having a suitable uncertainty at a given usage

(ISO 13528).

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2 DEFINITIONS

CVr : standard deviation of the x measurements divided by the average of those x measurements by % [(Standard deviation / average) by %],

CVR : reproducibility variation coefficient equal to the standard deviation of the averages of the measurements divided by the average of the averages of the measurements by %,

CVrep : mean repeatability variation coefficient, average of the CV4 of the participants,

Standard deviation : standard deviation of x measurements,

Population standard : standard deviation of the measurement averages,

deviation

ICR : reproducibility confidence interval,

ICr : repeatability confidence interval,

Average : average of x measurements,

Population average : average of the measurement averages,

Number of decimals : number imposed in the instruction formula,

σ : robust standard deviation for assessing the aptitude (stipulated, perceived or s*: robust standard deviation for evaluating the aptitude obtained using the algorithm A),

z score : performance criteria provided to each participant making it possible to measure its deviation relative to the assigned value. The assigned value is the robust average,

s* : robust standard deviation for assessing the aptitude obtained using the algorithm A,

SL : inter-laboratory standard deviation,

SR : reproducibility standard deviation,

Sr : repeatability standard deviation,

ux* : standard uncertainty ux ,

UXMRC : standard uncertainty resulting from the certificate for the certified test material,

w* : robust standard deviation obtained using algorithm S,

x* : robust average obtained using algorithm A,

XMRC : reference value resulting from the certificate for the certified reference material.

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3 REFERENCE DOCUMENTS

Decree of March 11, 2010 : Decree pertaining to approval terms for laboratories or entities for certain types of samples and analyses upon the emission of substances into the atmosphere (NOR: DEVE1007687A)

LAB-CIL REF 02 : COFRAC (French organism of accreditation) reference document relative to the organizers of inter-laboratory comparisons – Accreditation requirements – Revision 03 – March 2011,

LAB REF 22 : COFRAC reference document relative to specific requirements – Air quality – Emissions from fixed sources – Revision 00 – June 2009,

EN ISO/CEI 17043 : general requirements concerning aptitude tests – April 2010,

ISO 5725-1 : applications of the statistics – Accuracy (correctness and faithfulness) of the results and measurement methods – Part 1: general principles and definitions – December 1994,

ISO 5725-2 : application of the statistics – Accuracy (correctness and faithfulness) of the measurement results – Part 2: basic method for determining the repeatability and reproducibility of a standardized measurement method – December 1994,

ISO 5725-5 : application of the statistics – Accuracy (correctness and faithfulness) of the measurement results – Part 5: alternative methods for determining the faithfulness of a standardized measurement method – December 1998,

ISO 13528 : statistical methods used in aptitude tests by inter-laboratory comparisons – December 2005,

ISO 3534-2 : vocabulary and symbols Part 2: Applied statistics – December 2006,

NF X06-050 : application of the statistics – Study of the normality of a distribution – December 1995.

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4 CLIENTS

Laboratories having participated in the inter-laboratory comparison.

5 ORGANIZATION OF THE INTER-LABORATORY COMPARISONS

The inter-laboratory comparisons (ILC) were organized and implemented by the

authorized personnel cited in table 1 below:

Organization of the "Air" inter-laboratory comparisons

First and Last Names ILCA Function

INERIS Parc Technologique

Alata

60550 VERNEUIL-EN-HALATTE

03.44.55.66.77

03.44.55.66.99

Eva LEOZ ILT Steering

Sylvain BAILLEUL ILT coordinator

Sylvain BAILLEUL Test material

preparer

José GUARNERI

Website management

Design of the

statistical processing

tool

6 PRESENTATION OF THE REPORT

This report cancels and replaces the initial provisional report referenced DRC-11-119507-08855A distributed on 07/11/2011. It is accessible on the site http://www.ineris.fr/eil/.

7 INTRODUCTION

These tests were organized by the INERIS according to a program developed in agreement with the Steering Committee for the tests bringing together three experts designated by the MEDDTL (Ministry of Ecology, Sustainable Development, Transportation and Housing), members of the “Laboratory or Entity Approval Committee for the performance of certain types of sampling and analyses upon emission of substances into the atmosphere.”

One of the purposes of these tests is to determine the analytical repeatability and reproducibility standard deviations obtained in the implementation of the reference methods defined by the aforementioned decree and detecting any bias or factors influencing the measuring quality. Participation in these inter-laboratory tests was mandatory for the approved laboratories.

Outside this regulatory context, participation in inter-laboratory tests is an essential

tool in monitoring the mastery of the implementation of chemical analysis methods. To that end, it is subject to a COFRAC requirement in the context of accreditation according to referential EN ISO/CEI 17025 and leads to verification of the proper

execution of this requirement during evaluations.

http://www.ineris.fr/eil/

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Until now, participation in these inter-laboratory tests has been dedicated to companies/laboratories carrying out emission controls on stacks in France for regulatory purposes, for which an “agrément” from the ministry in charge of environment is necessary. This year, INERIS has decided to extend the participation to any European laboratory willing to take part.

8 ILT PROGRAM

In 2011, the analytical inter-laboratory comparisons in the air field pertained to the analyses of parameters relative to approvals 3b, 4b, 5b, 6b, 10b and 16b of the decree dated March 11, 2010 by the Ministry of Ecology, Energy, Sustainable Development and the Sea “pertaining to approval terms for laboratories or entities to perform certain types of samples and analyses upon the emission of substances into the atmosphere.”

The concerned substances were :

mercury (Hg) gas,

hydrochloric acid (HCl) gas,

fluorhydric acid (HF) gas and particles,

metals gases and particles: arsenic (As), cadmium (Cd), chromium (Cr), cobalt (Co), copper (Cu), manganese (Mn), nickel (Ni), lead (Pb), antimony (Sb), thallium (Tl), vanadium (V),

sulfur dioxide (SO2),

ammonia (NH3).

The annual program for these analytical inter-laboratory comparisons (M1540AB_11_119507») was developed in cooperation with the advisory group. This group is made up at least of technical experts competent on the matrix, the analysis

methods, and an expert of recognized skill in statistical data processing.

The general organization of the inter-laboratory comparison and the different statistical processing procedures are presented in annex 1 of this report.

9 TEST PARTICIPANTS

Twenty-nine laboratories, consisting of analysis laboratories and sampling entities having an in-house analysis laboratory, participated in this test. This population is broken down by programs as indicated below:

11 participants for measuring mercury in a permanganate medium,

15 participants for measuring mercury in a dichromate medium,

19 participates for measuring mercury in hydrochloric acid,

17 participates for measuring fluorinated compounds,

14 participants for measuring metals,

18 participants for measuring sulfur dioxide,

21 participants for measuring ammonia.

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The equipment used by the participants as well as the methodologies applied and the results relative to the tests are presented in this report anonymously, using the confidential codes assigned to the participants when they registered for the tests.

10 DESCRIPTION OF THE TEST MATERIALS

10.1 DESCRIPTION AND INSTRUCTIONS

The same operator or team should perform all of the analyses for a given parameter, in a short time interval, specified for each compound below.

These analyses should be considered independent tests: all of the operations were to be repeated, from sampling in the bottles to expression of the final result.

10.1.1 Total mercury in permanganate medium

An absorption solution was prepared according to the stipulations of standard EN 13211, then was used as flushing solution on the INERIS test block where combustion gases were generated, in order to create a matrix as close as possible (presence of interferents) to samples usually analyzed.

This absorption solution, made up of 2% of KMnO4 and 10% of H2SO4 was analyzed, then spiked to make up the test material referenced 11/119507_Hg _KMnO4.

Two samples (X and Y) were taken out to be sent to each participant in order to determine the so-called Hg gas content.

The analysis of these two samples was to follow the stipulations of standard EN 13211. Two measurements were requested per bottle provided, or a total of 4 measurements expressed in µg Hg/L with zero decimals.

It was strongly recommended to analyze these solutions within a maximum of 15 days (Cf EN 13211), the stability not being verified beyond that period.

10.1.2 Total mercury in dichromate medium


This absorption solution made up of 4 % of K2Cr2O7 and 20% of HNO3 was analyzed, then spiked to make up the test material referenced 11/119507_Hg _ K2Cr2O7.

Two samples (X and Y) were taken out to be sent to each participant in order to determine the so-called Hg gas content.

