REPORT 23/12/2011 N DRC B

Transcription

1 REPORT 23/12/2011 N DRC B 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

2

3 ANALYTICAL INTER-LABORATORY COMPARISONS ORGANIZED FOR THE LABORATORIES INVOLVED IN REGULATORY EMISSIONS CHECKS Campaign : HCl, HF, NH 3, SO 2, total Hg, Heavy metals FINAL REPORT D R C B D E C E M B E R 23, 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 DRC B Page 3 sur 171

4 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» Chronic Risks Division Head of Characterization of the Environment Department Chronic Risks Division Signature DRC B Page 4 sur 171

5 TABLE OF CONTENTS 1 GLOSSARY DEFINITIONS REFERENCE DOCUMENTS CLIENTS ORGANIZATION OF THE INTER-LABORATORY COMPARISONS PRESENTATION OF THE REPORT INTRODUCTION ILT PROGRAM TEST PARTICIPANTS DESCRIPTION OF THE TEST MATERIALS DESCRIPTION AND INSTRUCTIONS Total mercury in permanganate medium Total mercury in dichromate medium Hydrochloric acid Fluorhydric acid Metals (and metalloids) Sulfur dioxide Ammonia SHIPPING HOMOGENEITY AND STABILITY OF THE SAMPLES HOMOGENEITY OF THE MATERIALS STABILITY OF THE TEST MATERIALS RESULTS OF THE INTER-LABORATORY COMPARISON EXPLOITATION OF THE DATA FROM THE TEST MATERIALS General information Presentation of the results Test material "11/119507_Hg_KMnO 4" Test material "11/119507_Hg_K 2Cr 2O 7" Test material "11_119507_HCl" Test material "11_119507_HF_Solution" Test material "11_119507_HF_Poussière" Test material "11/119507_Metaux_solution" Test material "11/119507_Metaux_Poussiére" free protocol Test material "11/119507_Métaux_Poussiére" imposed protocol Test material "11_119507_SO 2" Test material "11_119507_NH 3" LIST OF ANNEXES ANNEX 1 GENERAL ORGANIZATION, DESCRIPTION OF TESTS AND ALGORITHMS General organization of the test Prior checking of the data before launching statistical calculations Materials prepared by the INERIS : Statistical performance tests ANNEX 2 DATA RECEIVED, AVERAGES AND REPEATABILITY STANDARD DEVIATIONS FOR THE LABORATORIES AND VALUES DISMISSED BY EXPERT OPINION Table HCl Water Hydrochloric acid Raw data in mg/liter Table HF Sodium hydroxide (NaOH) Fluorhydric Acid - Raw data in mg/liter Table HF Dust Fluorhydric Acid Raw data in mg/g Table NH3 Sulfuric acid - Ammonia Raw data in mg/liter Table SO2 Hydroperoxide Sulfur dioxide Raw data in mg/liter Table Hg_ K2Cr2O7 Nitric acid - Dichromate (HNO3-K2Cr2O7) - Mercury Raw data in µg/liter Table Hg_KMnO4 Sulfuric acid - Permanganate (H2SO4-KMnO4) - Mercury Raw Data in µg/liter.. 88 Tables 8 to Metals_solution Raw data in µg/liter DRC B Page 5 sur 171

6 Tables 19 to Metals Dust Free protocol Raw Data in µg/g Table 30 à Metals Dust Imposed protocol- Raw Data in µg/g ANNEX 3 STATISTICAL DISTRIBUTION CURVES HF Acide Fluorhydrique HF Poussière - Acide Fluorhydrique NH3 Ammoniac SO2 Dioxyde de soufre Hg K2Cr2O7 - Mercure Hg_KMnO4 - Mercure Métaux_solution (11 figures) Métaux Poussière Protocole libre (11 figures) Métaux Poussière Protocole imposé (11 figures) ANNEX 4 GENERAL ORGANIZATION, DESCRIPTION OF TESTS AND ALGORITHMS Figure 1 : 11/119507_Métaux solution (part 1 to 3) Figure 2: 11/119507_Métaux poussière Free Protocol (part 1 to 3) Figure 3: 11/119507_Métaux poussière Imposed Protocole (part 1 to 2) DRC B Page 6 sur 171

7 1 GLOSSARY ILC ILT Extract QL Test material Matrix CRM ILCA Spiking solution Assigned value 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, 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, Obtained either from extracted water, or from a solvent spiked by all of the sought substances, Quantification limit, Matrix of interest containing the element subject to the interlaboratory comparison, potentially added using a spiking solution. The test matrices are also called, in the referential, LAB-CIL REF 02, comparison substrate, 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, Certified reference material, Inter-laboratory comparison analyzer, Concentration solution with known substance(s) dissolved in a solvent, Value assigned to a particular and recognized size, sometimes by convention, as having a suitable uncertainty at a given usage (ISO 13528). DRC B Page 7 sur 171

8 2 DEFINITIONS CV r CV R CV rep Standard deviation Population standard deviation IC R IC r Average Population average Number of decimals : standard deviation of the x measurements divided by the average of those x measurements by % [(Standard deviation / average) by %], : 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 %, : mean repeatability variation coefficient, average of the CV 4 of the participants, : standard deviation of x measurements, : standard deviation of the measurement averages, : reproducibility confidence interval, : repeatability confidence interval, : average of x measurements, : average of the measurement averages, : 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, S L : inter-laboratory standard deviation, S R : reproducibility standard deviation, S r : repeatability standard deviation, u x* : standard uncertainty u x, U XMRC : 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, X MRC : reference value resulting from the certificate for the certified reference material. DRC B Page 8 sur 171

9 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: DEVE A) 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 : general requirements concerning aptitude tests April 2010, ISO : applications of the statistics Accuracy (correctness and faithfulness) of the results and measurement methods Part 1: general principles and definitions December 1994, ISO : 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 : 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 : statistical methods used in aptitude tests by inter-laboratory comparisons December 2005, ISO : vocabulary and symbols Part 2: Applied statistics December 2006, NF X : application of the statistics Study of the normality of a distribution December DRC B Page 9 sur 171

10 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 INERIS Parc Technologique Alata VERNEUIL- EN-HALATTE First and Last Names Eva LEOZ Sylvain BAILLEUL Sylvain BAILLEUL José GUARNERI ILCA Function ILT Steering ILT coordinator Test material preparer Website management Design of the statistical processing tool 6 PRESENTATION OF THE REPORT This report cancels and replaces the initial provisional report referenced DRC A distributed on 07/11/2011. It is accessible on the site 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 and leads to verification of the proper execution of this requirement during evaluations. DRC B Page 10 sur 171

11 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 (SO 2 ), ammonia (NH 3 ). 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. DRC B Page 11 sur 171

12 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 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 KMnO 4 and 10% of H 2 SO 4 was analyzed, then spiked to make up the test material referenced 11/119507_Hg _KMnO 4. 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 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 Total mercury in dichromate 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 4 % of K 2 Cr 2 O 7 and 20% of HNO 3 was analyzed, then spiked to make up the test material referenced 11/119507_Hg _ K 2 Cr 2 O 7. 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 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. DRC B Page 12 sur 171

13 Hydrochloric acid An absorption solution was prepared according to the stipulations of standard EN 1911, 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 H 2 O 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 Two measurements were requested per bottle provided, or a total of 4 measurements expressed in mg HCl/L with one decimal Fluorhydric acid Solution An absorption solution was prepared according to the stipulations of standard NF X , 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 Dusts Dusts coming from a household waste incineration unit, previously analyzed, were dried and shredded to be spiked with fluorinated salts (NaF, CaF and K 2 SiF 6 ), 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 s 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. DRC B Page 13 sur 171

14 Metals (and metalloids) Solution An absorption solution was prepared according to the stipulations of standard EN 14385, 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 3% of HNO 3 and 1.5% of H 2 O 2 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 Two measurements were requested per bottle provided, or a total of 4 measurements expressed in µg/l with zero decimals 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 Sulfur dioxide An absorption solution was prepared according to the stipulations of standard EN 14791, 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 3% of H 2 O 2 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 SO 2 content level. The analysis of these two samples was to follow the stipulations of standard EN Two measurements were requested per bottle provided, or a total of 4 measurements expressed in mg SO 2 /L with one decimal. DRC B Page 14 sur 171

15 Ammonia An absorption solution was prepared according to the stipulations of standard NF X , then was used as flushing solution on the INERIS test block where combustion gases were generated. This absorption solution made up of H 2 SO 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 NH 3 content level. The s have been done using standard laboratory methods. Two measurements were requested per bottle provided, or a total of 4 measurements expressed in mg NH 3 /L with one decimal. Note: The participants were also alerted to the presence, in standard NF X , 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 and EN ISO 11732). 11 SHIPPING A first shipment was done on May 17, 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, 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. DRC B Page 15 sur 171

16 Test materials Homogeneity of the test materials Homogeneity according to ISO Comments 11/119507_Hg_K 2 Cr 2 O 7 Compliant - 11/119507_Hg_KMnO 4 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 11/119507_Metaux_Poussiére Compliant for 9 of the 11 elements to be assayed Compliant for 10 of the 11 elements to be assayed Co, Pb: Taking inhomogeneity into account in calculating the z score As: Taking inhomogeneity into account in calculating the z score 11/119507_NH 3 Compliant - 11/119507_SO 2 Compliant 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. DRC B Page 16 sur 171

17 The following observations were made: past the 12 th day, a variation in the ammonia content in the vicinity of 3 % was shown.: no laboratory was affected, past the 6 th 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 6 th day to reach 15 % on the 29 th day was shown: no laboratory was affected, dusts: - a variation of the As content level was showed past the 17 th day: no laboratory was affected, - a variation of the Co content level in the vicinity of 10% was shown past the 17 th day: no laboratory was affected, - a variation of the Cu content level in the vicinity of 9% was shown past the 17 th day: no laboratory was affected. 13 RESULTS OF THE INTER-LABORATORY COMPARISON 13.1 EXPLOITATION OF THE DATA FROM THE TEST MATERIALS 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 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. DRC B Page 17 sur 171

18 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 Z i 3 : 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). DRC B Page 18 sur 171

19 Test material "11/119507_Hg_KMnO 4 " Values observed before application of statistical algorithms Parameter (µg/liter) Value targeted by spiking Population Average Population Standard Deviation CV R (%) CV rep (%) Mercury % 5.74% Population 10 S L 3.9 S R 4.0 S r 1.0 Values observed after application of statistical algorithms Parameters (µg/liter) Value targeted by spiking Mercury 12 x* 11.5 s* 1.7 u X* 0.7 w* 1.0 S L 1.6 S R 1.9 S r 1.0 Relative IC R (%) 39.0% Relative IC r (%) 21.1% DRC B Page 19 sur 171

20 Averages, standard deviations and z scores for the laboratories Laboratory Identification x µg/l s r µg/l Mercury s r % Z scores % Not analyzed % Not analyzed Not analyzed % % Not analyzed % < % (-5.22)* Not analyzed < % (-3.24)* % % % Not analyzed Not analyzed Not analyzed ()*: Z score calculated relative to the threshold value rendered. NB: the absolute value is bounded from below. Remarks and comments : Laboratories and 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. DRC B Page 20 sur 171

21 Laboratory was marked as abnormal by the Mandel k test due to its intralaboratory dispersion Test material "11/119507_Hg_K 2 Cr 2 O 7 " Values observed before application of statistical algorithms Parameters (µg/liter) Value targeted by spiking Mercury 12 Population Average 11.3 Population Standard Deviation CV R (%) CV rep (%) % 3.25% Population 14 S L 1.75 S R 1.82 S r 0.51 Values observed after application of statistical algorithms Parameters (µg/liter) Value targeted by spiking Mercury 12 x* 11.3 s* 1.7 u X* 0.6 w* 0.5 S L 1.7 S R 1.7 S r 0.5 Relative IC R (%) 33.6% Relative IC r (%) 10.0% DRC B Page 21 sur 171

22 Averages, standard deviations and z scores for the laboratories Laboratory Identification x µg/l s r µg/l Mercury Not analyzed s r % Z Scores Not analyzed < (-0.71)* Not analyzed Not analyzed ()*: Z score calculated relative to the threshold value rendered. NB: the absolute value is bounded from below. Remarks and comments : Laboratory obtained a z score between 2 and 3. Laboratory rendered a threshold value of 10 µg/l. It was excluded from the robust statistical processing by expert opinion. DRC B Page 22 sur 171

23 Laboratory has a higher intra-laboratory dispersion than the rest of the population Test material "11_119507_HCl" Values observed before application of statistical algorithms Parameter (mg/liter) Value targeted by spiking Hydrochloric_acid 19.3 Population Average Population Standard Deviation CV R (%) CV rep (%) % 1.44% Population 18 S L 0.97 S R 1.06 S r 0.45 Values observed after application of statistical algorithms Parameter (mg/liter) Value targeted by spiking Hydrochloric_acid 19.3 x* s* 1.02 u X* 0.30 w* 0.34 S L 1.01 S R 1.06 S r 0.34 Relative IC R (%) 11.7% Relative IC r (%) 3.72% DRC B Page 23 sur 171

24 Averages, standard deviations and z scores for the laboratories Laboratory Identification x mg/l Hydrochloric_Acid s r mg/l s r % Z Scores % % % % % % % % % % % % % % % % % % 0.33 Remarks and comments : Laboratory has a higher intra-laboratory dispersion than the rest of the population. DRC B Page 24 sur 171

