REPORT 23/12/2011 N DRC-11-119507-08855B Analytical Proficiency Tests relating to measurements of hydrochloric acid, hydrofluoric acid, ammonia, sulphur dioxide, mercury, and metals (and metalloids) in samples coming from stationary source emissions. FINAL REPORT
ANALYTICAL INTER-LABORATORY COMPARISONS ORGANIZED FOR THE LABORATORIES INVOLVED IN REGULATORY EMISSIONS CHECKS. 2011 Campaign : HCl, HF, NH 3, SO 2, total Hg, Heavy metals FINAL REPORT D R C - 11-1 1 9 5 0 7-0 8 8 5 5 B D E C E M B E R 23, 2 0 1 1 Sylvain BAILLEUL Characterization of the Environment Department Chronic Risks Division List of persons having taken part in the study : S. BAILLEUL, H. BIAUDET, F. DEL-GRATTA, J. POULLEAU, L. MEUNIER, B. DEFRENNE DRC-11-119507-08855B Page 3 sur 171
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-11-119507-08855B Page 4 sur 171
TABLE OF CONTENTS 1 GLOSSARY... 7 2 DEFINITIONS... 8 3 REFERENCE DOCUMENTS... 9 4 CLIENTS... 10 5 ORGANIZATION OF THE INTER-LABORATORY COMPARISONS... 10 6 PRESENTATION OF THE REPORT... 10 7 INTRODUCTION... 10 8 ILT PROGRAM... 11 9 TEST PARTICIPANTS... 11 10 DESCRIPTION OF THE TEST MATERIALS... 12 10.1 DESCRIPTION AND INSTRUCTIONS... 12 10.1.1 Total mercury in permanganate medium... 12 10.1.2 Total mercury in dichromate medium... 12 10.1.3 Hydrochloric acid... 13 10.1.4 Fluorhydric acid... 13 10.1.5 Metals (and metalloids)... 14 10.1.6 Sulfur dioxide... 14 10.1.7 Ammonia... 15 11 SHIPPING... 15 12 HOMOGENEITY AND STABILITY OF THE SAMPLES... 15 12.1 HOMOGENEITY OF THE MATERIALS... 15 12.2 STABILITY OF THE TEST MATERIALS... 16 13 RESULTS OF THE INTER-LABORATORY COMPARISON... 17 13.1 EXPLOITATION OF THE DATA FROM THE TEST MATERIALS... 17 13.1.1 General information... 17 13.1.2 Presentation of the results... 17 13.1.3 Test material "11/119507_Hg_KMnO 4"... 19 13.1.4 Test material "11/119507_Hg_K 2Cr 2O 7"... 21 13.1.5 Test material "11_119507_HCl"... 23 13.1.6 Test material "11_119507_HF_Solution"... 25 13.1.7 Test material "11_119507_HF_Poussière"... 27 13.1.8 Test material "11/119507_Metaux_solution"... 29 13.1.9 Test material "11/119507_Metaux_Poussiére" free protocol... 41 13.1.10 Test material "11/119507_Métaux_Poussiére" imposed protocol... 53 13.1.11 Test material "11_119507_SO 2"... 67 13.1.12 Test material "11_119507_NH 3"... 69 14 LIST OF ANNEXES... 71 ANNEX 1 GENERAL ORGANIZATION, DESCRIPTION OF TESTS AND ALGORITHMS... 72 General organization of the test... 73 Prior checking of the data before launching statistical calculations... 75 Materials prepared by the INERIS :... 77 Statistical performance tests... 79 ANNEX 2 DATA RECEIVED, AVERAGES AND REPEATABILITY STANDARD DEVIATIONS FOR THE LABORATORIES AND VALUES DISMISSED BY EXPERT OPINION... 81 Table 1-11 119507 HCl Water Hydrochloric acid Raw data in mg/liter... 82 Table 2-11 119507 HF Sodium hydroxide (NaOH) Fluorhydric Acid - Raw data in mg/liter... 83 Table 3-11 119507 HF Dust Fluorhydric Acid Raw data in mg/g... 84 Table 4-11 119507 NH3 Sulfuric acid - Ammonia Raw data in mg/liter... 85 Table 5-11 119507 SO2 Hydroperoxide Sulfur dioxide Raw data in mg/liter... 86 Table 6-11 119507 Hg_ K2Cr2O7 Nitric acid - Dichromate (HNO3-K2Cr2O7) - Mercury Raw data in µg/liter... 87 Table 7-11 119507 Hg_KMnO4 Sulfuric acid - Permanganate (H2SO4-KMnO4) - Mercury Raw Data in µg/liter.. 88 Tables 8 to 18-11 119507 Metals_solution Raw data in µg/liter... 89 DRC-11-119507-08855B Page 5 sur 171
Tables 19 to 29-11 119507 Metals Dust Free protocol Raw Data in µg/g... 100 Table 30 à 40-11 119507 Metals Dust Imposed protocol- Raw Data in µg/g... 111 ANNEX 3 STATISTICAL DISTRIBUTION CURVES... 122 11 119507 HF Acide Fluorhydrique... 124 11 119507 HF Poussière - Acide Fluorhydrique... 125 11 119507 NH3 Ammoniac... 126 11 119507 SO2 Dioxyde de soufre... 127 11 119507 Hg K2Cr2O7 - Mercure... 128 11 119507 Hg_KMnO4 - Mercure... 129 11 119507 Métaux_solution (11 figures)... 130 11 119507 Métaux Poussière Protocole libre (11 figures)... 141 11 119507 Métaux Poussière Protocole imposé (11 figures)... 152 ANNEX 4 GENERAL ORGANIZATION, DESCRIPTION OF TESTS AND ALGORITHMS... 163 Figure 1 : 11/119507_Métaux solution (part 1 to 3)... 164 Figure 2: 11/119507_Métaux poussière Free Protocol (part 1 to 3)... 167 Figure 3: 11/119507_Métaux poussière Imposed Protocole (part 1 to 2)... 170 DRC-11-119507-08855B Page 6 sur 171