The analysis of these two samples was to follow the stipulations of standard EN 13211. Two measurements were requested per bottle provided, or a total of 4 measurements expressed in µg Hg/L with zero decimals.

It was strongly recommended to analyze these solutions within a maximum of 15 days (Cf EN 13211), the stability not being verified beyond that period.

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10.1.3 Hydrochloric acid


This absorption solution made up H2O was analyzed, then spiked to make up the test material referenced 11/119507_HCl.

Two samples (X and Y) were taken out to be sent to each participant in order to determine the so-called HCl gas content.

The analysis of these two samples was to follow the stipulations of standard EN 1911. Two measurements were requested per bottle provided, or a total of 4 measurements expressed in mg HCl/L with one decimal.

10.1.4 Fluorhydric acid

10.1.4.1 Solution

An absorption solution was prepared according to the stipulations of standard NF X 43-304, then was used as flushing solution on the INERIS test block where combustion gases were generated, in order to create a matrix as close as possible (presence of interferents) to samples usually analyzed.

This absorption solution made up NaOH 0.1 N was analyzed, then spiked to make up the test material referenced 11/119507_HF solution.

Two samples (X and Y) were taken out to be sent to each participant in order to determine the so-called HF gas content.

The measurements have been done using standard laboratory methods. Two measurements were requested per bottle provided, or a total of 4 measurements expressed in mg HF/L with one decimal.

10.1.4.2 Dusts

Dusts coming from a household waste incineration unit, previously analyzed, were dried and shredded to be spiked with fluorinated salts (NaF, CaF and K2SiF6), also dried and shredded. The whole was homogenized in order to make up the final test material referenced 11/119507_HF Poussiére.

Two samples (X and Y) were taken out to be sent to each participant in order to determine the fluorinated compound content level.

The Measurements have been done using standard laboratory methods. Two measurements were requested per bottle provided, or a total of 4 measurements expressed in mg HF/g with two decimals.

It was recommended to carry out an extractive phase and the fusion phase for each test, the final result corresponding to the sum of the results of the two phases.

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10.1.5 Metals (and metalloids)

10.1.5.1 Solution


This absorption solution made up 3% of HNO3 and 1.5% of H2O2 was analyzed, then spiked to make up the test material referenced 11/119507_Metaux solution.

Two samples (X and Y) were taken out to be sent to each participant in order to determine the content level in As, Cd, Cr, Co, Cu, Mn, Ni, Pb, Sb, Tl and V.

The analysis of these two samples was to follow the stipulations of standard EN 14385. Two measurements were requested per bottle provided, or a total of 4 measurements expressed in µg/L with zero decimals.

10.1.5.2 Dusts

Dusts coming from a glassworks manufacturing plant, previously analyzed, were dried and shredded to be spiked with oxides, also dried and shredded. The whole was homogenized in order to make up the final test material referenced 11/119507_Metaux Poussières.

Two samples (X and Y) were taken out to be sent to each participant in order to determine the content level in As, Cd, Cr, Co, Cu, Mn, Ni, Pb, Sb, Tl and V expressed in µg /g with one decimal.

The laboratories were asked to respect the following two protocols:

free protocol: Usual practice of the laboratory in measuring particulate metals (EN 14385),

imposed protocol: Free protocol with the requirement of not filtering the mineral residues before analysis.

10.1.6 Sulfur dioxide


This absorption solution made up of 3% of H2O2 was analyzed, then spiked to make up the test material referenced 11/119507_SO2.

Two samples (X and Y) were taken out to be sent to each participant in order to determine the SO2 content level.

The analysis of these two samples was to follow the stipulations of standard EN 14791. Two measurements were requested per bottle provided, or a total of 4 measurements expressed in mg SO2/L with one decimal.

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10.1.7 Ammonia

An absorption solution was prepared according to the stipulations of standard NF X 43-303, then was used as flushing solution on the INERIS test block where combustion gases were generated.

This absorption solution made up of H2SO4 0.1 N was analyzed, then spiked to make up the test material referenced 11/119507_NH3.

Two samples (X and Y) were taken out to be sent to each participant in order to determine the NH3 content level.

The Measurements have been done using standard laboratory methods. Two measurements were requested per bottle provided, or a total of 4 measurements expressed in mg NH3/L with one decimal.

Note: The participants were also alerted to the presence, in standard NF X 43-303, of errors in the description of the colorimetric method using indophenol blue and that it was preferable to refer to other standards (For example: NF T 90-015-2 and EN ISO 11732).

11 SHIPPING

A first shipment was done on May 17, 2011. For reasons inherent to our service provider, this first shipment was cancelled, requiring the production of new lots of test materials for the sensitive parameters (Hg).

A second shipment was done on May 24, 2011.

12 HOMOGENEITY AND STABILITY OF THE SAMPLES

12.1 HOMOGENEITY OF THE MATERIALS

The homogeneity of the materials was verified at the time of their distribution, according to the methodology explained in annex 1.

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Homogeneity of the test materials

Test materials Homogeneity

according to ISO 13528

Comments

11/119507_Hg_K2Cr2O7 Compliant -

11/119507_Hg_KMnO4 Non-compliant Taking inhomogeneity into account in calculating the z

score

11/119507_HCl Compliant -

11/119507_HF_Solution Compliant -

11/119507_HF_Poussiére Compliant -

11/119507_Metaux_solution Compliant for 9 of the 11 elements to

be assayed

Co, Pb: Taking inhomogeneity into account in calculating the z

score

11/119507_Metaux_Poussiére Compliant for 10 of the 11 elements to

be assayed

As: Taking inhomogeneity into account in calculating the z

score

11/119507_NH3 Compliant -

11/119507_SO2 Compliant -

12.2 STABILITY OF THE TEST MATERIALS

For each lot of test materials, 9 samples were randomly taken so as to establish the stability of the materials at the time of their distribution and during the analysis period by the participants.

Three samples were analyzed once per week for three weeks in double determination.

The stability of the materials was verified according to the methodology presented in annex 1.

Note: Because of internal analytical problem, the stability study of HCl has not been validated. Nevertheless, the study of the distribution of laboratory measures by time showed no significant trend due to a time effect.

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The following observations were made:

past the 12th day, a variation in the ammonia content in the vicinity of 3 % was shown.: no laboratory was affected,

past the 6th day, a variation in the sulfur dioxid content in the vicinity of 5 % was shown.: no laboratory was affected,

solution: a variation in the Cd content in the vicinity of 11 % on the 6th day to reach 15 % on the 29th day was shown: no laboratory was affected,

dusts:

- a variation of the As content level was showed past the 17th day: no laboratory was affected,

- a variation of the Co content level in the vicinity of 10% was shown past the 17th day: no laboratory was affected,

- a variation of the Cu content level in the vicinity of 9% was shown past the 17th day: no laboratory was affected.

13 RESULTS OF THE INTER-LABORATORY COMPARISON

13.1 EXPLOITATION OF THE DATA FROM THE TEST MATERIALS

13.1.1 General information

The details of the statistical processing are recalled in annex 1.

In the context of this test, the assigned values were defined as follows:

the value assigned to the average is taken to be equal to the robust average of the results provided by the participants in the inter-laboratory comparison,

the reference value of the standard deviation for assessing the aptitude is taken to be equal to the robust standard deviation.

The statistical processing applied to the data made it possible to determine:

- the reference value (or assigned value) of each parameter for each test and its associated uncertainty,

- each participant’s performance relative to the reference values via the z score indicator,

- suspicious or absurd results,

- the repeatability and reproducibility confidence intervals for each compound and each test material.

13.1.2 Presentation of the results

In this section, the results obtained before and after statistical processing, averages, repeatability standard deviations and performance of each laboratory (z score) are presented for each test material. A distribution diagram of the z scores making it possible to situate each laboratory globally relative to the other laboratories is also provided.

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The legend below is used :

Legend

1,4 Z i< 2: satisfactory score

2,3 Laboratory having a 2

Z i 3: debatable score requiring monitoring or

preventive action

3,56 Laboratory having a 3iZ : unsatisfactory score requiring corrective action

(the analysis results are not acceptable)

The other results relative to each test material are grouped together in :

annex 2: raw data for each participant: average, repeatability standard deviation, repeatability variability coefficient, and the values dismissed by expert opinion.

annex 3: statistical distribution curves: Sort by Averages: Values comprised between (x* - 3s*) and (x* + 3s*).

annex 4: histogram of the z scores obtained by each laboratory for all analytes of a test (Available for materials 11/119507_Metals_ solution and 11/119507_Metals_dust).