25 Test material "11_119507_HF_Solution" Values observed before application of statistical algorithms Parameter (mg/liter) Value targeted by spiking Fluorhydric_acid 1.92 Population Average 1.89 Population Standard Deviation CV R (%) CV rep (%) % 1.95% Population 17 S L 0.09 S R 0.10 S r 0.05 Values observed after application of statistical algorithms Parameter (mg/liter) Value targeted by spiking Fluorhydric_acid 1.92 x* 1.88 s* 0.10 u X* 0.03 w* 0.04 S L 0.10 S R 0.11 S r 0.04 Relative IC R (%) 12.4% Relative IC r (%) 5.06% DRC B Page 25 sur 171

26 Averages, standard deviations and z scores for the laboratories Laboratory Identification x mg/l Fluorhydric Acid s r mg/l s r % Z Scores % % % % % % % % % % % % % % % % % 0.40 DRC B Page 26 sur 171

27 Remarks and comments : Laboratories and have a higher intra-laboratory dispersion than the other laboratories Test material "11_119507_HF_Poussière" Values observed before application of statistical algorithms Parameter (in mg/g) Value targeted by spiking Fluorinated compounds expressed in HF 15.7 Population Average Population Standard Deviation CV R (%)%) CV rep (%)%) % 7.10% Population 16 S L 5.04 S R 5.12 S r 0.87 Values observed after application of statistical algorithms Parameter (mg/g) Value targeted by spiking Fluorinated compounds expressed in HF 15.7 x* 9.91 s* 4.97 u X* 1.55 w* 0.83 S L S R S r Relative IC R (%) 108.0% Relative IC r (%) 17.8% DRC B Page 27 sur 171

28 Averages, standard deviations and z scores for the laboratories Laboratory Identification x mg/g Fluorinated compounds expressed in HF s r mg/g s r % Z Scores % % % % Not analyzed % % % % % % % % % % % % 0.64 DRC B Page 28 sur 171

29 Remarks and comments : Laboratory 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 Test material "11/119507_Metaux_solution" Values observed before application of statistical algorithms Parameter (µg/liter) Antimony Arsenic Cadmium Chromium Cobalt Copper Manganese Nickel Lead Thallium Vanadium Values targeted by spiking Population Average Population Standard Deviation CV R (%)%) CV rep (%) % 6.72% 21.9% 10.8% 11.3% 10.4% 12.4% 11.4% 3.59% 15.7% 11.0% 0.80% 1.69% 1.34% 1.31% 0.99% 1.10% 1.11% 1.43% 0.72% 1.86% 1.11% Population S L S R S r DRC B Page 29 sur 171

30 Values observed after application of statistical algorithms Parameters (µg/liter) Values targeted by spiking Antimony Arsenic Cadmium Chromium Cobalt Copper Manganese Nickel Lead Thallium Vanadium x* s* u X* w* S L S R S r Relative IC R (%) Relative IC r (%) 10.6% 16.9% 9.28% 9.68% 8.56% 14.6% 7.39% 13.0% 8.88% 12.3% 13.8% 2.00% 4.54% 0.00% 3.31% 2.63% 2.59% 2.69% 3.79% 1.50% 0.00% 2.99% Averages, standard deviations and z scores for the laboratories Laboratory Identification x µg/l s r µg/l Antimony s r % Z Scores x µg/l s r µg/l Arsenic s r % Z Scores % % % % % % % % % % % % % % % % % % % % % % % % % % % % 0.73 DRC B Page 30 sur 171

31 Remarks and comments : Antimony : Laboratory obtained a z score between 2 and 3 and its intra-laboratory dispersion is higher than the rest of the population. DRC B Page 31 sur 171

32 Averages, standard deviations and z scores for the laboratories Laboratory Identification x µg/l s r µg/l Cadmium s r % Z scores x µg/l Chromium s r µg/l s r % Z scores % % % % % % % % % % % % % % % % % % % % % % % % % % % % 0.94 DRC B Page 32 sur 171

33 Remarks and Comments : Cadmium : Laboratories and obtained z scores greater than 3. Laboratory has a higher intra-laboratory dispersion than the rest of the population. Chromium : Laboratory obtained a z score greater than 3. Laboratory has a higher intra-laboratory dispersion than the rest of the population. DRC B Page 33 sur 171

34 Averages, standard deviations and z scores for the laboratories Laboratory Identification x µg/l s r µg/l Cobalt s r % Z scores x µg/l s r µg/l Copper s r % Z scores % % % % % % % % % % % % % % % % % % % % % % % % % % % % DRC B Page 34 sur 171

35 Remarks and Comments : Cobalt : Laboratory obtained a z score greater than 3. Laboratory obtained a z score between 2 and 3. Laboratory has a higher intra-laboratory dispersion than the rest of the population. Copper : Laboratory obtained a z score greater than 3. Laboratory has a higher intra-laboratory dispersion than the rest of the population. DRC B Page 35 sur 171

36 Averages, standard deviations and z scores for the laboratories Laboratory Identification x µg/l Manganese s r µg/l s r % Z Scores x µg/l s r µg/l Nickel s r % Z Scores % % % % % % % % % % % % % % % % % % % % % % % % % % % % 0.60 DRC B Page 36 sur 171

37 Remarks and Comments : Manganese : Laboratory obtained a z score greater than 3. Nickel : Laboratory obtained a z score greater than 3. DRC B Page 37 sur 171

38 Averages, standard deviations and z scores for the laboratories Laboratory Identification x µg/l s r µg/l Lead s r % Z Scores x µg/l s r µg/l Thallium s r % Z Scores % % % % % 0.71 < % (-8.73)* % % % % % % % % % % % % % % % % % % % % % % 0.51 ()* : Z score calculated relative to the threshold value rendered. NB: the absolute value is bounded from below. DRC B Page 38 sur 171

39 Remarks and comments : Lead : Laboratory has a higher intra-laboratory dispersion than the rest of the population. Thallium : Laboratory returned results in the form of a measurement threshold of < 10 µg/l. It was excluded from the robust statistical processing. Laboratory 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 B Page 39 sur 171

40 Averages, standard deviations and z scores for the laboratories Laboratory Identification x µg/l Vanadium s r µg/l s r % Z Scores % % % % % % % % % % % % % % Remarks and comments : Laboratory obtained a z score greater than 3. Conclusion on this test : This histograms shown in annex 4 made it possible to observe the following situation: laboratory must undertake corrective actions for 73% of the analytes measured. DRC B Page 40 sur 171

41 Test material "11/119507_Metaux_Poussiére" free protocol Values observed before application of statistical algorithms Parameter (µg/lg) Value targeted by spiking Population Average Population Standard Deviation CV R (%)%) CV rep (%)%) Antimony Arsenic Cadmium Chromium Cobalt Copper Manganese Nickel Lead Thallium Vanadium * * * % 39.7% 46.2% 83.7% 14.7% 12.3% 24.7% 29.1% 13.8% 38.4% 15.4% 4.6% 3.0% 2.9% 12.2% 4.5% 3.1% 5.1% 3.7% 3.1% 4.6% 3.8% Population S L S R S r * Compounds for which it was not necessary to add a dopant. Values observed after application of statistical algorithms Parameter (µg/g) Value targeted by spiking Antimony Arsenic Cadmium Chromium Cobalt Copper Manganese Nickel Lead Thallium Vanadium * * * x* s* u X* w* S L S R S r Relative IC R (%) Relative IC r (%) 26.9% 74.4% 37.7% 213.3% 29.5% 23.5% 51.3% 40.2% 31.6% 50.7% 39.0% 6.9% 7.3% 9.2% 14.1% 12.8% 6.6% 14.2% 6.5% 6.4% 10.4% 9.1% * Compounds for which it was not necessary to add a dopant. DRC B Page 41 sur 171

42 Laboratory Identification Averages, standard deviations and z scores for the laboratories x µg/g s r µg/g Antimony s r % Z Scores x µg/g s r µg/g Arsenic s r % Z Scores % % % % % % % % % % % % Not analyzed Not analyzed % % % % % % % % % % % % % % 2.98 DRC B Page 42 sur 171

43 Remarks and Comments : Antimony : Laboratories and have higher intra-laboratory dispersions than the rest of the population. Arsenic : Laboratory 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 DRC B Page 43 sur 171

44 Laboratory Identification Averages, standard deviations and z scores for the laboratories x µg/g s r µg/g Cadmium s r % Z Scores x µg/g Chromium s r µg/g s r % Z Scores % % % % % % % % % % % % Not analyzed Not analyzed % % % % % % % % % % % % % % DRC B Page 44 sur 171

45 Remarks and comments : Cadmium : Laboratory obtained a Z score greater than 3. Laboratory has a greater intra-laboratory dispersion than the rest of the population. Chromium : Laboratories and are marked by the Cochran test as having significant intra-laboratory dispersions relative to those of the rest of the population. DRC B Page 45 sur 171

46 Averages, standard deviations and z scores for the laboratories Laboratory Identification x µg/g s r µg/g Cobalt s r % Z Scores x µg/g s r µg/g Copper s r % Z Scores % % % % % % % % % % % % Not analyzed Not analyzed % % % % % % % % % % % % % % 0.23 DRC B Page 46 sur 171

47 Remarks and comments : Cobalt : Laboratories and obtained z scores between 2 and 3. According to the Mandel test, laboratory has a higher intra-laboratory dispersion than the rest of the population. Copper : Laboratory obtained a z score between 2 and 3. Laboratory is marked by the Cochran test as having significant intra-laboratory dispersions relative to the rest of the population. DRC B Page 47 sur 171

48 Averages, standard deviations and z scores for the laboratories Laboratory Identification x µg/g Manganese s r µg/g s r % Z Scores x µg/g s r µg/g Nickel s r % Z Scores % % % % % % % % % % % % Not analyzed Not analyzed % % % % % % % % % % % % % % 0.53 DRC B Page 48 sur 171

49 Remarks and comments : Manganese : Laboratory obtained a z score between 2 and 3. Nickel : Laboratory obtained a z score greater than 3. Laboratories and are marked by the Cochran and Mandel k tests as having higher intra-laboratory dispersions than the rest of the population. DRC B Page 49 sur 171

50 Averages, standard deviations and z scores for the laboratories Laboratory Identification x µg/g s r µg/g Lead s r % Z Scores x µg/g s r µg/g Thallium s r % Z Scores % % % % % % % % % % % % Not analyzed Not analyzed % % % % % % % % % % % % % % 4.17 DRC B Page 50 sur 171

51 Remarks and comments : Lead : Laboratory is marked by the Cochran and Mandel k tests as having a higher intralaboratory dispersion than the rest of the population. Thallium : Laboratories 11212, and obtained z scores greater than 3. Laboratory was excluded from the robust statistical tests by expert opinion for delivering 2 results, 1 in threshold form. DRC B Page 51 sur 171

52 Averages, standard deviations and z scores for the laboratories Laboratory Identification x µg/g Vanadium s r µg/g s r % Z Scores % % % % % % Not analyzed % % % % % % % 0.87 Remarks and comments : Laboratory is marked by the Cochran and Mandel k tests as having a higher intralaboratory dispersion than the rest of the population. Conclusion on this test : 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. Laboratory 11279: 3 analytes out of 11 require monitoring and/or correction. Laboratory 11288: 2 analytes out of 11 require monitoring and/or correction. DRC B Page 52 sur 171

53 Test material "11/119507_Métaux_Poussiére" imposed protocol Values observed before application of statistical algorithms Parameter (µg/g) Value targeted by spiking Population Average Population Standard Deviation CV R (%) CV rep (%) Antimony Arsenic Cadmium Chromium Cobalt Copper Manganese Nickel Lead Thallium Vanadium * * * % 35.6% 56.9% 59.0% 9.5% 8.5% 15.8% 26.3% 12.6% 27.2% 11.2% 3.2% 4.0% 2.7% 17.1% 4.4% 3.6% 4.2% 2.7% 4.1% 8.4% 3.9% Population S L S R S r * Compounds for which it was not necessary to add a dopant. Values observed after application of statistical algorithms Parameter (µg/g) Value targeted by spiking Antimony Arsenic Cadmium Chromium Cobalt Copper Manganese Nickel Lead Thallium Vanadium * * * x* s* u X* w* S L S R S r Relative IC R (%) Relative IC r (%) 17.6% 51.7% 38.1% 150.7% 22.2% 20.9% 21.9% 25.1% 17.5% 41.9% 29.6% 6.3% 12.1% 8.1% 34.2% 12.1% 9.5% 13.5% 7.4% 11.1% 15.8% 10.7% * Compounds for which it was not necessary to add a dopant. DRC B Page 53 sur 171

54 Averages, standard deviations and z scores for the laboratories Laboratory Identification x µg/g s r µg/g Antimony s r % Z Scores x µg/g s r µg/g Arsenic s r % Z Scores % % Not analyzed Not analyzed % % % % % % % % Not analyzed Not analyzed % % Not analyzed Not analyzed % % Not analyzed Not analyzed % % % % % % 4.07 DRC B Page 54 sur 171

55 Remarks and comments : Antimony : Laboratory is marked by the Cochran and Mandel k tests as having a higher intralaboratory dispersion than the rest of the population. Arsenic : Laboratory obtained a z score greater than 3. Laboratories and are marked by the Cochran and Mandel k tests as having a higher intra-laboratory dispersion than the rest of the population. DRC B Page 55 sur 171