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13.1.3 Test material "11/119507_Hg_KMnO4"

Values observed before application of statistical algorithms

Parameter (µg/liter)

Mercury

Value targeted by spiking

12

Population Average

9.8

Population Standard Deviation

4.0

CVR (%)

40.5%

CVrep (%)

5.74%

Population 10

SL 3.9

SR 4.0

Sr 1.0

Values observed after application of statistical algorithms

Parameters (µg/liter)

Mercury


12

x* 11.5

s* 1.7

uX*

0.7

w* 1.0

SL 1.6

SR 1.9

Sr 1.0

Relative ICR (%) 39.0%

Relative ICr (%) 21.1%

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Averages, standard deviations and z scores for the laboratories

Laboratory Identification

Mercury

x µg/L

sr µg/L

sr %

Z scores

11201 8.5 1.0 11.7% -1.50

11207 Not analyzed

11209 10.2 1.5 14.6% -0.64

11210 Not analyzed

11212 Not analyzed

11236 13.2 2.2 16.7% 0.85

11249 12.0 0.0 0.0% 0.23

11250 Not analyzed

11255 10.5 0.6 5.5% -0.51

11262 < 1.0 0.0 0.0% (-5.22)*

11273 Not analyzed

11275 < 5.0 0.0 0.0% (-3.24)*

11279 12.5 0.6 4.6% 0.48

11281 13.0 0.0 0.0% 0.73

11283 11.8 0.5 4.3% 0.11

11285 Not analyzed

11288 Not analyzed

11291 Not analyzed

()*: Z score calculated relative to the threshold value rendered. NB: the absolute value is bounded from below.

Remarks and comments :

Laboratories 11262 and 11275 delivered results in the form of measurement thresholds respectively of < 1 and < 5 µg/L. They were excluded from the robust statistical processing by expert opinion.

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Laboratory 11236 was marked as abnormal by the Mandel k test due to its intra-laboratory dispersion.

13.1.4 Test material "11/119507_Hg_K2Cr2O7"



Mercury


12

Population Average 11.3


1.8

CVR (%)

15.6%

CVrep (%)

3.25%

Population 14

SL 1.75

SR 1.82

Sr 0.51



Mercury


12

x* 11.3

s* 1.7

uX*

0.6

w* 0.5

SL 1.7

SR 1.7

Sr 0.5



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Mercury

x µg/L

sr µg/L

sr %

Z Scores

11201 Not analyzed

11207 12.50 1.29 10.33 0.69

11209 Not analyzed

11210 11.48 0.13 1.10 0.27

11212 < 10.00 0.00 0.00 (-0.71)*

11236 9.25 0.50 5.41 -1.14

11249 9.75 0.50 5.13 -0.86

11250 12.25 0.06 0.51 0.41

11255 11.50 0.58 5.02 0.13

11262 10.00 0.00 0.00 -0.71

11273 10.50 0.58 5.50 -0.43

11275 15.75 0.50 3.17 2.51

11279 Not analyzed

11281 Not analyzed

11283 11.25 0.50 4.44 -0.01

11285 13.00 0.00 0.00 0.97

11288 9.30 0.08 0.88 -1.28

11291 12.25 0.50 4.08 0.55

()*: Z score calculated relative to the threshold value rendered. NB: the absolute value is bounded from below.


Laboratory 11275 obtained a z score between |2| and |3|.

Laboratory 11212 rendered a threshold value of 10 µg/L. It was excluded from the robust statistical processing by expert opinion.

DRC-11-119507-08855B Page 23 sur 171

Laboratory 11207 has a higher intra-laboratory dispersion than the rest of the population.

13.1.5 Test material "11_119507_HCl"


Parameter (mg/liter)

Hydrochloric_acid


19.3



0.99

CVR (%)

5.13%

CVrep (%)

1.44%

Population 18

SL 0.97

SR 1.06

Sr 0.45



Hydrochloric_acid


19.3

x* 19.27

s* 1.02

uX* 0.30

w* 0.34

SL 1.01

SR 1.06

Sr 0.34



DRC-11-119507-08855B Page 24 sur 171



Hydrochloric_Acid

x mg/L

sr mg/L

sr %

Z Scores

11207 18.65 0.13 0.69% -0.60

11210 21.15 0.41 1.95% 1.84

11212 18.48 0.05 0.27% -0.77

11222 19.60 0.08 0.42% 0.33

11226 19.25 0.06 0.30% -0.01

11236 19.40 0.47 2.42% 0.13

11249 19.20 0.00 0.00% -0.06

11251 19.58 0.10 0.49% 0.30

11255 20.78 1.47 7.09% 1.48

11259 19.40 0.00 0.00% 0.13

11262 18.15 0.53 2.93% -1.09

11273 18.08 0.57 3.17% -1.16

11275 18.40 0.08 0.44% -0.85

11279 19.78 0.10 0.48% 0.50

11281 17.98 0.34 1.89% -1.26

11283 21.28 0.46 2.15% 1.96

11288 18.88 0.22 1.17% -0.38

11291 19.60 0.00 0.00% 0.33



DRC-11-119507-08855B Page 25 sur 171

13.1.6 Test material "11_119507_HF_Solution"



Fluorhydric_acid


1.92



0.10

CVR (%)

5.04%

CVrep (%)

1.95%

Population 17

SL 0.09

SR 0.10

Sr 0.05



Fluorhydric_acid


1.92

x* 1.88

s* 0.10

uX* 0.03

w* 0.04

SL 0.10

SR 0.11

Sr 0.04



DRC-11-119507-08855B Page 26 sur 171



Fluorhydric Acid

x mg/L

sr mg/L

sr %

Z Scores

11209 1.81 0.03 1.47% -0.77

11210 1.88 0.10 5.34% -0.04

11212 1.75 0.01 0.57% -1.35

11214 1.93 0.03 1.77% 0.42

11226 1.75 0.07 3.81% -1.33

11236 1.87 0.02 1.19% -0.16

11249 1.83 0.02 1.30% -0.57

11250 1.95 0.03 1.48% 0.59

11255 2.01 0.09 4.71% 1.18

11262 1.83 0.03 1.75% -0.50

11273 1.88 0.05 2.39% -0.01

11275 1.91 0.01 0.50% 0.28

11279 1.98 0.01 0.25% 0.96

11283 1.96 0.04 1.82% 0.74

11285 1.75 0.01 0.29% -1.33

11288 2.08 0.06 3.10% 1.88

11291 1.93 0.03 1.50% 0.40

DRC-11-119507-08855B Page 27 sur 171


Laboratories 11255 and 11210 have a higher intra-laboratory dispersion than the other laboratories.

13.1.7 Test material "11_119507_HF_Poussière"


Parameter (in mg/g)

Fluorinated compounds expressed in HF


15.7



5.16

CVR (%)%)

50.4%

CVrep (%)%)

7.10%

Population 16

SL 5.04

SR 5.12

Sr 0.87


Parameter (mg/g)



15.7

x* 9.91

s* 4.97

uX*

1.55

w* 0.83

SL

4.96

SR

5.02

Sr

0.83



DRC-11-119507-08855B Page 28 sur 171




x mg/g

sr mg/g

sr %

Z Scores

11209 14.03 1.05 7.46% 0.83

11210 21.88 1.93 8.80% 2.40

11212 9.30 0.68 7.29% -0.12

11214 12.75 0.97 7.59% 0.57

11226 Not analyzed

11236 6.25 0.17 2.77% -0.74

11249 12.00 0.42 3.54% 0.42

11250 11.70 0.16 1.40% 0.36

11255 4.48 0.21 4.61% -1.09

11262 3.63 0.24 6.52% -1.26

11273 14.13 1.63 11.51% 0.85

11275 13.25 0.54 4.11% 0.67

11279 1.00 0.10 10.00% -1.79

11283 9.40 0.52 5.51% -0.10

11285 9.60 0.35 3.61% -0.06

11288 5.17 1.28 24.76% -0.95

11291 13.10 0.55 4.18% 0.64

DRC-11-119507-08855B Page 29 sur 171


Laboratory 11210 is beyond the monitoring limit and has a larger repeatability standard deviation than the rest of the population.

Given the high inter-laboratory dispersion, the calculation of the z score does not make it possible to judge each laboratory’s performance precisely. To situate their results, the laboratories are therefore advised to compare, for information, their averages values to the spiking value even if it is not the reference value for the exercise.

Despite harmonization in the measuring of the particulate fluorinated compounds by quasi-systematic integration of alkali fusion, the inter-laboratory dispersion in the vicinity of 50% remains relatively significant for this analysis. The data collected via the online entry form does not make it possible to clearly explain this phenomenon.

Nevertheless, it would be interesting to set certain parameters that can unbalance the robustness of the method, such as test-taking, for example. In fact, the impossibility of distributing filters to the laboratories on which a constant and homogenous quantity of dust is deposited leaves a broad choice in the initial test-taking.

13.1.8 Test material "11/119507_Metaux_solution"


Parameter (µg/liter)

Antimony Arsenic Cadmium Chromium Cobalt Copper Manganese Nickel Lead Thallium Vanadium

Values targeted

by spiking 450 130 20 190 220 230 210 220 480 20 190

Population Average 455.5 132.3 20.9 189.9 215.0 224.8 214.2 212.4 488.9 20.2 185.5


22.2 8.9 4.6 20.5 24.3 23.5 26.5 24.3 17.5 3.2 20.4

CVR (%)%) 4.87% 6.72% 21.9% 10.8% 11.3% 10.4% 12.4% 11.4% 3.59% 15.7% 11.0%

CVrep (%) 0.80% 1.69% 1.34% 1.31% 0.99% 1.10% 1.11% 1.43% 0.72% 1.86% 1.11%

Population 14 14 14 14 14 14 14 14 14 14 14

SL 22.1 8.8 4.6 20.5 24.3 23.4 26.4 24.2 17.3 3.2 20.3

SR 22.6 9.2 4.6 20.7 24.4 23.6 26.6 24.4 18.1 3.2 20.5

Sr 4.9 2.8 0.4 2.9 2.5 2.9 2.5 3.5 5.2 0.7 2.4

DRC-11-119507-08855B Page 30 sur 171




Values targeted

by spiking 450 130 20 190 220 230 210 220 480 20 190

x* 456.8 132.3 20.4 194.0 220.8 228.7 220.3 216.9 488.9 20.9 189.1

s* 22.1 10.1 0.9 8.3 8.4 15.3 7.2 12.6 19.9 1.2 11.8

uX* 7.4 3.4 0.3 2.8 2.8 5.1 2.4 4.2 6.6 0.4 3.9

w* 4.2 2.8 0.0 3.0 2.7 2.7 2.7 3.8 3.4 0.0 2.6

SL 22.0 10.0 0.9 8.2 8.3 15.2 7.0 12.5 19.8 1.2 11.7

SR 22.4 10.4 0.9 8.7 8.7 15.4 7.5 13.1 20.1 1.2 12.0

Sr 4.2 2.8 0.0 3.0 2.7 2.7 2.7 3.8 3.4 0.0 2.6

Relative ICR (%)

10.6% 16.9% 9.28% 9.68% 8.56% 14.6% 7.39% 13.0% 8.88% 12.3% 13.8%

Relative ICr (%)

2.00% 4.54% 0.00% 3.31% 2.63% 2.59% 2.69% 3.79% 1.50% 0.00% 2.99%



Antimony Arsenic

x µg/L

sr µg/L

sr %

Z Scores

x µg/L

sr µg/L

sr %

Z Scores

11210 468.2 2.2 0.47% 0.49 125.5 1.3 1.03% -0.64

11212 467.2 1.5 0.32% 0.45 135.2 1.0 0.71% 0.28

11232 487.5 0.6 0.12% 1.32 118.8 5.6 4.73% -1.27

11236 458.0 3.6 0.78% 0.05 144.5 2.5 1.74% 1.15

11240 446.5 1.9 0.43% -0.44 126.8 0.5 0.39% -0.52

11249 490.0 2.2 0.44% 1.42 134.5 1.3 0.96% 0.21

11250 445.7 1.6 0.37% -0.47 125.3 1.7 1.32% -0.66

11255 438.0 5.7 1.29% -0.80 144.0 2.7 1.88% 1.10

11262 406.0 13.3 3.27% -2.18 127.5 1.0 0.78% -0.45

11273 465.8 6.4 1.37% 0.38 142.5 1.3 0.91% 0.96

11275 448.2 1.0 0.21% -0.37 117.5 0.6 0.49% -1.39

11279 458.0 6.9 1.51% 0.05 135.5 2.5 1.86% 0.30

11283 430.2 0.5 0.12% -1.14 134.2 4.2 3.12% 0.19

11288 467.8 2.5 0.53% 0.47 140.0 5.2 3.69% 0.73

DRC-11-119507-08855B Page 31 sur 171


Antimony :

Laboratory 11262 obtained a z score between |2| and |3| and its intra-laboratory dispersion is higher than the rest of the population.

DRC-11-119507-08855B Page 32 sur 171



Cadmium Chromium

x

µg/L

sr

µg/L

sr

% Z scores

x

µg/L

sr

µg/L

sr

% Z scores

11210 21.0 0.0 0.00% 0.65 197.5 1.3 0.65% 0.39

11212 21.0 0.0 0.00% 0.65 199.2 1.0 0.48% 0.59

11232 12.8 0.5 3.92% -8.28 122.2 3.5 2.86% -8.20

11236 21.0 0.0 0.00% 0.65 193.2 1.3 0.65% -0.09

11240 20.0 0.0 0.00% -0.43 194.0 1.6 0.84% -0.01

11249 21.0 0.0 0.00% 0.65 191.0 1.8 0.96% -0.35

11250 19.6 0.4 1.84% -0.70 190.1 0.6 0.34% -0.46

11255 20.0 0.0 0.00% -0.43 187.5 3.7 1.97% -0.75

11262 20.2 0.5 2.47% -0.16 193.8 1.5 0.77% -0.03

11273 19.5 0.6 2.96% -0.97 200.2 2.4 1.18% 0.71

11275 21.0 0.0 0.00% 0.65 181.2 0.5 0.28% -1.46

11279 35.0 0.0 0.00% 15.81 198.2 6.1 3.06% 0.48

11283 19.5 0.6 2.96% -0.97 207.2 3.2 1.54% 1.51

11288 20.8 1.0 4.61% 0.38 202.2 5.4 2.69% 0.94

DRC-11-119507-08855B Page 33 sur 171

Remarks and Comments :

Cadmium :

Laboratories 11232 and 11279 obtained z scores greater than |3|.


Chromium :

Laboratory 11232 obtained a z score greater than |3|.


DRC-11-119507-08855B Page 34 sur 171



Cobalt Copper

x

µg/L

sr

µg/L

sr

%

Z scores x

µg/L

sr

µg/L

sr

%

Z scores

11210 225.0 1.4 0.63% 0.45 236.0 0.8 0.35% 0.45

11212 227.8 1.0 0.42% 0.74 243.5 1.3 0.53% 0.92

11232 135.0 4.2 3.14% -9.18 155.2 4.4 2.85% -4.57

11236 229.5 0.6 0.25% 0.93 244.8 1.0 0.39% 1.00

11240 216.0 1.4 0.65% -0.51 229.0 1.6 0.71% 0.02

11249 227.8 1.7 0.75% 0.74 241.2 1.9 0.78% 0.78

11250 215.2 1.2 0.55% -0.59 225.0 0.9 0.40% -0.21

11255 200.8 4.3 2.13% -2.15 208.2 7.1 3.43% -1.27

11262 218.5 1.9 0.88% -0.25 240.5 2.4 0.99% 0.73

11273 219.8 1.5 0.68% -0.11 233.0 3.6 1.53% 0.27

11275 215.0 0.0 0.00% -0.62 202.8 1.0 0.47% -1.61

11279 226.5 4.6 2.06% 0.61 231.0 0.8 0.35% 0.14

11283 225.2 0.5 0.22% 0.48 232.5 2.9 1.24% 0.24

11288 228.8 3.5 1.53% 0.85 225.2 3.0 1.33% -0.21

DRC-11-119507-08855B Page 35 sur 171


Cobalt :




Copper :