56 Averages, standard deviations and z scores for the laboratories Laboratory Identification x µg/g s r µg/g Cadmium s r % Z Scores x µg/g Chromium s r µg/g s r % Z Scores % % Not analyzed Not analyzed % % % % % % % % Not analyzed Not analyzed % % Not analyzed Not analyzed % % Not analyzed Not analyzed % % % % % % DRC B Page 56 sur 171

57 Remarks and comments : Cadmium : Laboratory has a z score greater than 3. Chromium : Laboratories 11210, and are marked by the Cochran test as having a higher intra-laboratory dispersion than the rest of the population. DRC B Page 57 sur 171

58 Averages, standard deviations and z scores for the laboratories Laboratory Identification x µg/g s r µg/g Cobalt s r % Z Scores x µg/g s r µg/g Copper s r % Z Scores % % Not analyzed Not analyzed % % % % % % % % Not analyzed Not analyzed % % Not analyzed Not analyzed % % Not analyzed Not analyzed % % % % % % DRC B Page 58 sur 171

59 Remarks and comments : Cobalt : Laboratory obtained a Z score between 2 and 3. Laboratory is marked by the Mandel k test as having a higher intra-laboratory dispersion than the rest of the population. Copper : Laboratories and are marked by the Cochran test as having a higher intralaboratory dispersion than the rest of the population. DRC B Page 59 sur 171

60 Averages, standard deviations and z scores for the laboratories Laboratory Identification x µg/g Manganese s r µg/g s r % Z Scores x µg/g s r µg/g Nickel s r % Z Scores % % Not analyzed Not analyzed % % % % % % % % Not analyzed Not analyzed % % Not analyzed Not analyzed % % Not analyzed Not analyzed % % % % % % 0.25 DRC B Page 60 sur 171

61 Remarks and comments : Manganese : Laboratory obtained a Z score between 2 and 3. Laboratory obtained a z score greater than 3. Laboratory is marked by the Mandel k test as having a higher intra-laboratory dispersion than the rest of the population. Nickel : Laboratory obtained a z score greater than 3. Laboratory is marked by the Mandel k test as having a higher intra-laboratory dispersion than the rest of the population. DRC B Page 61 sur 171

62 Averages, standard deviations and z scores for the laboratories Laboratory Identification x µg/g s r µg/g Lead s r % Z Scores x µg/g s r µg/g Thallium s r % Z Scores % % Not analyzed Not analyzed % % % % % % % % Not analyzed Not analyzed % % Not analyzed % % Not analyzed Not analyzed % % % % % % 3.20 DRC B Page 62 sur 171

63 Remarks and comments : Lead : Laboratories and obtained z scores greater than 3. Laboratories 11210, and are marked by the Cochran test as having a higher intra-laboratory dispersion than the rest of the population. Thallium : Laboratory obtained z scores greater than 3. Laboratory obtained a Z score between 2 and 3. Laboratory is marked by the Cochran and Mandel k tests as having a higher intralaboratory dispersion than the rest of the population. DRC B Page 63 sur 171

64 Averages, standard deviations and z scores for the laboratories Laboratory Identification x µg/g Vanadium s r µg/g s r % Z Scores % Not analyzed % % % % Not analyzed % Not analyzed % Not analyzed % % % 0.80 Remarks and comments : Laboratory is marked by the Cochran and Mandel k tests as having a higher intralaboratory dispersion than the rest of the population. DRC B Page 64 sur 171

65 Conclusion on this test : 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 (µg/g) Values targeted by spiking Cadmium Chromium Cobalt Copper Manganese Nickel Thallium Vanadium Free protocol x* Recovery rate % 94.6% 45.3% 97.0% 101.9% 94.2% 86.4% 91.4% 93.5% Absolute S R Relative S R 17.3% 97.9% 13.5% 10.8% 23.5% 18.5% 23.3% 17.9% Imposed protocol x* Recovery rate % 100.6% 61.0% 101.4% 105.7% 104.2% 92.6% 103.1% 98.1% Absolute S R Relative S R 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 interlaboratory 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. DRC B Page 65 sur 171

66 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. DRC B Page 66 sur 171

67 Test material "11_119507_SO 2 " Values observed before application of statistical algorithms Parameter (mg/liter) Value targeted by spiking Sulfur_dioxide 96.1 Population Average Population Standard Deviation CV R (%) CV rep (%) % 1.35% Population 17 S L S R S r 2.04 Values observed after application of statistical algorithms Parameter (mg/liter) Value targeted by spiking Sulfur_dioxide 96.1 x* s* 6.68 u X* 2.03 w* 1.29 S L 6.65 S R 6.78 S r 1.29 Relative IC R (%) 14.7% Relative IC r (%) 2.79% DRC B Page 67 sur 171

68 Averages, standard deviations and z scores for the laboratories Laboratory Identification x mg/l Sulfur dioxide s r mg/l s r % Z Scores % % % % % % % % % % % % % % % % % Remarks and comments : Laboratory obtained a z score greater than 3. It appears that the results were expressed in mg SO 4 2- /L whereas it was asked to express them in mg SO 2 /L. Laboratories 11255, and were shown, through the Cochran and Mandel k tests, as having a greater intra-laboratory dispersion than the rest of the population. DRC B Page 68 sur 171

69 Test material "11_119507_NH 3 " Values observed before application of statistical algorithms Parameter (mg/liter) Value targeted by spiking Ammonia 57.6 Population Average Population Standard Deviation CV R (%) CV rep (%) % 2.39% Population 21 S L 5.49 S R 5.82 S r 1.96 Values observed after application of statistical algorithms Parameter (mg/liter) Value targeted by spiking Ammonia 57.6 x* s* 3.56 u X* 0.97 w* 1.26 S L 3.50 S R 3.72 S r 1.26 Relative IC R (%) 13.8% Relative IC r (%) 4.66% Averages, standard deviations and z scores for the laboratories DRC B Page 69 sur 171

70 Laboratory Identification x mg/l s r mg/l Ammonia s r % Z Scores % % % % % % % % % % % % % % % % % % % % % 0.92 Remarks and comments : Laboratories and obtained z scores beyond the admissible value of 3. Laboratory obtained a z score between 2 and 3. According to the Mandel k test, laboratories and have intra-laboratory dispersions that are distinguished as being higher than the rest of the population. DRC B Page 70 sur 171

71 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 , 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 Annex 3 Data received, averages and repeatability standard deviations for the laboratories and values dismissed by expert opinion. Statistical distribution curves: Sorted by Average Values comprised between (x * - 3s * ) and (x * + 3s * ) Annex 4 Histogram of z scores obtained by each laboratory for all analytes in a test 9 DRC B Page 71 sur 171

72

73 ANNEX 1 GENERAL ORGANIZATION, DESCRIPTION OF TESTS AND ALGORITHMS DRC B Page 72 sur 171

74

75 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 participating in the test A minimum number of 10 participants with 4 results per participant is required, as that number, according to standard NF ISO ( 6.3.3), makes it possible to obtain a low level of uncertainty in estimates of the repeatability and reproducibility standard deviations. The number of results can be modified during the development of the campaign plan depending on the needs of the inter-laboratory tests. NB: Non-compliance with this minimum number of participants can lead to postponing the inter-laboratory tests to a later time so that the minimum number is reached. Prior checks on the test materials Before the distribution of the test materials, the organizer must demonstrate that the material being tested is stable and homogenous enough. In certain cases, the homogeneity tests cannot be done before distribution for technical, historical and logistical reasons 1. In our case, the homogeneity and stability monitoring is done during the analysis by the laboratories due to a distance of several years on this type of substances and matrices. These two parameters were verified based on the assessment criteria of Annex B of standard NF ISO The homogeneity of the material is verified during its distribution, i.e. from the analytical results obtained on D+1. The formulas are those cited in standard ISO 13528, with: - average standard deviation of the determinations on D+1, S x, - intra-sample standard deviation S w, - inter-sample standard deviation S S. 1 Organizers of inter-laboratory comparisons, requirements for Accreditation Document LAB-CIL REF02 from the COFRAC. DRC B Page 73 sur 171

76 - S ( xt X )²/( g 1) x, with : x t = the determination values, X = average of the g x t, g = number of samples subject to homogeneity verification - Sw wt² / 2g, with w t = x t1 x t2, - S S Sx² ( Sw² / 2) After statistical processing of the data sent by the participants, the coordinator introduces, into each spreadsheet, the average m and standard deviation assessing the aptitude of the population. values for For each parameter, the coordinator examines the homogeneity criterion. The test material will be considered to have a satisfactory homogeneity if and only if S s / 0.3. In the case where S s ² is negative, then the ratio S X / is examined. With : descriptor of the population variability, robust standard deviation or preestablished value. In the event of an inter-laboratory test material that cannot be considered homogenous (S s / > 0.3), the coordinator reserves the right, pursuant to chapter B2 c of standard NF ISO 13528, to include the inter-sample standard deviation in the standard deviation of the aptitude tests 2 2 s n S with - Inter-sample standard deviation S S. - : standard deviation of the aptitude assessment - n: new standard deviation of the aptitude assessment taking into account the inter-sample dispersion. The stability of the material is verified at a frequency defined in cooperation with the advisory group, depending on each team s planning possibilities. Calculation of the averages : - average of the determinations on D+1, X, - average of the determinations on D+X, Y. The assessment starts with a comparison of the values obtained at moment D+1 to the values obtained at moment D+X while taking the intra-laboratory dispersion into account. If the average values overlap with plus or minus two standard deviations, then the stability is verified. If an instability is detected, then the coordinator examines the stability criterion using the assessment criterion of standard NF ISO according to the following procedure. DRC B Page 74 sur 171

77 After the statistical processing of the data sent by the participants, the coordinator introduces the average m and standard deviation σ values into each spreadsheet for the population aptitude assessment. For each parameter, the coordinator examines the stability criterion by using the assessment criterion of standard ISO : the general average of the determinations obtained during verification of the homogeneity (at D+1, X) is compared to the general average of the results obtained during verification of the stability (on D+X, Y). The samples are considered stable enough if X Y / or, if necessary, X Y / n Otherwise, the coordinator examines the results with the concerned technical experts and the statistician expert in order to decide how to continue the campaign for the concerned parameter or family of parameters. The statistical processing considered to analyze the data obtained from the ILT is done from the recommendations of standards NF ISO The confirmation of the verification of the hypotheses formulated in the part (NF ISO ) make it possible to use other parts to analyze the data. PRIOR CHECKING OF THE DATA BEFORE LAUNCHING STATISTICAL CALCULATIONS Study of the raw data All of the raw data collected at the end of an ILT first undergoes an expert opinion step in order to eliminate, if necessary, certain values during the calculation of the assigned value. This is in particular the case for : values returned below the quantification limit ; values entered equal to 0 ; values for which a dilution or retrieval error in the imposed unit is shown (for example by a factor of 1000). Methodology : Retrieval of 4 values Data received Data taken into account 1 st case C, C, C, <LQ C, C, C 2 nd case C, C, <LQ, <LQ C, C 3 rd case C, <LQ, C, <LQ C, C 4 th case C, <LQ, <LQ, <LQ / DRC B Page 75 sur 171

78 Retrieval of 2 values Data received Data taken into account 1 st case C, <LQ / 2 nd case <LQ, <LQ / The abnormal nature of these values may be viewed by Q-Q plot. These exclusions are presented for approval to the experts from the Advisory Group and drawn in the interlaboratory test report. Study of the data distribution The coordinator verifies, before launching the statistical processing, that all of the data follows a normal distribution. The method used to study the data distribution in order to show unexpected sources of variability is the Q-Q plot. Abnormal value and coherence tests Standard ISO ( 6.1.4), making it possible to determine the repeatability and reproducibility of a measuring method, recommends applying the abnormal value test (Grubbs test and Cochran test) and coherence test (Mandel h and k statistics) to the data, so that the participants and organizer, in a procedure to improve the implementation of the analysis methods, look, in particular based on the comments provided by the laboratories in the results form or the observations, for the origin of the abnormal nature of the values detected as incoherent (for example computation error, or conversion error, etc.). All of the abnormal value and coherence tests are outlined in the inter-laboratory test report. Cochran test The Cochran test consists of comparing the variability within each participant to that of the entire population. The Cochran test is carried out iteratively until no more abnormal or questionable values are detected. Upon each iteration, the population is reduced by one individual. Grubbs test To look for an abnormal observation, the simple test is used. This test consists of comparing each extreme value (maximum average X max or minimum average X min ) to the average of the entire population. The Grubbs test is carried out iteratively, alternatively at the upper extreme and lower extreme of the population, until no more abnormal or questionable values are detected. Upon each iteration, the population is reduced by one individual. If the simple test thus carried out does not detect any abnormal values, the double Grubbs test is applied. Coherence tests. The h and k coherence tests lead to a graphic representation by histogram of the data and make it possible to detect the incoherent data visually. DRC B Page 76 sur 171

79 MATERIALS PREPARED BY THE INERIS : The methodology used to determine the assigned value, its associated uncertainty and the standard deviation for the test materials prepared by the INERIS is presented below: Principle of the robust analysis of the tests The basic method for determining the repeatability and reproducibility of a measuring method described in standard ISO requires the use of tests of abnormal values (Cochran and Grubbs tests) in order to identify the data that must be excluded from the statistical calculations. However, in practice, in applying abnormal value tests, the data analyst may be called upon to exercise judgment to decide what data must actually be excluded (for example if the tests detect an abnormal value and several questionable values for a laboratory: partial or elimination or elimination of all of its data?). The data analyst s decision may therefore, in certain cases, have a substantial influence on the calculated values of the repeatability and reproducibility standard deviations, as well as the calculation of the average used as reference value and to assess the performance (laboratory score). The interest of the robust analysis of the data as described in standard ISO , relative to the basic analysis, is to calculate the assigned value and other statistical parameters from all of the data, including that which may be judged suspicious by expert statement or an abnormal value test: the applied data processing minimizes the weight of suspicious values, i.e. extreme values, so that the latter do not have a significant impact on the value of that assigned value. Thus, the calculations of the assigned value (reference value), confidence intervals and performance statistics are not affected by the data analyst s judgment. The participants results are processed completely impartially and transparently. Determination of the assigned value The assigned value for each parameter subject to an inter-comparison test is determined according to standards ISO and ISO The assigned value is taken to be equal to the robust average of the results provided by the participants in the inter-comparison test (cf. Annex C of standard ISO 13528). Even if abnormal values are detected by coherence and abnormal value tests, they are not excluded to calculate the robust average. The robust average x * is calculated by applying algorithm A. The iterations are repeated until the convergence is ensured, i.e. the 3 rd rounded decimal place of the robust average and of the robust standard deviation no longer changes. The average x i of each of the p participants is calculated, then the p averages are ranked by increasing order. - The initial value of the robust average x * is equal to the median of the p averages. x * median of ( i 1,2,... p ) x i The initial value of the robust standard deviation s * is equal to: DRC B Page 77 sur 171

80 s * median of x i x * ( i 1,2,... p ) - The value of x * is updated as follows: 1.5 s * For each value x i, one calculates: x * if x i* x * if xi x * if not i x i x * - x * The new robust average value is equal to: x* p i 1 x i p * The new robust standard deviation is equal to: s* p i 1 ( x i p x 1 *)² Determination of the uncertainty associated with the assigned value (robust method) The uncertainty of the assigned value u x* is estimated by: u x 1.25 s* / * p When u 0.3 ˆ x*, chapter 4.2 of standard NF ISO recommends neglecting the uncertainty of the assigned value and not including it in the interpretation of the results of the aptitude test, i.e. in the statistical performance test. For u 0.3 ˆ i.e. 0.3 *, the number of participants in the inter-laboratory x* u x * s comparisons must be p 16. The tests must be organized with at least 10 participants. If the number of participants is between 10 and 15, it is therefore appropriate to take the uncertainty of the assigned value into account in the interpretation of the results of the statistical performance test. Determination of the standard deviation for the aptitude ˆ assessment Among the 5 methods proposed by standard NF ISO to calculate the standard deviation ˆ for the aptitude assessment (i.e. to assess the laboratories performance), the determination from the participants results is used. When the inter-laboratory test medium does not correspond to a Certified Reference Material, the standard deviation for assessing the aptitude ˆ is determined from the participants results. It is taken to be equal to the robust standard deviation * s estimated by applying Algorithm A, as previously described. DRC B Page 78 sur 171

81 Particular case : Non-homogenous inter-comparison support When the homogeneity tests of the test materials find a lack of homogeneity, the coordinator takes the inter-sample standard deviation into account in the standard deviation of the aptitude tests, so as not to impute to the laboratories, during the performance test, the bias related to the variability of the distributed test materials. The standard deviation for assessing the aptitude is recalculated as follows: ^ ^ 2 1 S where 2 s ^ ^ 1 S s : : standard deviation for assessing the recalculated aptitude; : standard deviation for assessing the aptitude, calculated by the robust analysis; the inter-sample standard deviation of the distributed test materials. STATISTICAL PERFORMANCE TESTS The laboratories performance is assessed using the z score. Z score The Z score is calculated as follows: xi - Case of a test material prepared by the INERIS: zi ^ * x Where: ^ is the estimate of the standard deviation for assessing the aptitude calculated from algorithm A, x i is the average concentration measured by the laboratory i, X MRC and x* correspond to the considered assigned value. If the standard uncertainty associated with the assigned value is non-negligible : In the case of a certified reference material: If u 0.3, In the case of a test material prepared by the INERIS: If p<16 Then the standard uncertainty associated with the assigned value is taken into account and the z score is calculated as follows: x i MRC z i or ˆ ² X u X MRC ² z i ˆ x i 2 x* u 2 x* X MRC ^ DRC B Page 79 sur 171

82 If the test material prepared by the INERIS is not homogenous : The inter-sample standard uncertainty z i x ˆ i 2 x * S 2 s S s should be taken into account : NB: If necessary, both the standard uncertainty associated with the assigned value and the inter-sample standard uncertainty are taken into account. Assessment of each laboratory s performance : A laboratory having a z score greater than 3.0 or less than -3.0 causes an action signal. A z score greater than 2.0 or less than -2.0 causes a warning signal ( standard ISO 13528). DRC B Page 80 sur 171

83 ANNEX 2 DATA RECEIVED, AVERAGES AND REPEATABILITY STANDARD DEVIATIONS FOR THE LABORATORIES AND VALUES DISMISSED BY EXPERT OPINION For each studied matrix, all of the participants results are presented, including the values dismissed from the statistical calculations (expert opinion). For the latter, the reason those values are not taken into account is specified. DRC B Page 81 sur 171

84

85 TABLE HCL WATER HYDROCHLORIC ACID RAW DATA IN MG/LITER Laboratory Identification Beginning of analysis End of analysis Standard Average of measurements Standard Deviation of s ,8 18,7 18,5 18,6 27/05/ /05/2011 NF EN ,650 0,1291 0,7% OK CVrep by % EXPERT opinion Expert Opinion Comments ,5 21,5 20,9 20,7 10/06/ /06/2011 NF EN ,150 0,4123 1,9% OK ,5 18,5 18,4 18,5 31/05/ /05/2011 NF EN ,475 0,0500 0,3% OK ,6 19,7 19,6 19,5 06/06/ /06/2011 NF EN ,600 0,0816 0,4% OK ,3 19,2 19,3 19,2 06/06/ /06/2011 NF EN ,250 0,0577 0,3% OK ,8 19,1 18,9 19,8 10/06/ /06/2011 NF EN ,400 0,4690 2,4% OK ,2 19,2 19,2 19,2 08/06/ /06/2011 NF EN ,200 0,0000 0,0% OK ,7 19,5 19,5 19,6 09/06/ /06/2011 NF EN ,575 0,0957 0,5% OK ,5 22,0 19,5 22,1 27/05/ /05/2011 NF EN ,775 1,4728 7,1% OK ,4 19,4 19,4 19,4 15/06/ /06/2011 Autre, à préciser (Observations) 19,400 0,0000 0,0% OK ,6 17,8 18,5 18,7 01/06/ /06/2011 NF EN ,150 0,5323 2,9% OK ,4 18,6 18,0 17,3 10/06/ /06/2011 NF EN ,075 0,5737 3,2% OK ,5 18,3 18,4 18,4 31/05/ /06/2011 NF EN ,400 0,0816 0,4% OK ,7 19,9 19,7 19,8 27/05/ /06/2011 NF EN ,775 0,0957 0,5% OK ,7 18,4 17,7 18,1 10/06/ /06/2011 NF EN ,975 0,3403 1,9% OK ,5 20,8 21,8 21,0 01/06/ /06/2011 NF EN ,275 0,4573 2,1% OK ,0 18,6 18,8 19,1 30/05/ /05/2011 NF EN ,875 0,2217 1,2% OK ,6 19,6 19,6 19,6 07/06/ /06/2011 NF EN ,600 0,0000 0,0% OK DRC B Page 82 sur 171

86 TABLE HF SODIUM HYDROXIDE (NAOH) FLUORHYDRIC ACID - RAW DATA IN MG/LITER Laboratory Identification Beginning of analysis End of analysis Standard Average of measurements Standard Deviation of s CVrep by % EXPERT opinion Expert Opinion Comments ,77 1,80 1,82 1,83 14/06/ /06/2011 NF X Décembre ,805 0,0265 1,5% OK ,94 1,79 1,99 1,80 10/06/ /06/2011 NF X Décembre ,880 0,1003 5,3% OK ,74 1,76 1,74 1,74 31/05/ /05/2011 NF X Décembre ,745 0,0100 0,6% OK ,88 1,94 1,96 1,93 07/06/ /06/2011 NF X Décembre ,928 0,0340 1,8% OK ,69 1,81 1,80 1,69 06/06/ /06/2011 NF X Décembre ,748 0,0665 3,8% OK ,89 1,84 1,86 1,88 10/06/ /06/2011 NF X Décembre ,868 0,0222 1,2% OK ,85 1,84 1,80 1,81 07/06/ /06/2011 NF X Décembre ,825 0,0238 1,3% OK ,92 1,97 1,97 1,92 01/06/ /06/2011 NF X Décembre ,945 0,0289 1,5% OK ,87 2,03 2,03 2,09 27/05/ /06/2011 NF X Décembre ,005 0,0943 4,7% OK ,81 1,82 1,88 1,82 01/06/ /06/2011 NF X Décembre ,833 0,0320 1,7% OK ,91 1,82 1,88 1,92 10/06/ /06/2011 NF X Décembre ,883 0,0450 2,4% OK ,92 1,92 1,90 1,91 31/05/ /05/2011 NF X Décembre ,913 0,0096 0,5% OK ,98 1,98 1,98 1,99 27/05/ /06/2011 NF X Décembre ,983 0,0050 0,3% OK ,92 1,94 1,99 1,99 01/06/ /06/2011 NF X Décembre ,960 0,0356 1,8% OK ,74 1,75 1,75 1,75 06/06/ /06/2011 NF X Décembre ,748 0,0050 0,3% OK ,17 2,06 2,06 2,02 30/05/ /06/2011 NF X Décembre ,078 0,0645 3,1% OK ,90 1,90 1,95 1,95 16/06/ /06/2011 NF X Décembre ,925 0,0289 1,5% OK DRC B Page 83 sur 171

87 TABLE HF DUST FLUORHYDRIC ACID RAW DATA IN MG/G Laboratory Identification Beginning of analysis End of analysis Standard Average of measurements Standard Deviation of s ,0 13,3 15,2 14,6 14/06/ /06/2011 NF X Décembre ,025 1,0468 7,5% OK CVrep by % EXPERT opinion Expert Opinion Comments ,1 22,5 19,7 24,2 09/06/ /06/2011 NF X Décembre ,875 1,9259 8,8% OK ,3 9,1 9,0 8,8 06/06/ /06/2011 NF X Décembre ,300 0,6782 7,3% OK ,0 12,1 14,1 12,8 07/06/ /06/2011 NF X Décembre ,750 0,9678 7,6% OK Faites votre choix Non analysé Non analysé Non analysé Exclus ,0 6,3 6,4 6,3 20/06/ /06/2011 NF X Décembre ,250 0,1732 2,8% OK ,6 11,9 11,6 11,9 17/06/ /06/2011 NF X Décembre ,000 0,4243 3,5% OK ,5 11,7 11,7 11,9 31/05/ /05/2011 NF X Décembre ,700 0,1633 1,4% OK ,7 4,6 4,3 4,3 27/05/ /06/2011 NF X Décembre ,475 0,2062 4,6% OK ,3 3,6 3,8 3,8 08/06/ /06/2011 NF X Décembre ,625 0,2363 6,5% OK ,9 12,9 15,1 12,6 14/06/ /06/2011 NF X Décembre ,125 1, ,5% OK ,5 13,4 13,8 13,3 30/05/ /06/2011 NF X Décembre ,250 0,5447 4,1% OK ,9 1,0 1,1 15/06/ /06/2011 NF X Décembre ,000 0, ,0% OK ,9 8,7 9,5 9,6 01/06/ /06/2011 NF X Décembre ,425 0,5123 5,4% OK ,3 9,3 9,9 9,9 14/06/ /06/2011 NF X Décembre ,600 0,3464 3,6% OK ,6 6,5 3,7 5,9 30/05/ /06/2011 NF X Décembre ,175 1, ,4% OK ,7 12,4 13,0 13,3 16/06/ /06/2011 Autre, à préciser (Observations) 13,100 0,5477 4,2% OK DRC B Page 84 sur 171