DRC-11-119507-08855B Page 36 sur 171



Manganese Nickel

x µg/L

sr µg/L

sr %

Z Scores

x µg/L

sr µg/L

sr %

Z Scores

11210 224.0 0.8 0.36% 0.49 229.0 0.8 0.36% 0.90

11212 225.8 1.0 0.42% 0.72 227.8 1.0 0.42% 0.81

11232 124.2 4.0 3.24% -12.74 135.2 4.4 3.22% -6.12

11236 227.2 1.9 0.83% 0.92 227.8 1.0 0.42% 0.81

11240 212.5 1.3 0.61% -1.03 218.8 1.7 0.78% 0.14

11249 225.0 1.4 0.63% 0.62 219.0 2.2 0.99% 0.15

11250 216.2 1.6 0.76% -0.54 213.1 1.0 0.45% -0.26

11255 210.5 3.7 1.76% -1.30 199.8 5.9 2.96% -1.29

11262 218.8 2.8 1.26% -0.20 203.8 3.0 1.47% -0.99

11273 223.0 2.9 1.32% 0.36 217.0 3.8 1.76% 0.00

11275 216.8 1.0 0.44% -0.47 205.0 2.9 1.44% -0.90

11279 229.2 1.7 0.74% 1.19 226.2 5.5 2.43% 0.70

11283 222.5 2.9 1.30% 0.29 226.8 1.3 0.55% 0.74

11288 223.0 4.2 1.87% 0.36 225.0 6.4 2.83% 0.60

DRC-11-119507-08855B Page 37 sur 171


Manganese :


Nickel :


DRC-11-119507-08855B Page 38 sur 171



Lead Thallium

x µg/L

sr µg/L

sr %

Z Scores

x µg/L

sr µg/L

sr %

Z Scores

11210 496.0 3.2 0.64% 0.32 22.0 0.0 0.00% 0.91

11212 496.8 1.0 0.19% 0.36 22.2 0.5 2.25% 1.11

11232 504.5 1.7 0.34% 0.71

DRC-11-119507-08855B Page 39 sur 171


Lead :


Thallium :

Laboratory 11232 returned results in the form of a measurement threshold of < 10 µg/L. It was excluded from the robust statistical processing.

Laboratory 11236 obtained a z score between |2| and |3|. Furthermore, it is marked by the Cochran and Mandel k tests as having an excessively high intra-laboratory dispersion.

DRC-11-119507-08855B Page 40 sur 171



Vanadium

x µg/L

sr µg/L

sr %

Z Scores

11210 196.5 0.6 0.29% 0.59

11212 198.5 0.6 0.29% 0.76

11232 122.5 4.2 3.43% -5.34

11236 196.2 1.0 0.49% 0.57

11240 188.8 1.7 0.90% -0.03

11249 201.2 1.9 0.94% 0.98

11250 181.7 0.4 0.25% -0.59

11255 186.5 3.8 2.03% -0.21

11262 188.5 1.0 0.53% -0.05

11273 194.5 3.8 1.95% 0.43

11275 182.2 0.5 0.27% -0.55

11279 184.0 4.1 2.22% -0.41

11283 205.8 1.0 0.47% 1.34

11288 170.2 2.5 1.47% -1.51



Conclusion on this test :

This histograms shown in annex 4 made it possible to observe the following situation: laboratory 11232 must undertake corrective actions for 73% of the analytes measured.

DRC-11-119507-08855B Page 41 sur 171

13.1.9 Test material "11/119507_Metaux_Poussiére" free protocol


Parameter (µg/lg)


Value targeted

by spiking * * 201 1564 1786 1906 1681 1804 * 255 1533

Population Average

5760.7 1853.8 215.0 729.9 1755.4 1953.4 1617.7 1644.6 35461.6 235.2 1446.4


695.0 736.4 99.3 610.8 258.9 241.1 400.3 478.6 4883.7 90.2 222.1

CVR (%)%)

12.1% 39.7% 46.2% 83.7% 14.7% 12.3% 24.7% 29.1% 13.8% 38.4% 15.4%

CVrep (%)%)

4.6% 3.0% 2.9% 12.2% 4.5% 3.1% 5.1% 3.7% 3.1% 4.6% 3.8%

Population 13 13 13 13 13 13 13 13 13 13 13

SL 635.7 728.6 99.8 611.3 234.5 211.6 395.3 480.2 4748.5 84.4 211.7

SR 715.9 733.6 100.0 617.3 254.3 225.9 407.0 487.4 4957.1 85.0 225.7

Sr 329.3 85.7 7.6 85.7 98.2 79.0 97.1 83.2 1422.8 10.1 78.2

* Compounds for which it was not necessary to add a dopant.


Parameter (µg/g)


Value targeted

by spiking * * 201 1564 1786 1906 1681 1804 * 255 1533

x* 5753.9 1720.0 190.2 708.5 1731.9 1943.0 1583.2 1558.5 34973.5 233.1 1433.5

s* 693.7 585.3 32.1 692.6 217.3 203.1 361.7 285.1 4997.1 53.4 251.1

uX* 240.5 202.9 11.1 240.1 75.3 70.4 125.4 98.8 1732.4 18.5 87.1

w* 181.4 57.8 8.0 45.9 102.1 58.9 103.5 46.6 1029.3 11.2 60.2

SL 687.5 584.5 31.9 692.2 211.0 200.9 357.8 284.1 4969.4 53.1 249.2

SR 711.0 587.4 32.9 693.7 234.4 209.4 372.5 287.9 5074.9 54.2 256.4

Sr 181.4 57.8 8.0 45.9 102.1 58.9 103.5 46.6 1029.3 11.2 60.2

Relative ICR (%)

26.9% 74.4% 37.7% 213.3% 29.5% 23.5% 51.3% 40.2% 31.6% 50.7% 39.0%

Relative ICr (%)

6.9% 7.3% 9.2% 14.1% 12.8% 6.6% 14.2% 6.5% 6.4% 10.4% 9.1%


DRC-11-119507-08855B Page 42 sur 171



Antimony Arsenic

x µg/g

sr µg/g

sr %

Z Scores

x µg/g

sr µg/g

sr %

Z Scores

11210 5781.5 132.1 2.28% 0.04 1475.8 61.2 4.15% -0.38

11212 5988.0 164.9 2.75% 0.32 1449.8 34.9 2.40% -0.42

11232 5046.2 14.9 0.30% -0.96 1405.0 52.6 3.74% -0.49

11236 6702.8 166.9 2.49% 1.29 2443.0 66.9 2.74% 1.12

11240 6037.8 30.3 0.50% 0.39 1805.5 23.4 1.30% 0.13

11249 5615.8 105.5 1.88% -0.19 1335.5 26.4 1.98% -0.60

11250 Not analyzed Not analyzed

11255 5910.5 114.2 1.93% 0.21 1516.5 32.8 2.16% -0.32

11262 4406.0 200.4 4.55% -1.84 1342.8 14.9 1.11% -0.58

11273 6092.2 877.9 14.41% 0.46 1762.5 198.9 11.28% 0.07

11275 5603.8 4.4 0.08% -0.20 2850.0 47.6 1.67% 1.75

11279 4458.0 1080.5 24.24% -1.77 975.0 1.4 0.15% -1.15

11283 6385.5 149.7 2.34% 0.86 1653.5 31.9 1.93% -0.10

11288 6210.2 130.4 2.10% 0.62 3645.2 181.5 4.98% 2.98

DRC-11-119507-08855B Page 43 sur 171


Antimony :

Laboratories 11273 and 11279 have higher intra-laboratory dispersions than the rest of the population.

Arsenic :

Laboratory 11288 obtained a Z score between |2| and |3|. Furthermore, according to the Cochran and Mandel k tests, it has a higher intra-laboratory dispersion than the rest of the population. This last observation is also valid for laboratory 11273.

DRC-11-119507-08855B Page 44 sur 171



Cadmium Chromium

x

µg/g

sr

µg/g

sr

%

Z Scores

x

µg/g

sr

µg/g

sr

%

Z Scores

11210 209.0 14.5 6.93% 0.55 932.2 17.4 1.87% 0.31

11212 177.0 2.2 1.22% -0.39 1421.2 28.7 2.02% 0.97

11232 145.0 3.5 2.39% -1.33 32.5 3.0 9.23% -0.92

11236 205.8 8.6 4.17% 0.46 200.0 99.2 49.59% -0.69

11240 194.2 3.3 1.70% 0.12 1599.5 29.5 1.84% 1.22

11249 175.0 3.6 2.03% -0.45 1345.8 50.3 3.73% 0.87


11255 185.0 1.2 0.62% -0.15 673.0 11.9 1.77% -0.05

11262 196.2 3.3 1.68% 0.18 10.5 1.7 16.50% -0.95

11273 225.5 11.7 5.18% 1.04 970.2 267.1 27.52% 0.36

11275 172.2 2.1 1.20% -0.53 42.8 0.5 1.17% -0.91

11279 129.0 5.7 4.39% -1.80 173.0 55.2 31.88% -0.73

11283 530.2 13.2 2.49% 10.00 1470.0 53.1 3.61% 1.04

11288 207.5 7.0 3.40% 0.51 339.5 28.7 8.44% -0.50

DRC-11-119507-08855B Page 45 sur 171


Cadmium :

Laboratory 11283 obtained a Z score greater than |3|.