88 TABLE NH3 SULFURIC ACID - AMMONIA RAW DATA IN MG/LITER Laboratory Identification Beginning of analysis End of analysis Standard Average of measurements Standard Deviation of s ,6 58,3 59,4 56,7 27/05/ /05/2011 NF X ,500 1,3292 2,3% OK CVrep by % EXPERT opinion Expert Opinion Comments ,9 58,1 57,4 58,9 06/06/ /06/2011 Autre, à préciser (Observations) 58,075 0,6238 1,1% OK ,1 54,7 57,8 56,9 30/05/ /05/2011 Autre, à préciser (Observations) 56,875 1,5370 2,7% OK ,3 56,8 56,7 56,5 06/06/ /06/2011 NF X ,575 0,2217 0,4% OK ,7 60,0 57,8 60,5 31/05/ /06/2011 Autre, à préciser (Observations) 59,000 1,4583 2,5% OK ,8 59,2 49,6 49,4 10/06/ /06/2011 NF X ,500 5, ,6% OK ,5 52,5 52,8 52,8 06/06/ /06/2011 Autre, à préciser (Observations) 52,650 0,1732 0,3% OK ,8 54,9 55,5 55,1 08/06/ /06/2011 NF X ,075 0,3096 0,6% OK ,1 42,8 42,8 41,8 31/05/ /05/2011 NF X ,625 0,5679 1,3% OK ,0 39,3 38,9 38,5 27/05/ /06/2011 Autre, à préciser (Observations) 39,175 0,6397 1,6% OK ,8 55,0 56,1 55,9 07/06/ /06/2011 Autre, à préciser (Observations) 55,450 0,6455 1,2% OK ,6 57,9 58,1 57,5 31/05/ /05/2011 NF X ,025 0,4573 0,8% OK ,7 56,9 57,8 57,1 07/06/ /06/2011 Autre, à préciser (Observations) 57,375 0,4425 0,8% OK ,1 56,7 57,3 57,2 21/06/ /06/2011 NF X ,075 0,2630 0,5% OK ,2 56,5 52,9 52,9 01/06/ /06/2011 NF X ,375 1,7840 3,3% OK ,2 44,1 53,3 53,3 01/06/ /06/2011 NF X ,725 5, ,8% OK ,2 60,8 59,8 61,4 08/06/ /06/2011 NF X ,800 0,7118 1,2% OK ,1 59,5 58,9 58,9 01/06/ /06/2011 NF X ,350 0,5745 1,0% OK ,1 56,7 53,6 53,9 30/05/ /05/2011 NF X ,075 1,9190 3,5% OK ,9 60,2 60,9 61,9 31/05/ /05/2011 NF X ,975 0,6994 1,1% OK ,3 57,9 61,6 59,3 30/05/ /05/2011 Autre, à préciser (Observations) 59,525 1,5327 2,6% OK DRC B Page 85 sur 171

89 TABLE SO2 HYDROPEROXIDE SULFUR DIOXIDE RAW DATA IN MG/LITER Laboratory Identification Beginning of analysis End of analysis Standard Average of measurements Standard Deviation of s ,1 94,5 93,8 93,5 27/05/ /05/2011 NF EN ,225 0,7182 0,8% OK CVrep by % EXPERT opinion Expert Opinion Comments ,7 103,9 104,6 103,4 10/06/ /06/2011 NF EN ,150 0,6137 0,6% OK ,2 99,7 100,2 100,1 31/05/ /05/2011 NF EN ,050 0,2380 0,2% OK ,9 92,1 91,4 91,8 06/06/ /06/2011 NF EN ,800 0,2944 0,3% OK ,0 93,3 94,5 93,3 06/06/ /06/2011 NF EN ,775 0,5852 0,6% OK ,6 90,9 92,4 91,1 10/06/ /06/2011 NF EN ,250 0,7937 0,9% OK ,8 91,9 91,3 91,0 08/06/ /06/2011 NF EN ,750 0,7937 0,9% OK ,1 101,5 101,4 101,8 26/05/ /05/2011 NF EN ,200 5,2694 5,1% OK ,5 93,4 93,7 93,6 09/06/ /06/2011 Autre, à préciser (Observations) 93,550 0,1291 0,1% OK ,4 109,8 100,2 105,7 27/05/ /06/2011 NF EN ,775 4,0385 3,9% OK ,2 99,3 100,1 98,8 10/06/ /06/2011 NF EN ,600 1,6872 1,7% OK ,3 109,7 103,5 102,5 31/05/ /06/2011 NF EN ,500 4,0694 3,8% OK ,1 96,3 96,7 96,5 27/05/ /06/2011 NF EN ,400 0,2582 0,3% OK ,2 139,1 139,1 136,4 10/06/ /06/2011 NF EN ,450 1,3675 1,0% OK ,3 102,0 102,3 100,3 01/06/ /06/2011 NF EN ,725 0,9605 0,9% OK ,7 90,7 92,7 92,7 30/05/ /05/2011 NF EN ,700 1,1547 1,3% OK ,4 93,1 92,9 92,1 07/06/ /06/2011 NF EN ,875 0,5560 0,6% OK DRC B Page 86 sur 171

90 TABLE HG_ K2CR2O7 NITRIC ACID - DICHROMATE (HNO3-K2CR2O7) - MERCURY RAW DATA IN µg/liter Laboratory Identification Beginning of analysis End of analysis Standard Average of measurements Standard Deviation of s CVrep by % EXPERT opinion Expert Opinion Comments Faites votre choix Non analysé Non analysé Non analysé Exclus /05/ /05/2011 NF EN ,500 1, ,3% OK Faites votre choix Non analysé Non analysé Non analysé Exclus /06/ /06/2011 NF EN NF EN ,750 0,5000 4,3% OK /06/ /06/2011 NF EN ,000 0,0000 0,0% Exclus Valeur rendue < /06/ /06/2011 NF EN ,250 0,5000 5,4% OK /06/ /06/2011 NF EN NF EN ,750 0,5000 5,1% OK /05/ /06/2011 Autre, à préciser (Observations) 12,000 0,0000 0,0% OK /05/ /05/2011 NF EN ,500 0,5774 5,0% OK /06/ /06/2011 NF EN ,000 0,0000 0,0% OK /06/ /06/2011 NF EN ,500 0,5774 5,5% OK /06/ /06/2011 NF EN ,750 0,5000 3,2% OK Faites votre choix Non analysé Non analysé Non analysé Exclus Faites votre choix Non analysé Non analysé Non analysé Exclus /06/ /06/2011 NF EN ,250 0,5000 4,4% OK /05/ /05/2011 NF EN ,000 0,0000 0,0% OK /05/ /06/2011 NF EN ,000 0,0000 0,0% OK /05/ /05/2011 NF EN NF EN ,250 0,5000 4,1% OK DRC B Page 87 sur 171

91 TABLE HG_KMNO4 SULFURIC ACID - PERMANGANATE (H2SO4-KMNO4) - MERCURY RAW DATA IN µg/liter Laboratory Identification Beginning of analysis End of analysis Standard Average of measurements Standard Deviation of s CVrep by % EXPERT opinion Expert Opinion Comments /06/ /06/2011 NF EN ,500 1, ,8% OK Faites votre choix Non analysé Non analysé Non analysé Exclus /06/ /06/2011 NF EN ,250 1, ,6% OK Faites votre choix Non analysé Non analysé Non analysé Exclus Faites votre choix Non analysé Non analysé Non analysé Exclus /06/ /06/2011 NF EN ,250 2, ,7% OK /06/ /06/2011 NF EN NF EN ,000 0,0000 0,0% OK Faites votre choix Non analysé Non analysé Non analysé Exclus /05/ /05/2011 NF EN ,500 0,5774 5,5% OK /06/ /06/2011 NF EN ,000 0,0000 0,0% Exclus Valeur rendue < Faites votre choix Non analysé Non analysé Non analysé Exclus /06/ /06/2011 NF EN ,000 0,0000 0,0% Exclus Valeur rendue < /05/ /05/2011 NF EN ,500 0,5774 4,6% OK /06/ /06/2011 NF EN ,000 0,0000 0,0% OK /06/ /06/2011 NF EN ,750 0,5000 4,3% OK Faites votre choix Non analysé Non analysé Non analysé Exclus Faites votre choix Non analysé Non analysé Non analysé Exclus Faites votre choix Non analysé Non analysé Non analysé Exclus DRC B Page 88 sur 171

92 TABLES 8 TO METALS_SOLUTION RAW DATA IN µg/liter Table Metals_solution Nitric acid hydroperoxide Antimony Raw Data in µg/liter Laboratory Identification Beginning of analysis End of analysis Standard Average of measurements Standard Deviation of s CVrep by % EXPERT opinion Expert Opinion Comments /06/ /06/2011 NF EN ,250 2,2174 0,5% OK /05/ /05/2011 NF EN ,250 1,5000 0,3% OK /06/ /06/2011 Autre, à préciser (Observations) 487,500 0,5774 0,1% OK /06/ /06/2011 NF EN ,000 3,5590 0,8% OK /06/2011 NF EN ,500 1,9149 0,4% OK /06/ /06/2011 NF EN ,000 2,1602 0,4% OK /06/ /06/2011 NF EN ,750 1,5000 0,3% OK /05/ /06/2011 NF EN ,000 5,6569 1,3% OK /06/ /06/2011 Autre, à préciser (Observations) 406,000 13,2916 3,3% OK /06/ /06/2011 NF EN ,750 6,3966 1,4% OK /06/ /06/2011 NF EN ,250 0,9574 0,2% OK /05/ /05/2011 NF EN ,000 6,9282 1,5% OK /06/ /06/2011 NF EN ,250 0,5000 0,1% OK /05/ /05/2011 NF EN ,750 2,5000 0,5% OK DRC B Page 89 sur 171

93 Table Metals_solution Nitric acid hydroperoxide - Arsenic Raw data in µg/liter Laboratory Identification Beginning of analysis End of analysis Standard Average of measurements Standard Deviation of s CVrep by % EXPERT opinion Expert Opinion Comments /06/ /06/2011 NF EN ,500 1,2910 1,0% OK /05/ /05/2011 NF EN ,250 0,9574 0,7% OK /06/ /06/2011 Autre, à préciser (Observations) 118,750 5,6199 4,7% OK /06/ /06/2011 NF EN ,500 2,5166 1,7% OK /06/2011 NF EN ,750 0,5000 0,4% OK /06/ /06/2011 NF EN ,500 1,2910 1,0% OK /06/ /06/2011 NF EN ,250 1,7078 1,4% OK /05/ /06/2011 NF EN ,000 2,7080 1,9% OK /06/ /06/2011 Autre, à préciser (Observations) 127,500 1,0000 0,8% OK /06/ /06/2011 NF EN ,500 1,2910 0,9% OK /06/ /06/2011 NF EN ,500 0,5774 0,5% OK /05/ /05/2011 NF EN ,500 2,5166 1,9% OK /06/ /06/2011 NF EN ,250 4,1932 3,1% OK /05/ /05/2011 NF EN ,000 5,1640 3,7% OK DRC B Page 90 sur 171

94 Table Metals_solution Nitric acid hydroperoxide - Cadmium Raw data in µg/liter Laboratory Identification Beginning of analysis End of analysis Standard Average of measurements Standard Deviation of s CVrep by % EXPERT opinion Expert Opinion Comments /06/ /06/2011 NF EN ,000 0,0000 0,0% OK /05/ /05/2011 NF EN ,000 0,0000 0,0% OK /06/ /06/2011 Autre, à préciser (Observations) 12,750 0,5000 3,9% OK /06/ /06/2011 NF EN ,000 0,0000 0,0% OK /06/2011 NF EN ,000 0,0000 0,0% OK /06/ /06/2011 NF EN ,000 0,0000 0,0% OK /06/ /06/2011 NF EN ,750 0,5000 2,5% OK /05/ /06/2011 NF EN ,000 0,0000 0,0% OK /06/ /06/2011 Autre, à préciser (Observations) 20,250 0,5000 2,5% OK /06/ /06/2011 NF EN ,500 0,5774 3,0% OK /06/ /06/2011 NF EN ,000 0,0000 0,0% OK /05/ /05/2011 NF EN ,000 0,0000 0,0% OK /06/ /06/2011 NF EN ,500 0,5774 3,0% OK /05/ /05/2011 NF EN ,750 0,9574 4,6% OK DRC B Page 91 sur 171

95 Table Metals_solution Nitric acid hydroperoxide Chromium Raw data in µg/liter Laboratory Identification Beginning of analysis End of analysis Standard Average of measurements Standard Deviation of s CVrep by % EXPERT opinion Expert Opinion Comments /06/ /06/2011 NF EN ,500 1,2910 0,7% OK /05/ /05/2011 NF EN ,250 0,9574 0,5% OK /06/ /06/2011 Autre, à préciser (Observations) 122,250 3,5000 2,9% OK /06/ /06/2011 NF EN ,250 1,2583 0,7% OK /06/2011 NF EN ,000 1,6330 0,8% OK /06/ /06/2011 NF EN ,000 1,8257 1,0% OK /06/ /06/2011 NF EN ,000 0,8165 0,4% OK /05/ /06/2011 NF EN ,500 3,6968 2,0% OK /06/ /06/2011 Autre, à préciser (Observations) 193,750 1,5000 0,8% OK /06/ /06/2011 NF EN ,250 2,3629 1,2% OK /06/ /06/2011 NF EN ,250 0,5000 0,3% OK /05/ /05/2011 NF EN ,250 6,0759 3,1% OK /06/ /06/2011 NF EN ,250 3,2016 1,5% OK /05/ /05/2011 NF EN ,250 5,4391 2,7% OK DRC B Page 92 sur 171

96 Table Metals_solution Nitric acid hydroperoxide - Cobalt Raw Data in µg/liter in µg/liter Laboratory Identification Beginning of analysis End of analysis Standard Average of measurements Standard Deviation of s CVrep by % EXPERT opinion Expert Opinion Comments /06/ /06/2011 NF EN ,000 1,4142 0,6% OK /05/ /05/2011 NF EN ,750 0,9574 0,4% OK /06/ /06/2011 Autre, à préciser (Observations) 135,000 4,2426 3,1% OK /06/ /06/2011 NF EN ,500 0,5774 0,3% OK /06/2011 NF EN ,000 1,4142 0,7% OK /06/ /06/2011 NF EN ,750 1,7078 0,7% OK /06/ /06/2011 NF EN ,250 1,2583 0,6% OK /05/ /06/2011 NF EN ,750 4,2720 2,1% OK /06/ /06/2011 Autre, à préciser (Observations) 218,500 1,9149 0,9% OK /06/ /06/2011 NF EN ,750 1,5000 0,7% OK /06/ /06/2011 NF EN ,000 0,0000 0,0% OK /05/ /05/2011 NF EN ,500 4,6547 2,1% OK /06/ /06/2011 NF EN ,250 0,5000 0,2% OK /05/ /05/2011 NF EN ,750 3,5000 1,5% OK DRC B Page 93 sur 171

97 Table Metals_solution Nitric acid hydroperoxide Copper Raw data in µg/liter Laboratory Identification Beginning of analysis End of analysis Standard Average of measurements Standard Deviation of s CVrep by % EXPERT opinion Expert Opinion Comments /06/ /06/2011 NF EN ,000 0,8165 0,3% OK /05/ /05/2011 NF EN ,500 1,2910 0,5% OK /06/ /06/2011 Autre, à préciser (Observations) 155,250 4,4253 2,9% OK /06/ /06/2011 NF EN ,750 0,9574 0,4% OK /06/2011 NF EN ,000 1,6330 0,7% OK /06/ /06/2011 NF EN ,250 1,8930 0,8% OK /06/ /06/2011 NF EN ,250 0,9574 0,4% OK /05/ /06/2011 NF EN ,250 7,1356 3,4% OK /06/ /06/2011 Autre, à préciser (Observations) 240,500 2,3805 1,0% OK /06/ /06/2011 NF EN ,000 3,5590 1,5% OK /06/ /06/2011 NF EN ,750 0,9574 0,5% OK /05/ /05/2011 NF EN ,000 0,8165 0,4% OK /06/ /06/2011 NF EN ,500 2,8868 1,2% OK /05/ /05/2011 NF EN ,250 2,9861 1,3% OK DRC B Page 94 sur 171

98 Table Metals_solution Nitric acid hydroperoxide - Manganese Raw data in µg/liter Laboratory Identification Beginning of analysis End of analysis Standard Average of measurements Standard Deviation of s CVrep by % EXPERT opinion Expert Opinion Comments /06/ /06/2011 NF EN ,000 0,8165 0,4% OK /05/ /05/2011 NF EN ,750 0,9574 0,4% OK /06/ /06/2011 Autre, à préciser (Observations) 124,250 4,0311 3,2% OK /06/ /06/2011 NF EN ,250 1,8930 0,8% OK /06/2011 NF EN ,500 1,2910 0,6% OK /06/ /06/2011 NF EN ,000 1,4142 0,6% OK /06/ /06/2011 NF EN ,250 1,7078 0,8% OK /05/ /06/2011 NF EN ,500 3,6968 1,8% OK /06/ /06/2011 Autre, à préciser (Observations) 218,750 2,7538 1,3% OK /06/ /06/2011 NF EN ,000 2,9439 1,3% OK /06/ /06/2011 NF EN ,750 0,9574 0,4% OK /05/ /05/2011 NF EN ,250 1,7078 0,7% OK /06/ /06/2011 NF EN ,500 2,8868 1,3% OK /05/ /05/2011 NF EN ,000 4,1633 1,9% OK DRC B Page 95 sur 171

99 Table Metals_solution Nitric acid hydroperoxide - Nickel Raw Data in µg/liter in µg/liter Laboratory Identification Beginning of analysis End of analysis Standard Average of measurements Standard Deviation of s CVrep by % EXPERT opinion Expert Opinion Comments /06/ /06/2011 NF EN ,000 0,8165 0,4% OK /05/ /05/2011 NF EN ,750 0,9574 0,4% OK /06/ /06/2011 Autre, à préciser (Observations) 135,250 4,3493 3,2% OK /06/ /06/2011 NF EN ,750 0,9574 0,4% OK /06/2011 NF EN ,750 1,7078 0,8% OK /06/ /06/2011 NF EN ,000 2,1602 1,0% OK /06/ /06/2011 NF EN ,500 1,0000 0,5% OK /05/ /06/2011 NF EN ,750 5,9090 3,0% OK /06/ /06/2011 Autre, à préciser (Observations) 203,750 2,9861 1,5% OK /06/ /06/2011 NF EN ,000 3,8297 1,8% OK /06/ /06/2011 NF EN ,000 2,9439 1,4% OK /05/ /05/2011 NF EN ,250 5,5000 2,4% OK /06/ /06/2011 NF EN ,750 1,2583 0,6% OK /05/ /05/2011 NF EN ,000 6,3770 2,8% OK DRC B Page 96 sur 171

100 Table Metals_solution Nitric acid hydroperoxide Lead Raw Data in µg/liter Laboratory Identification Beginning of analysis End of analysis Standard Average of measurements Standard Deviation of s CVrep by % EXPERT opinion Expert Opinion Comments /06/ /06/2011 NF EN ,000 3,1623 0,6% OK /05/ /05/2011 NF EN ,750 0,9574 0,2% OK /06/ /06/2011 Autre, à préciser (Observations) 504,500 1,7321 0,3% OK /06/ /06/2011 NF EN ,750 2,8723 0,6% OK /06/2011 NF EN ,750 2,5000 0,5% OK /06/ /06/2011 NF EN ,500 3,1091 0,6% OK /06/ /06/2011 NF EN ,000 0,0000 0,0% OK /05/ /06/2011 NF EN ,500 1,9149 0,4% OK /06/ /06/2011 Autre, à préciser (Observations) 469,750 16,3172 3,5% OK /06/ /06/2011 NF EN ,500 4,1231 0,8% OK /06/ /06/2011 NF EN ,750 2,5000 0,5% OK /05/ /05/2011 NF EN ,500 2,3805 0,5% OK /06/ /06/2011 NF EN ,250 0,9574 0,2% OK /05/ /05/2011 NF EN ,500 5,9722 1,2% OK DRC B Page 97 sur 171

101 Table Metals_solution Nitric acid hydroperoxide - Thallium Raw Data in µg/liter Laboratory Identification Beginning of analysis End of analysis Standard Average of measurements Standard Deviation of s CVrep by % EXPERT opinion Expert Opinion Comments /06/ /06/2011 NF EN ,000 0,0000 0,0% OK /05/ /05/2011 NF EN ,250 0,5000 2,2% OK /06/ /06/2011 Autre, à préciser (Observations) 10,000 0,0000 0,0% Exclus Valeur rendue < /06/ /06/2011 NF EN ,000 2,0000 8,3% OK /06/2011 NF EN ,000 0,0000 0,0% OK /06/ /06/2011 NF EN ,000 0,0000 0,0% OK /06/ /06/2011 NF EN ,000 0,0000 0,0% OK /05/ /06/2011 NF EN ,000 0,0000 0,0% OK /06/ /06/2011 Autre, à préciser (Observations) 20,750 0,9574 4,6% OK /06/ /06/2011 NF EN ,000 0,0000 0,0% OK /06/ /06/2011 NF EN ,000 0,0000 0,0% OK /05/ /05/2011 NF EN ,000 0,0000 0,0% OK /06/ /06/2011 NF EN ,000 1,1547 5,5% OK /05/ /05/2011 NF EN ,500 1,0000 4,7% OK DRC B Page 98 sur 171

102 Table Metals_solution Nitric acid hydroperoxide - Vanadium Raw Data in µg/liter Laboratory Identification Beginning of analysis End of analysis Standard Average of measurements Standard Deviation of s CVrep by % EXPERT opinion Expert Opinion Comments /06/ /06/2011 NF EN ,500 0,5774 0,3% OK /05/ /05/2011 NF EN ,500 0,5774 0,3% OK /06/ /06/2011 Autre, à préciser (Observations) 122,500 4,2032 3,4% OK /06/ /06/2011 NF EN ,250 0,9574 0,5% OK /06/2011 NF EN ,750 1,7078 0,9% OK /06/ /06/2011 NF EN ,250 1,8930 0,9% OK /06/ /06/2011 NF EN ,750 0,5000 0,3% OK /05/ /06/2011 NF EN ,500 3,7859 2,0% OK /06/ /06/2011 Autre, à préciser (Observations) 188,500 1,0000 0,5% OK /06/ /06/2011 NF EN ,500 3,7859 1,9% OK /06/ /06/2011 NF EN ,250 0,5000 0,3% OK /05/ /05/2011 NF EN ,000 4,0825 2,2% OK /06/ /06/2011 NF EN ,750 0,9574 0,5% OK /05/ /05/2011 NF EN ,250 2,5000 1,5% OK DRC B Page 99 sur 171

103 TABLES 19 TO METALS DUST FREE PROTOCOL RAW DATA IN µg/g Table Metals Dust Free protocol Antimony Raw Data in µg/g Laboratory Identification Beginning of analysis End of analysis Standard Average of measurements Standard Deviation of s CVrep by % EXPERT opinion Expert Opinion Comments /06/ /06/2011 NF EN , ,0871 2,3% OK /06/ /06/2011 NF EN , ,9040 2,8% OK /06/ /06/2011 Autre, à préciser (Observations) 5046,250 14,9304 0,3% OK /06/ /06/2011 NF EN , ,8819 2,5% OK /06/ /06/2011 NF EN ,750 30,2696 0,5% OK /06/ /06/2011 NF EN , ,5221 1,9% OK Faites votre choix Non analysé Non analysé Non analysé Exclus /05/ /06/2011 NF EN , ,1943 1,9% OK /06/ /06/2011 Autre, à préciser (Observations) 4406, ,4063 4,5% OK /06/ /06/2011 NF EN , , ,4% OK /06/ /06/2011 NF EN ,750 4,3493 0,1% OK /06/ /06/2011 NF EN , , ,2% OK /06/ /06/2011 NF EN , ,7253 2,3% OK /05/ /06/2011 NF EN , ,4412 2,1% OK DRC B Page 100 sur 171

104 Table Metals Dust Free protocol - Arsenic - Raw Data in µg/g Laboratory Identification Beginning of analysis End of analysis Standard Average of measurements Standard Deviation of s CVrep by % EXPERT opinion Expert Opinion Comments /06/ /06/2011 NF EN ,750 61,2066 4,1% OK /06/ /06/2011 NF EN ,750 34,8557 2,4% OK /06/ /06/2011 Autre, à préciser (Observations) 1405,000 52,5991 3,7% OK /06/ /06/2011 NF EN ,000 66,8581 2,7% OK /06/ /06/2011 NF EN ,500 23,4165 1,3% OK /06/ /06/2011 NF EN ,500 26,4386 2,0% OK Faites votre choix Non analysé Non analysé Non analysé Exclus /05/ /06/2011 NF EN ,500 32,8278 2,2% OK /06/ /06/2011 Autre, à préciser (Observations) 1342,750 14,9304 1,1% OK /06/ /06/2011 NF EN , , ,3% OK /06/ /06/2011 NF EN ,000 47,6095 1,7% OK /06/ /06/2011 NF EN ,000 1,4142 0,1% OK /06/ /06/2011 NF EN ,500 31,8904 1,9% OK /05/ /06/2011 NF EN , ,5441 5,0% OK DRC B Page 101 sur 171

105 Table Metals Dust Free protocol - Cadmium - Raw Data in µg/g Laboratory Identification Beginning of analysis End of analysis Standard Average of measurements Standard Deviation of s CVrep by % EXPERT opinion Expert Opinion Comments /06/ /06/2011 NF EN ,000 14,4914 6,9% OK /06/ /06/2011 NF EN ,000 2,1602 1,2% OK /06/ /06/2011 Autre, à préciser (Observations) 145,000 3,4641 2,4% OK /06/ /06/2011 NF EN ,750 8,5781 4,2% OK /06/ /06/2011 NF EN ,250 3,3040 1,7% OK /06/ /06/2011 NF EN ,000 3,5590 2,0% OK Faites votre choix Non analysé Non analysé Non analysé Exclus /05/ /06/2011 NF EN ,000 1,1547 0,6% OK /06/ /06/2011 Autre, à préciser (Observations) 196,250 3,3040 1,7% OK /06/ /06/2011 NF EN ,500 11,6762 5,2% OK /06/ /06/2011 NF EN ,250 2,0616 1,2% OK /06/ /06/2011 NF EN ,000 5,6569 4,4% OK /06/ /06/2011 NF EN ,250 13,2004 2,5% OK /05/ /06/2011 NF EN ,500 7,0475 3,4% OK DRC B Page 102 sur 171

106 Tableau Metals Dust Free protocol Chromium Raw Data in µg/g Laboratory Identification Beginning of analysis End of analysis Standard Average of measurements Standard Deviation of s CVrep by % EXPERT opinion Expert Opinion Comments /06/ /06/2011 NF EN ,250 17,4428 1,9% OK /06/ /06/2011 NF EN ,250 28,7214 2,0% OK /06/ /06/2011 Autre, à préciser (Observations) 32,500 3,0000 9,2% OK /06/ /06/2011 NF EN ,000 99, ,6% OK /06/ /06/2011 NF EN ,500 29,4562 1,8% OK /06/ /06/2011 NF EN ,750 50,2618 3,7% OK Faites votre choix Non analysé Non analysé Non analysé Exclus /05/ /06/2011 NF EN ,000 11,9164 1,8% OK /06/ /06/2011 Autre, à préciser (Observations) 10,500 1, ,5% OK /06/ /06/2011 NF EN , , ,5% OK /06/ /06/2011 NF EN ,750 0,5000 1,2% OK /06/ /06/2011 NF EN ,000 55, ,9% OK /06/ /06/2011 NF EN ,000 53,0786 3,6% OK /05/ /06/2011 NF EN ,500 28,6647 8,4% OK DRC B Page 103 sur 171