Laboratory 11210 has a greater intra-laboratory dispersion than the rest of the population.

Chromium :

Laboratories 11236 and 11273 are marked by the Cochran test as having significant intra-laboratory dispersions relative to those of the rest of the population.

DRC-11-119507-08855B Page 46 sur 171



Cobalt Copper

x

µg/g

sr

µg/g

sr

%

Z Scores

x

µg/g

sr

µg/g

sr

%

Z Scores

11210 1651.5 136.9 8.29% -0.35 1846.2 33.9 1.83% -0.45

11212 1705.2 106.6 6.25% -0.12 1963.0 37.5 1.91% 0.09

11232 1502.5 62.0 4.13% -1.00 1662.5 36.6 2.20% -1.30

11236 2285.5 145.1 6.35% 2.41 2359.0 11.9 0.50% 1.93

11240 1828.5 21.2 1.16% 0.42 2077.2 44.1 2.12% 0.62

11249 1594.0 100.5 6.30% -0.60 1902.8 66.2 3.48% -0.19


11255 1674.0 91.5 5.47% -0.25 1844.0 48.4 2.62% -0.46

11262 1642.8 36.0 2.19% -0.39 1844.2 50.4 2.73% -0.46

11273 1986.8 188.2 9.47% 1.11 2139.2 233.6 10.92% 0.91

11275 1844.5 7.0 0.38% 0.49 2112.5 15.0 0.71% 0.79

11279 1212.5 36.1 2.97% -2.26 1371.0 91.9 6.70% -2.66

11283 1671.2 19.3 1.16% -0.26 1989.5 21.4 1.08% 0.22

11288 1949.8 86.2 4.42% 0.95 1991.5 60.7 3.05% 0.23

DRC-11-119507-08855B Page 47 sur 171


Cobalt :

Laboratories 11236 and 11279 obtained z scores between |2| and |3|.

According to the Mandel test, laboratory 11273 has a higher intra-laboratory dispersion than the rest of the population.

Copper :


Laboratory 11273 is marked by the Cochran test as having significant intra-laboratory dispersions relative to the rest of the population.

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Manganese Nickel

x µg/g

sr µg/g

sr %

Z Scores x

µg/g sr

µg/g sr %

Z Scores

11210 1148.2 50.6 4.41% -1.14 1542.0 10.1 0.65% -0.05

11212 1623.2 37.4 2.30% 0.10 1589.5 23.6 1.48% 0.10

11232 1450.0 52.1 3.59% -0.35 1186.2 19.3 1.63% -1.23

11236 1993.5 128.0 6.42% 1.07 3020.0 57.1 1.89% 4.84

11240 2493.5 15.9 0.64% 2.38 1563.0 35.2 2.25% 0.01

11249 1585.8 172.9 10.91% 0.01 1463.0 37.1 2.53% -0.32


11255 1545.5 84.9 5.49% -0.10 1575.8 44.8 2.84% 0.06

11262 900.8 160.5 17.82% -1.78 1024.0 176.9 17.27% -1.77

11273 1797.5 169.2 9.41% 0.56 1848.5 205.9 11.14% 0.96

11275 1725.2 6.1 0.35% 0.37 1751.2 21.0 1.20% 0.64

11279 1175.0 25.5 2.17% -1.07 1260.5 9.2 0.73% -0.99

11283 1680.8 30.5 1.82% 0.25 1644.2 37.9 2.30% 0.28

11288 1690.2 15.2 0.90% 0.28 1719.8 28.9 1.68% 0.53

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Manganese :


Nickel :


Laboratories 11262 and 11273 are marked by the Cochran and Mandel k tests as having higher intra-laboratory dispersions than the rest of the population.

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Lead Thallium

x µg/g

sr µg/g

sr %

Z Scores

x µg/g

sr µg/g

sr %

Z Scores

11210 33350.8 1080.6 3.24% -0.31 238.2 6.13 2.57% -0.07

11212 36977.5 1064.8 2.88% 0.38 78.6 3.24 4.12% -3.76

11232 33625.0 1532.7 4.56% -0.25 232.0 2.45 1.06% -0.21

11236 45203.2 1185.6 2.62% 1.93 258.8 15.44 5.97% 0.41

11240 35515.2 474.3 1.34% 0.10 245.2 2.22 0.90% 0.09

11249 34408.0 980.1 2.85% -0.11 218.2 13.00 5.96% -0.53


11255 31392.0 523.8 1.67% -0.68 244.8 10.72 4.38% 0.08

11262 35527.0 361.1 1.02% 0.10 249.8 6.29 2.52% 0.20

11273 27593.2 4065.2 14.73% -1.40 289.8 18.30 6.32% 1.12

11275 42825.0 250.0 0.58% 1.48 184.2 4.35 2.36% -1.31

11279 28951.0 455.4 1.57% -1.14 56.5 10.61 18.77% -4.27

11283 34649.5 258.5 0.75% -0.06 250.5 2.38 0.95% 0.22

11288 37728.2 771.5 2.05% 0.52 421.8 15.90 3.77% 4.17

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Lead :

Laboratory 11273 is marked by the Cochran and Mandel k tests as having a higher intra-laboratory dispersion than the rest of the population.

Thallium :

Laboratories 11212, 11279 and 11288 obtained z scores greater than |3|.

Laboratory 11279 was excluded from the robust statistical tests by expert opinion for delivering 2 results, 1 in threshold form.

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Vanadium

x µg/g

sr µg/g

sr %

Z Scores

11210 1463.8 66.7 4.56% 0.11

11212 1616.0 35.9 2.22% 0.69

11232 1052.5 17.6 1.67% -1.43

11236 1326.8 27.6 2.08% -0.40

11240 1768.2 10.8 0.61% 1.26

11249 1352.2 74.0 5.47% -0.31

11250 Not analyzed

11255 1398.5 27.3 1.95% -0.13

11262 1469.2 44.2 3.01% 0.13

11273 1604.8 217.8 13.57% 0.64

11275 1198.8 17.5 1.46% -0.88

11279 1102.5 44.6 4.04% -1.25

11283 1613.5 93.2 5.78% 0.68

11288 1664.5 56.9 3.42% 0.87




The histograms shown in annex 4 made is possible to observe the following situations :

Laboratory 11236: 2 analytes out of 11 require monitoring and/or correction.



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13.1.10 Test material "11/119507_Métaux_Poussiére" imposed protocol


Parameter (µg/g)


Value targeted

by spiking * * 201 1564 1786 1906 1681 1804 * 255 1533

Population Average

6138.0 1886.5 243.6 931.4 1831.7 2034.7 1837.5 1783.3 36066.4 272.4 1511.2


402.9 671.2 138.6 549.3 174.0 172.8 290.6 469.9 4549.1 74.2 169.2

CVR (%)

6.6% 35.6% 56.9% 59.0% 9.5% 8.5% 15.8% 26.3% 12.6% 27.2% 11.2%

CVrep (%)

3.2% 4.0% 2.7% 17.1% 4.4% 3.6% 4.2% 2.7% 4.1% 8.4% 3.9%

Population 10 10 10 10 10 10 10 10 10 10 10

SL 343.7 676.4 141.2 543.3 170.8 163.6 291.2 479.7 4581.3 67.2 166.0

SR 463.1 685.5 141.4 585.2 195.9 194.7 309.0 486.3 4907.7 69.5 188.8

Sr 310.4 111.7 6.8 217.5 95.9 105.6 103.6 79.9 1759.7 17.8 90.1



Parameter (µg/g)


Value targeted

by spiking * * 201 1564 1786 1906 1681 1804 * 255 1533

x* 6173.4 1724.2 202.2 953.5 1811.6 2015.3 1752.4 1671.0 35922.3 263.0 1504.2

s* 456.9 386.4 33.5 622.9 157.3 171.2 143.7 179.1 2326.9 46.1 187.2

uX* 180.6 152.7 13.2 246.2 62.2 67.7 56.8 70.8 919.8 18.2 74.0

w* 173.1 92.2 7.2 144.1 96.9 84.4 104.5 54.7 1765.7 18.4 71.1

SL 448.1 383.5 33.3 618.5 149.2 165.6 133.3 176.9 2142.9 45.1 183.6

SR 480.4 394.4 34.1 635.0 177.9 185.9 169.3 185.2 2776.6 48.7 196.9

Sr 173.1 92.2 7.2 144.1 96.9 84.4 104.5 54.7 1765.7 18.4 71.1

Relative ICR (%) 17.6% 51.7% 38.1% 150.7% 22.2% 20.9% 21.9% 25.1% 17.5% 41.9% 29.6%

Relative ICr (%) 6.3% 12.1% 8.1% 34.2% 12.1% 9.5% 13.5% 7.4% 11.1% 15.8% 10.7%


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Antimony Arsenic

x µg/g

sr µg/g

sr %

Z Scores

x µg/g

sr µg/g

sr %

Z Scores

11210 6318.0 171.4 2.71% 0.29 1561.8 80.3 5.14% -0.36


11232 5535.0 97.1 1.75% -1.30 1482.5 64.0 4.31% -0.53

11236 6807.8 115.9 1.70% 1.29 2402.8 94.8 3.94% 1.50

11240 6044.0 55.8 0.92% -0.26 1828.5 51.0 2.79% 0.23

11249 5870.0 31.7 0.54% -0.62 1398.5 41.7 2.98% -0.72


11255 6063.8 109.8 1.81% -0.22 1512.8 15.7 1.04% -0.47


11273 6092.2 877.9 14.41% -0.17 1762.5 198.9 11.28% 0.08


11279 6844.5 354.3 5.18% 1.37 1370.5 20.5 1.50% -0.78

11283 5948.0 36.9 0.62% -0.46 1717.2 11.0 0.64% -0.02

11288 6210.2 130.4 2.10% 0.08 3570.2 229.2 6.42% 4.07

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Antimony :


Arsenic :


Laboratories 11273 and 11288 are marked by the Cochran and Mandel k tests as having a higher intra-laboratory dispersion than the rest of the population.

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Cadmium Chromium

x µg/g

sr µg/g

sr %

Z Scores

x µg/g

sr µg/g

sr %

Z Scores

11210 231.2 8.6 3.73% 0.81 865.8 196.8 22.73% -0.13


11232 160.2 2.5 1.56% -1.16 32.8 1.5 4.58% -1.37

11236 212.0 8.1 3.83% 0.27 649.0 563.1 86.77% -0.45

11240 197.0 3.6 1.81% -0.14 1684.5 65.3 3.88% 1.09

11249 175.5 2.6 1.51% -0.74 1375.8 3.9 0.28% 0.63


11255 193.5 7.8 4.06% -0.24 650.8 32.3 4.97% -0.45


11273 225.5 11.7 5.18% 0.65 970.2 267.1 27.52% 0.03


11279 167.0 1.4 0.85% -0.98 1373.0 103.2 7.52% 0.63

11283 628.5 4.5 0.72% 11.84 1593.5 68.3 4.29% 0.96

11288 207.5 7.0 3.40% 0.15 339.5 28.7 8.44% -0.92

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Cadmium :

Laboratory 11283 has a z score greater than |3|.

Chromium :

Laboratories 11210, 11236 and 11273 are marked by the Cochran test as having a higher intra-laboratory dispersion than the rest of the population.

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Cobalt Copper

x µg/g

sr µg/g

sr %

Z Scores

x µg/g

sr µg/g

sr %

Z Scores

11210 1764.5 119.9 6.80% -0.28 2003.8 89.3 4.46% -0.06


11232 1760.0 22.0 1.25% -0.30 1907.5 29.9 1.57% -0.59

11236 2208.5 74.7 3.38% 2.35 2376.8 50.6 2.13% 1.96

11240 1832.5 97.4 5.31% 0.12 2207.5 170.0 7.70% 1.04

11249 1645.5 36.5 2.22% -0.98 1942.5 39.6 2.04% -0.40


11255 1654.8 59.9 3.62% -0.93 1807.2 23.1 1.28% -1.13


11273 1984.2 186.4 9.40% 1.02 2139.2 233.6 10.92% 0.67


11279 1752.0 49.5 2.83% -0.35 1854.5 2.1 0.11% -0.87

11283 1725.0 89.2 5.17% -0.51 2026.8 58.4 2.88% 0.06

11288 1949.8 86.2 4.42% 0.82 1991.5 60.7 3.05% -0.13

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Cobalt :

Laboratory 11236 obtained a Z score between |2| and |3|.

Laboratory 11273 is marked by the Mandel k test as having a higher intra-laboratory dispersion than the rest of the population.

Copper :

Laboratories 11240 and 11273 are marked by the Cochran test as having a higher intra-laboratory dispersion than the rest of the population.

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Manganese Nickel

x µg/g

sr µg/g

sr %

Z Scores

x µg/g

sr µg/g

sr %

Z Scores

11210 1791.5 113.2 6.32% 0.25 1698.0 68.6 4.04% 0.14


11232 1621.2 26.6 1.64% -0.85 1338.8 11.8 0.88% -1.72

11236 2197.0 71.2 3.24% 2.88 3051.8 92.1 3.02% 7.17

11240 2507.2 198.4 7.91% 4.89 1608.5 15.5 0.96% -0.32

11249 1653.8 27.2 1.65% -0.64 1550.5 35.3 2.28% -0.63


11255 1664.0 64.9 3.90% -0.57 1542.0 16.1 1.04% -0.67


11273 1797.5 169.2 9.41% 0.29 1848.5 205.9 11.14% 0.92


11279 1672.5 21.9 1.31% -0.52 1634.0 2.8 0.17% -0.19

11283 1697.8 91.1 5.37% -0.35 1766.5 35.1 1.99% 0.50

11288 1690.2 15.2 0.90% -0.40 1719.8 28.9 1.68% 0.25

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Manganese :




Nickel :



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Lead Thallium

x µg/g

sr µg/g

sr %

Z Scores x

µg/g sr

µg/g sr %

Z Scores

11210 36311.5 2269.2 6.25% 0.16 282.8 6.1 2.15% 0.40


11232 36650.0 640.3 1.75% 0.29 271.2 10.3 3.80% 0.17

11236 46105.0 1348.4 2.92% 4.07 291.0 28.3 9.73% 0.57

11240 36359.2 372.7 1.02% 0.17 251.0 16.8 6.69% -0.24

11249 35136.8 697.5 1.99% -0.31 207.5 3.1 1.50% -1.12


11255 33351.2 537.4 1.61% -1.03 257.2 3.9 1.50% -0.12

11262 Not analyzed

11273 27593.2 4065.2 14.73% -3.33 289.8 18.3 6.32% 0.54


11279 36891.5 3165.7 8.58% 0.39 125.0 56.6 45.25% -2.79

11283 34899.5 124.5 0.36% -0.41 253.5 7.8 3.10% -0.19

11288 37778.2 852.4 2.26% 0.74 421.8 15.9 3.77% 3.20

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Lead :

Laboratories 11236 and 11273 obtained z scores greater than |3|.

Laboratories 11210, 11273 and 11279 are marked by the Cochran test as having a higher intra-laboratory dispersion than the rest of the population.

Thallium :

Laboratory 11288 obtained z scores greater than |3|.



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Vanadium

x µg/g

sr µg/g

sr %

Z Scores

11210 1589.8 99.2 6.24% 0.43

11212 Not analyzed

11232 1300.0 0.0 0.00% -1.01

11236 1287.5 24.1 1.87% -1.08

11240 1806.2 85.5 4.73% 1.50

11249 1425.0 37.4 2.63% -0.39

11250 Not analyzed

11255 1386.5 18.3 1.32% -0.58

11262 Not analyzed

11273 1604.8 217.8 13.57% 0.50

11275 Not analyzed

11279 1414.5 7.8 0.55% -0.45

11283 1584.5 74.5 4.70% 0.40

11288 1664.5 56.9 3.42% 0.80



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More than the z score, which is only secondary in this test since it first and foremost involved testing an imposed methodology, it is the comparison of the inter-laboratory dispersions and recovery rates between the two protocols that is interesting.