107 Table Metals Dust Free protocol Cobalt Raw Data in µg/g Laboratory Identification Beginning of analysis End of analysis Standard Average of measurements Standard Deviation of s CVrep by % EXPERT opinion Expert Opinion Comments /06/ /06/2011 NF EN , ,8637 8,3% OK /06/ /06/2011 NF EN , ,6251 6,3% OK /06/ /06/2011 Autre, à préciser (Observations) 1502,500 61,9812 4,1% OK /06/ /06/2011 NF EN , ,0667 6,3% OK /06/ /06/2011 NF EN ,500 21,1739 1,2% OK /06/ /06/2011 NF EN , ,4656 6,3% OK Faites votre choix Non analysé Non analysé Non analysé Exclus /05/ /06/2011 NF EN ,000 91,4877 5,5% OK /06/ /06/2011 Autre, à préciser (Observations) 1642,750 35,9850 2,2% OK /06/ /06/2011 NF EN , ,2098 9,5% OK /06/ /06/2011 NF EN ,500 7,0475 0,4% OK /06/ /06/2011 NF EN ,500 36,0624 3,0% OK /06/ /06/2011 NF EN ,250 19,3111 1,2% OK /05/ /06/2011 NF EN ,750 86,1680 4,4% OK DRC B Page 104 sur 171

108 Table Metals - Dust - Free protocol - Copper - Raw Data in µg/g Laboratory Identification Beginning of analysis End of analysis Standard Average of measurements Standard Deviation of s CVrep by % Expert Opinion Expert Opinion Comments /06/ /06/2011 NF EN ,250 33,8760 1,8% OK /06/ /06/2011 NF EN ,000 37,5322 1,9% OK /06/ /06/2011 Autre, à préciser (Observations) 1662,500 36,6288 2,2% OK /06/ /06/2011 NF EN ,000 11,8884 0,5% OK /06/ /06/2011 NF EN ,250 44,1390 2,1% OK /06/ /06/2011 NF EN ,750 66,2388 3,5% OK Faites votre choix Non analysé Non analysé Non analysé Exclus /05/ /06/2011 NF EN ,000 48,3942 2,6% OK /06/ /06/2011 Autre, à préciser (Observations) 1844,250 50,4273 2,7% OK /06/ /06/2011 NF EN , , ,9% OK /06/ /06/2011 NF EN ,500 15,0000 0,7% OK /06/ /06/2011 NF EN ,000 91,9239 6,7% OK /06/ /06/2011 NF EN ,500 21,4398 1,1% OK /05/ /06/2011 NF EN ,500 60,6658 3,0% OK DRC B Page 105 sur 171

109 Table Metals - Dust - Free protocol - Manganese - Raw Data in µg/g Laboratory Identification Beginning of analysis End of analysis Standard Average of measurements Standard Deviation of s CVrep by % EXPERT opinion Expert Opinion Comments /06/ /06/2011 NF EN ,250 50,6384 4,4% OK /06/ /06/2011 NF EN ,250 37,3486 2,3% OK /06/ /06/2011 Autre, à préciser (Observations) 1450,000 52,1217 3,6% OK /06/ /06/2011 NF EN , ,0352 6,4% OK /06/ /06/2011 NF EN ,500 15,9269 0,6% OK /06/ /06/2011 NF EN , , ,9% OK Faites votre choix Non analysé Non analysé Non analysé Exclus /05/ /06/2011 NF EN ,500 84,9215 5,5% OK /06/ /06/2011 Autre, à préciser (Observations) 900, , ,8% OK /06/ /06/2011 NF EN , ,1498 9,4% OK /06/ /06/2011 NF EN ,250 6,0759 0,4% OK /06/ /06/2011 NF EN ,000 25,4558 2,2% OK /06/ /06/2011 NF EN ,750 30,5109 1,8% OK /05/ /06/2011 NF EN ,250 15,1959 0,9% OK DRC B Page 106 sur 171

110 Table Metals - Dust - Free protocol - Nickel - Raw Data in µg/g Laboratory Identification Beginning of analysis End of analysis Standard Average of measurements Standard Deviation of s CVrep by % EXPERT opinion Expert Opinion Comments /06/ /06/2011 NF EN ,000 10,0995 0,7% OK /06/ /06/2011 NF EN ,500 23,5726 1,5% OK /06/ /06/2011 Autre, à préciser (Observations) 1186,250 19,3111 1,6% OK /06/ /06/2011 NF EN ,000 57,1431 1,9% OK /06/ /06/2011 NF EN ,000 35,1852 2,3% OK /06/ /06/2011 NF EN ,000 37,0855 2,5% OK Faites votre choix Non analysé Non analysé Non analysé Exclus /05/ /06/2011 NF EN ,750 44,7763 2,8% OK /06/ /06/2011 Autre, à préciser (Observations) 1024, , ,3% OK /06/ /06/2011 NF EN , , ,1% OK /06/ /06/2011 NF EN ,250 20,9662 1,2% OK /06/ /06/2011 NF EN ,500 9,1924 0,7% OK /06/ /06/2011 NF EN ,250 37,8627 2,3% OK /05/ /06/2011 NF EN ,750 28,9410 1,7% OK DRC B Page 107 sur 171

111 Table Metals - Dust - Free protocol - Lead - Raw Data in µg/g Laboratory Identification Beginning of analysis End of analysis Standard Average of measurements Standard Deviation of s CVrep by % EXPERT opinion Expert Opinion Comments /06/ /06/2011 NF EN , ,6549 3,2% OK /06/ /06/2011 NF EN , ,8122 2,9% OK /06/ /06/2011 Autre, à préciser (Observations) 33625, ,6991 4,6% OK /06/ /06/2011 NF EN , ,6102 2,6% OK /06/ /06/2011 NF EN , ,3405 1,3% OK /06/ /06/2011 NF EN , ,0684 2,8% OK Faites votre choix Non analysé Non analysé Non analysé Exclus /05/ /06/2011 NF EN , ,8479 1,7% OK /06/ /06/2011 Autre, à préciser (Observations) 35527, ,1214 1,0% OK /06/ /06/2011 NF EN , , ,7% OK /06/ /06/2011 NF EN , ,0000 0,6% OK /06/ /06/2011 NF EN , ,3768 1,6% OK /06/ /06/2011 NF EN , ,5401 0,7% OK /05/ /06/2011 NF EN , ,5441 2,0% OK DRC B Page 108 sur 171

112 Table Metals - Dust - Free protocol - Thallium - Raw Data in µg/g Laboratory Identification Beginning of analysis End of analysis Standard Average of measurements Standard Deviation of s CVrep by % EXPERT opinion Expert Opinion Comments /06/ /06/2011 NF EN ,250 6,1305 2,6% OK /06/ /06/2011 NF EN ,500 3,3166 4,2% OK /06/ /06/2011 Autre, à préciser (Observations) 232,000 2,4495 1,1% OK /06/ /06/2011 NF EN ,750 15,4353 6,0% OK /06/ /06/2011 NF EN ,250 2,2174 0,9% OK /06/ /06/2011 NF EN ,250 12,9968 6,0% OK Faites votre choix Non analysé Non analysé Non analysé Exclus /05/ /06/2011 NF EN ,750 10,7199 4,4% OK /06/ /06/2011 Autre, à préciser (Observations) 249,750 6,2915 2,5% OK /06/ /06/2011 NF EN ,750 18,3007 6,3% OK /06/ /06/2011 NF EN ,250 4,3493 2,4% OK /06/ /06/2011 NF EN ,500 10, ,8% Exclus 2 valeurs rendues dont 1 < /06/ /06/2011 NF EN ,500 2,3805 1,0% OK /05/ /06/2011 NF EN ,750 15,9034 3,8% OK DRC B Page 109 sur 171

113 Table Metals - Dust - Free protocol - Vanadium - Raw Data in µg/g Laboratory Identification Beginning of analysis End of analysis Standard Average of measurements Standard Deviation of s CVrep by % EXPERT opinion Expert Opinion Comments /06/ /06/2011 NF EN ,750 66,7052 4,6% OK /06/ /06/2011 NF EN ,000 35,9166 2,2% OK /06/ /06/2011 Autre, à préciser (Observations) 1052,500 17,5594 1,7% OK /06/ /06/2011 NF EN ,750 27,5847 2,1% OK /06/ /06/2011 NF EN ,250 10,7819 0,6% OK /06/ /06/2011 NF EN ,250 74,0197 5,5% OK Faites votre choix Non analysé Non analysé Non analysé Exclus /05/ /06/2011 NF EN ,500 27,2825 2,0% OK /06/ /06/2011 Autre, à préciser (Observations) 1469,250 44,2446 3,0% OK /06/ /06/2011 NF EN , , ,6% OK /06/ /06/2011 NF EN ,750 17,5000 1,5% OK /06/ /06/2011 NF EN ,500 44,5477 4,0% OK /06/ /06/2011 NF EN ,500 93,2255 5,8% OK /05/ /06/2011 NF EN ,500 56,8653 3,4% OK DRC B Page 110 sur 171

114 TABLE 30 À METALS DUST IMPOSED PROTOCOL- RAW DATA IN µg/g Table Metals - Dust - Imposed protocol - Antimony - Raw Data in µg/g Laboratory Identification Beginning of analysis End of analysis Standard Average of measurements Standard Deviation of s CVrep by % EXPERT opinion Expert Opinion Comments /06/ /06/2011 NF EN , ,4429 2,7% OK Faites votre choix Non analysé Non analysé Non analysé Exclus /06/ /06/2011 Autre, à préciser (Observations) 5535,000 97,1253 1,8% OK /06/ /06/2011 NF EN , ,8659 1,7% OK /06/ /06/2011 NF EN ,000 55,7913 0,9% OK /06/ /06/2011 NF EN ,000 31,6754 0,5% OK Faites votre choix Non analysé Non analysé Non analysé Exclus /05/ /05/2011 NF EN , ,8222 1,8% OK Faites votre choix Non analysé Non analysé Non analysé Exclus /06/ /06/2011 NF EN , , ,4% OK Faites votre choix Non analysé Non analysé Non analysé Exclus /06/ /06/2011 NF EN , ,2605 5,2% OK /06/ /06/2011 NF EN ,000 36,9414 0,6% OK /05/ /06/2011 NF EN , ,4412 2,1% OK DRC B Page 111 sur 171

115 Table Metals - Dust - Imposed protocol - Arsenic - Raw Data in µg/g Laboratory Identification Beginning of analysis End of analysis Standard Average of measurements Standard Deviation of s CVrep by % EXPERT opinion Expert Opinion Comments /06/ /06/2011 NF EN ,750 80,2553 5,1% OK Faites votre choix Non analysé Non analysé Non analysé Exclus /06/ /06/2011 Autre, à préciser (Observations) 1482,500 63,9661 4,3% OK /06/ /06/2011 NF EN ,750 94,7536 3,9% OK /06/ /06/2011 NF EN ,500 51,0065 2,8% OK /06/ /06/2011 NF EN ,500 41,7173 3,0% OK Faites votre choix Non analysé Non analysé Non analysé Exclus /05/ /05/2011 NF EN ,750 15,6924 1,0% OK Faites votre choix Non analysé Non analysé Non analysé Exclus /06/ /06/2011 NF EN , , ,3% OK Faites votre choix Non analysé Non analysé Non analysé Exclus /06/ /06/2011 NF EN ,500 20,5061 1,5% OK /06/ /06/2011 NF EN ,250 11,0265 0,6% OK /05/ /06/2011 NF EN , ,1468 6,4% OK DRC B Page 112 sur 171

116 Table Metals - Dust - Imposed protocol - Cadmium - Raw Data in µg/g Laboratory Identification Beginning of analysis End of analysis Standard Average of measurements Standard Deviation of s CVrep by % EXPERT opinion Expert Opinion Comments /06/ /06/2011 NF EN ,250 8,6168 3,7% OK Faites votre choix Non analysé Non analysé Non analysé Exclus /06/ /06/2011 Autre, à préciser (Observations) 160,250 2,5000 1,6% OK /06/ /06/2011 NF EN ,000 8,1240 3,8% OK /06/ /06/2011 NF EN ,000 3,5590 1,8% OK /06/ /06/2011 NF EN ,500 2,6458 1,5% OK Faites votre choix Non analysé Non analysé Non analysé Exclus /05/ /05/2011 NF EN ,500 7,8528 4,1% OK Faites votre choix Non analysé Non analysé Non analysé Exclus /06/ /06/2011 NF EN ,500 11,6762 5,2% OK Faites votre choix Non analysé Non analysé Non analysé Exclus /06/ /06/2011 NF EN ,000 1,4142 0,8% OK /06/ /06/2011 NF EN ,500 4,5092 0,7% OK /05/ /06/2011 NF EN ,500 7,0475 3,4% OK DRC B Page 113 sur 171

117 Table Metals - Dust - Imposed protocol - Chromium - Raw Data in µg/g Laboratory Identification Beginning of analysis End of analysis Standard Average of measurements Standard Deviation of s CVrep by % EXPERT opinion Expert Opinion Comments /06/ /06/2011 NF EN , , ,7% OK Faites votre choix Non analysé Non analysé Non analysé Exclus /06/ /06/2011 Autre, à préciser (Observations) 32,750 1,5000 4,6% OK /06/ /06/2011 NF EN , , ,8% OK /06/ /06/2011 NF EN ,500 65,3427 3,9% OK /06/ /06/2011 NF EN ,750 3,8622 0,3% OK Faites votre choix Non analysé Non analysé Non analysé Exclus /05/ /05/2011 NF EN ,750 32,3252 5,0% OK Faites votre choix Non analysé Non analysé Non analysé Exclus /06/ /06/2011 NF EN , , ,5% OK Faites votre choix Non analysé Non analysé Non analysé Exclus /06/ /06/2011 NF EN , ,2376 7,5% OK /06/ /06/2011 NF EN ,500 68,2862 4,3% OK /05/ /06/2011 NF EN ,500 28,6647 8,4% OK DRC B Page 114 sur 171

118 Table Metals - Dust - Imposed protocol - Cobalt - Raw Data in µg/g Laboratory Identification Beginning of analysis End of analysis Standard Average of measurements Standard Deviation of s CVrep by % EXPERT opinion Expert Opinion Comments /06/ /06/2011 NF EN , ,9152 6,8% OK Faites votre choix Non analysé Non analysé Non analysé Exclus /06/ /06/2011 Autre, à préciser (Observations) 1760,000 21,9848 1,2% OK /06/ /06/2011 NF EN ,500 74,6570 3,4% OK /06/ /06/2011 NF EN ,500 97,3465 5,3% OK /06/ /06/2011 NF EN ,500 36,4555 2,2% OK Faites votre choix Non analysé Non analysé Non analysé Exclus /05/ /05/2011 NF EN ,750 59,8909 3,6% OK Faites votre choix Non analysé Non analysé Non analysé Exclus /06/ /06/2011 NF EN , ,4213 9,4% OK Faites votre choix Non analysé Non analysé Non analysé Exclus /06/ /06/2011 NF EN ,000 49,4975 2,8% OK /06/ /06/2011 NF EN ,000 89,1665 5,2% OK /05/ /06/2011 NF EN ,750 86,1680 4,4% OK DRC B Page 115 sur 171

119 Table Metals - Dust - Imposed protocol - Copper - Raw Data in µg/g Laboratory Identification Beginning of analysis End of analysis Standard Average of measurements Standard Deviation of s CVrep by % EXPERT opinion Expert Opinion Comments /06/ /06/2011 NF EN ,750 89,3099 4,5% OK Faites votre choix Non analysé Non analysé Non analysé Exclus /06/ /06/2011 Autre, à préciser (Observations) 1907,500 29,8608 1,6% OK /06/ /06/2011 NF EN ,750 50,5791 2,1% OK /06/ /06/2011 NF EN , ,9598 7,7% OK /06/ /06/2011 NF EN ,500 39,6190 2,0% OK Faites votre choix Non analysé Non analysé Non analysé Exclus /05/ /05/2011 NF EN ,250 23,0705 1,3% OK Faites votre choix Non analysé Non analysé Non analysé Exclus /06/ /06/2011 NF EN , , ,9% OK Faites votre choix Non analysé Non analysé Non analysé Exclus /06/ /06/2011 NF EN ,500 2,1213 0,1% OK /06/ /06/2011 NF EN ,750 58,3745 2,9% OK /05/ /06/2011 NF EN ,500 60,6658 3,0% OK DRC B Page 116 sur 171

120 Table Metals - Dust - Imposed protocol - Manganese - Raw Data in µg/g Laboratory Identification Beginning of analysis End of analysis Standard Average of measurements Standard Deviation of s CVrep by % EXPERT opinion Expert Opinion Comments /06/ /06/2011 NF EN , ,1680 6,3% OK Faites votre choix Non analysé Non analysé Non analysé Exclus /06/ /06/2011 Autre, à préciser (Observations) 1621,250 26,5754 1,6% OK /06/ /06/2011 NF EN ,000 71,1946 3,2% OK /06/ /06/2011 NF EN , ,3959 7,9% OK /06/ /06/2011 NF EN ,750 27,2198 1,6% OK Faites votre choix Non analysé Non analysé Non analysé Exclus /05/ /05/2011 NF EN ,000 64,8896 3,9% OK Faites votre choix Non analysé Non analysé Non analysé Exclus /06/ /06/2011 NF EN , ,1498 9,4% OK Faites votre choix Non analysé Non analysé Non analysé Exclus /06/ /06/2011 NF EN ,500 21,9203 1,3% OK /06/ /06/2011 NF EN ,750 91,1386 5,4% OK /05/ /06/2011 NF EN ,250 15,1959 0,9% OK DRC B Page 117 sur 171

121 Table Metals - Dust - Imposed protocol - Nickel - Raw Data in µg/g Laboratory Identification Beginning of analysis End of analysis Standard Average of measurements Standard Deviation of s CVrep by % EXPERT opinion Expert Opinion Comments /06/ /06/2011 NF EN ,000 68,6343 4,0% OK Faites votre choix Non analysé Non analysé Non analysé Exclus /06/ /06/2011 Autre, à préciser (Observations) 1338,750 11,8145 0,9% OK /06/ /06/2011 NF EN ,750 92,1064 3,0% OK /06/ /06/2011 NF EN ,500 15,4596 1,0% OK /06/ /06/2011 NF EN ,500 35,2751 2,3% OK Faites votre choix Non analysé Non analysé Non analysé Exclus /05/ /05/2011 NF EN ,000 16,0831 1,0% OK Faites votre choix Non analysé Non analysé Non analysé Exclus /06/ /06/2011 NF EN , , ,1% OK Faites votre choix Non analysé Non analysé Non analysé Exclus /06/ /06/2011 NF EN ,000 2,8284 0,2% OK /06/ /06/2011 NF EN ,500 35,0856 2,0% OK /05/ /06/2011 NF EN ,750 28,9410 1,7% OK DRC B Page 118 sur 171

122 Table Metals - Dust - Imposed protocol - Lead - Raw Data in µg/g Laboratory Identification Beginning of analysis End of analysis Standard Average of measurements Standard Deviation of s CVrep by % EXPERT opinion Expert Opinion Comments /06/ /06/2011 NF EN , ,2308 6,2% OK Faites votre choix Non analysé Non analysé Non analysé Exclus /06/ /06/2011 Autre, à préciser (Observations) 36650, ,3124 1,7% OK /06/ /06/2011 NF EN , ,3578 2,9% OK /06/ /06/2011 NF EN , ,6601 1,0% OK /06/ /06/2011 NF EN , ,4804 2,0% OK Faites votre choix Non analysé Non analysé Non analysé Exclus /05/ /05/2011 NF EN , ,3499 1,6% OK Faites votre choix Non analysé Non analysé Non analysé Exclus /06/ /06/2011 NF EN , , ,7% OK Faites votre choix Non analysé Non analysé Non analysé Exclus /06/ /06/2011 NF EN , ,7171 8,6% OK /06/ /06/2011 NF EN , ,5298 0,4% OK /05/ /06/2011 NF EN , ,3968 2,3% OK DRC B Page 119 sur 171

123 Table Metals - Dust - Imposed protocol - Thallium - Raw Data in µg/g Laboratory Identification Beginning of analysis End of analysis Standard Average of measurements Standard Deviation of s CVrep by % EXPERT opinion Expert Opinion Comments /06/ /06/2011 NF EN ,750 6,0759 2,1% OK Faites votre choix Non analysé Non analysé Non analysé Exclus /06/ /06/2011 Autre, à préciser (Observations) 271,250 10,3078 3,8% OK /06/ /06/2011 NF EN ,000 28,3078 9,7% OK /06/ /06/2011 NF EN ,000 16,7929 6,7% OK /06/ /06/2011 NF EN ,500 3,1091 1,5% OK Faites votre choix Non analysé Non analysé Non analysé Exclus /05/ /05/2011 NF EN ,250 3,8622 1,5% OK Faites votre choix Non analysé Non analysé Non analysé Exclus /06/ /06/2011 NF EN ,750 18,3007 6,3% OK Faites votre choix Non analysé Non analysé Non analysé Exclus /06/ /06/2011 NF EN ,000 56, ,3% OK /06/ /06/2011 NF EN ,500 7,8528 3,1% OK /05/ /06/2011 NF EN ,750 15,9034 3,8% OK DRC B Page 120 sur 171

124 Table Metals - Dust - Imposed protocol - Vanadium - Raw Data in µg/g Laboratory Identification Beginning of analysis End of analysis Standard Average of measurements Standard Deviation of s CVrep by % EXPERT opinion Expert Opinion Comments /06/ /06/2011 NF EN ,750 99,2216 6,2% OK Faites votre choix Non analysé Non analysé Non analysé Exclus /06/ /06/2011 Autre, à préciser (Observations) 1300,000 0,0000 0,0% OK /06/ /06/2011 NF EN ,500 24,0901 1,9% OK /06/ /06/2011 NF EN ,250 85,4883 4,7% OK /06/ /06/2011 NF EN ,000 37,4344 2,6% OK Faites votre choix Non analysé Non analysé Non analysé Exclus /05/ /05/2011 NF EN ,500 18,2665 1,3% OK Faites votre choix Non analysé Non analysé Non analysé Exclus /06/ /06/2011 NF EN , , ,6% OK Faites votre choix Non analysé Non analysé Non analysé Exclus /06/ /06/2011 NF EN ,500 7,7782 0,5% OK /06/ /06/2011 NF EN ,500 74,5185 4,7% OK /05/ /06/2011 NF EN ,500 56,8653 3,4% OK DRC B Page 121 sur 171

125 ANNEX 3 STATISTICAL DISTRIBUTION CURVES Distribution curves are shown for each substance. They indicate the average and the standard deviation of the results for each participant. Each curve is bounded on the x-axis by the calculated reference values (robust average or reference average of the certified material). The lower bound is given by the reference value of the average minus three times the reference standard deviation, while the upper bound is obtained from the reference value of the average plus three times the reference standard deviation. Each participant is represented on the y-axis by its confidential code. The assay method used and the sample withdrawal or analysis date are specified for each participant. This type of representation allows each participant to view its own dispersion relative to that of the other laboratories. DRC B Page 122 sur 171

126

127 HCI ACIDE CHLORHYDRIQUE DRC B Page 123 sur 171

128 HF ACIDE FLUORHYDRIQUE DRC B Page 124 sur 171

129 HF POUSSIERE - ACIDE FLUORHYDRIQUE DRC B Page 125 sur 171

130 NH3 AMMONIAC DRC B Page 126 sur 171

131 SO2 DIOXYDE DE SOUFRE DRC B Page 127 sur 171

132 HG K2CR2O7 - MERCURE DRC B Page 128 sur 171

133 HG_KMNO4 - MERCURE DRC B Page 129 sur 171

134 METAUX_SOLUTION (11 FIGURES) DRC B Page 130 sur 171

135 DRC B Page 131 sur 171

136 DRC B Page 132 sur 171

137 DRC B Page 133 sur 171

138 DRC B Page 134 sur 171

139 DRC B Page 135 sur 171

140 DRC B Page 136 sur 171

141 DRC B Page 137 sur 171

142 DRC B Page 138 sur 171

143 DRC B Page 139 sur 171

144 DRC B Page 140 sur 171

145 METAUX POUSSIERE PROTOCOLE LIBRE (11 FIGURES) DRC B Page 141 sur 171

146 DRC B Page 142 sur 171

147 DRC B Page 143 sur 171

148 DRC B Page 144 sur 171

149 DRC B Page 145 sur 171

150 DRC B Page 146 sur 171

151 DRC B Page 147 sur 171

152 DRC B Page 148 sur 171

153 DRC B Page 149 sur 171

154 DRC B Page 150 sur 171

155 DRC B Page 151 sur 171

156 METAUX POUSSIERE PROTOCOLE IMPOSE (11 FIGURES) DRC B Page 152 sur 171

157 DRC B Page 153 sur 171

158 DRC B Page 154 sur 171

159 DRC B Page 155 sur 171

160 DRC B Page 156 sur 171

161 DRC B Page 157 sur 171

162 DRC B Page 158 sur 171

163 DRC B Page 159 sur 171

164 DRC B Page 160 sur 171

165 DRC B Page 161 sur 171

166 DRC B Page 162 sur 171

167 ANNEX 4 GENERAL ORGANIZATION, DESCRIPTION OF TESTS AND ALGORITHMS These histograms provide an overall view of all of the z scores obtained by the laboratory in a test material. DRC B Page 163 sur 171

168

169 FIGURE 1 : 11/119507_METAUX SOLUTION (PART 1 TO 3) DRC B Page 164 sur 171

170 11/119507_METAUX SOLUTION (PART 2) DRC B Page 165 sur 171

171 11/119507_METAUX SOLUTION (PART 3) DRC B Page 166 sur 171

172 FIGURE 2: 11/119507_METAUX POUSSIERE FREE PROTOCOL (PART 1 TO 3) DRC B Page 167 sur 171

173 11/119507_METAUX POUSSIERE FREE PROTOCOL (PART 2) DRC B Page 168 sur 171

174 11/119507_METAUX POUSSIERE FREE PROTOCOL (PART 3) DRC B Page 169 sur 171

175 FIGURE 3: 11/119507_METAUX POUSSIERE IMPOSED PROTOCOLE (PART 1 TO 2) DRC B Page 170 sur 171

176 11/119507_METAUX POUSSIERE IMPOSED PROTOCOL (PART 2) DRC B Page 171 sur 171