In fact, even if the spiking value is not the reference value, it can nevertheless be used as a basis for comparison in the two methods. Of course, the compounds for which no dopant has been added are not subject to that comparison.

Parameters Cadmium Chromium Cobalt Copper Manganese Nickel Thallium Vanadium

(µg/g)

Values targeted by spiking

201 1564 1786 1906 1681 1804 255 1533

Free protocol

x* 190.2 708.5 1731.9 1943 1583.2 1558.5 233.1 1433.5

Recovery rate % 94.6% 45.3% 97.0% 101.9% 94.2% 86.4% 91.4% 93.5%

Absolute SR 32.9 693.7 234.4 209.4 372.5 287.9 54.2 256.4

Relative SR 17.3% 97.9% 13.5% 10.8% 23.5% 18.5% 23.3% 17.9%

Imposed protocol

x* 202.2 953.5 1811.6 2015.3 1752.4 1671 263 1504.2

Recovery rate % 100.6% 61.0% 101.4% 105.7% 104.2% 92.6% 103.1% 98.1%

Absolute SR 34.1 635 177.9 185.9 169.3 185.2 48.7 196.9

Relative SR 16.9% 66.6% 9.8% 9.2% 9.7% 11.1% 18.5% 13.1%

Upon examining this table, one can see more or less significant improvements depending on the measured analytes. In fact, all of the compounds have favorably benefitted from the non-filtration of the mineral residues (imposed protocol) before analysis, whether in terms of recovery rate or inter-laboratory dispersion.

The elements for which the improvement is most remarkable are :

chromium, the recovery rate of which goes from 45 to 61% with a lower inter-laboratory dispersion (97 to 67%),

manganese, for which the inter-laboratory dispersion goes from 23.5 to 9.7%,

nickel, for which the inter-laboratory dispersion goes from 18.5 to 11.1%.

Despite these observations, and according to the feedback from several laboratories, the implementation of this imposed protocol causes some technical difficulties :

difficulty of homogenizing samples before injection, because there is no sampler equipped with agitation,

significant quantity of suspended matter causing plugging of the capillary columns when the mineralization is not complete,

influence of colloids disrupting the nebulization quality.

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In conclusion, although the establishment of this operating mode leads to improved accuracy of the method, it leads to limited effectiveness and is intended above all for laboratories having partial mineralization and which, as a result, are faced with the above-mentioned difficulties.

Thus, according to the preceding studies (multi-parameter study for the test conducted in 2005 and 2008) and aside from the alkali fusion, which remains complex and expensive, it appears desirable to optimize the mineralization techniques, and more particularly that involving microwaves, a technique primarily used by the laboratories.

For information and after consultation with a microwave oven supplier, it appears that the notion of transparency of the digestion flasks, i.e. the capacity of the containers to allow all of the microwave radiation to pass through to essentially reach the sample, is one element to be taken into consideration. This loss of transparency is all the more pronounced when the container is used by repeated digestions.

In order to limit that risk, a temperature measurement is most often done either through a so-called referring digestion flask in which the pressure and temperature are taken during the entire mineralization process, or through a measurement via an infrared sensor placed under the cap of each digestion flask. Nevertheless, if the temperature taken is erroneous and lower than the actual temperature, the reaction kinetics are affected and the mineralization is then incomplete. It therefore appears crucial to calibrate these probes periodically.

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13.1.11 Test material "11_119507_SO2"


Parameter (mg/liter) Sulfur_dioxide

Value targeted by spiking 96.1


Population Standard Deviation 11.29

CVR (%) 11.32%

CVrep (%) 1.35%

Population 17

SL 11.25

SR 11.43

Sr 2.04



Sulfur_dioxide


96.1

x* 97.96

s* 6.68

uX* 2.03

w* 1.29

SL 6.65

SR 6.78

Sr 1.29



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Sulfur dioxide

x mg/L

sr mg/L

sr %

Z Scores

11207 94.23 0.72 0.76% -0.56

11210 104.15 0.61 0.59% 0.93

11212 100.05 0.24 0.24% 0.31

11222 91.80 0.29 0.32% -0.92

11226 93.78 0.59 0.62% -0.63

11236 91.25 0.79 0.87% -1.00

11249 91.75 0.79 0.87% -0.93

11255 104.20 5.27 5.06% 0.93

11259 93.55 0.13 0.14% -0.66

11262 104.78 4.04 3.85% 1.02

11273 98.60 1.69 1.71% 0.10

11275 106.50 4.07 3.82% 1.28

11279 96.40 0.26 0.27% -0.23

11281 138.45 1.37 0.99% 6.06

11283 101.73 0.96 0.94% 0.56

11288 91.70 1.15 1.26% -0.94

11291 92.88 0.56 0.60% -0.76


Laboratory 11281 obtained a z score greater than |3|. It appears that the results were expressed in mg SO4

2-/L whereas it was asked to express them in mg SO2/L.

Laboratories 11255, 11262 and 11275 were shown, through the Cochran and Mandel k tests, as having a greater intra-laboratory dispersion than the rest of the population.

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13.1.12 Test material "11_119507_NH3"


Parameter (mg/liter) Ammonia



Population Standard Deviation 5.57

CVR (%) 10.1%

CVrep (%) 2.39%

Population 21

SL 5.49

SR 5.82

Sr 1.96


Parameter (mg/liter) Ammonia


x* 56.24

s* 3.56

uX* 0.97

w* 1.26

SL 3.50

SR 3.72

Sr 1.26




DRC-11-119507-08855B Page 70 sur 171


Ammonia

x mg/L

sr mg/L

sr %

Z Scores

11207 58.50 1.33 2.27% 0.64

11210 58.08 0.62 1.07% 0.52

11212 56.88 1.54 2.70% 0.18

11222 56.58 0.22 0.39% 0.10

11227 59.00 1.46 2.47% 0.78

11236 54.50 5.78 10.60% -0.49

11244 52.65 0.17 0.33% -1.01

11249 55.08 0.31 0.56% -0.33

11250 42.63 0.57 1.33% -3.82

11255 39.18 0.64 1.63% -4.79

11259 55.45 0.65 1.16% -0.22

11262 58.03 0.46 0.79% 0.50

11269 57.38 0.44 0.77% 0.32

11273 57.08 0.26 0.46% 0.24

11275 54.38 1.78 3.28% -0.52

11279 48.73 5.28 10.84% -2.11

11281 60.80 0.71 1.17% 1.28

11283 59.35 0.57 0.97% 0.87

11288 54.08 1.92 3.55% -0.61

11291 60.98 0.70 1.15% 1.33

11296 59.53 1.53 2.57% 0.92


Laboratories 11250 and 11255 obtained z scores beyond the admissible value of |3|.


According to the Mandel k test, laboratories 11236 and 11279 have intra-laboratory dispersions that are distinguished as being higher than the rest of the population.

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The relative inter-laboratory dispersion of 6.6% is satisfactory given the diversity of the methods used. In fact, given the INERIS warning regarding the operating mode described in standard NF X 43-303, colorimetry part, the laboratories applied or drew inspiration from other standards or internal operating modes (EN ISO 11732, VDI 3496, methods of air sampling and analysis, distillation/titration).

14 LIST OF ANNEXES

Reference Title Number of

pages

Annex 1 General organization, description of tests and algorithms 9

Annex 2 Data received, averages and repeatability standard

deviations for the laboratories and values dismissed by expert opinion.

41

Annex 3 Statistical distribution curves: Sorted by Average Values

comprised between (x* - 3s*) and (x* + 3s*). 41

Annex 4 Histogram of z scores obtained by each laboratory for all

analytes in a test 9

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ANNEX 1 GENERAL ORGANIZATION, DESCRIPTION OF TESTS AND ALGORITHMS

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GENERAL ORGANIZATION OF THE TEST

The organization can be broken down into five distinct phases:

March 10 to May 06, 2011: administrative phase including contacts, enrollment and transmission of the confidential code;

April 26 to June 22, 2011: Test material preparation and testing phase;

May 16 to June 22, 2011: Shipping, participant analysis, and results collection phase;

June 27 to July 13, 2011: Rapid statistical processing phase of the results, drafting and sending preliminary report;

July to October 2011: Statistical analysis phase according to the procedures described later in the report, drafting of the final report.

Number of laboratories par

Documents

Analytical Proficiency Tests relating to measurements of … · 2011. 12. 23. · ISO 13528 : statistical methods used in aptitude tests by inter-laboratory comparisons – December