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-11-119507-08855B Page 7 sur 171
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-11-119507-08855B Page 8 sur 171
3 REFERENCE DOCUMENTS Decree of March 11, 2010 : Decree pertaining to approval terms for laboratories or entities for certain types of samples and analyses upon the emission of substances into the atmosphere (NOR: DEVE1007687A) LAB-CIL REF 02 : COFRAC (French organism of accreditation) reference document relative to the organizers of inter-laboratory comparisons Accreditation requirements Revision 03 March 2011, LAB REF 22 : COFRAC reference document relative to specific requirements Air quality Emissions from fixed sources Revision 00 June 2009, EN ISO/CEI 17043 : general requirements concerning aptitude tests April 2010, ISO 5725-1 : applications of the statistics Accuracy (correctness and faithfulness) of the results and measurement methods Part 1: general principles and definitions December 1994, ISO 5725-2 : application of the statistics Accuracy (correctness and faithfulness) of the measurement results Part 2: basic method for determining the repeatability and reproducibility of a standardized measurement method December 1994, ISO 5725-5 : application of the statistics Accuracy (correctness and faithfulness) of the measurement results Part 5: alternative methods for determining the faithfulness of a standardized measurement method December 1998, ISO 13528 : statistical methods used in aptitude tests by inter-laboratory comparisons December 2005, ISO 3534-2 : vocabulary and symbols Part 2: Applied statistics December 2006, NF X06-050 : application of the statistics Study of the normality of a distribution December 1995. DRC-11-119507-08855B Page 9 sur 171
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 60550 VERNEUIL- EN-HALATTE 03.44.55.66.77 03.44.55.66.99 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-11-119507-08855A distributed on 07/11/2011. It is accessible on the site http://www.ineris.fr/eil/. 7 INTRODUCTION These tests were organized by the INERIS according to a program developed in agreement with the Steering Committee for the tests bringing together three experts designated by the MEDDTL (Ministry of Ecology, Sustainable Development, Transportation and Housing), members of the Laboratory or Entity Approval Committee for the performance of certain types of sampling and analyses upon emission of substances into the atmosphere. One of the purposes of these tests is to determine the analytical repeatability and reproducibility standard deviations obtained in the implementation of the reference methods defined by the aforementioned decree and detecting any bias or factors influencing the measuring quality. Participation in these inter-laboratory tests was mandatory for the approved laboratories. Outside this regulatory context, participation in inter-laboratory tests is an essential tool in monitoring the mastery of the implementation of chemical analysis methods. To that end, it is subject to a COFRAC requirement in the context of accreditation according to referential EN ISO/CEI 17025 and leads to verification of the proper execution of this requirement during evaluations. DRC-11-119507-08855B Page 10 sur 171
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-11-119507-08855B Page 11 sur 171
The equipment used by the participants as well as the methodologies applied and the results relative to the tests are presented in this report anonymously, using the confidential codes assigned to the participants when they registered for the tests. 10 DESCRIPTION OF THE TEST MATERIALS 10.1 DESCRIPTION AND INSTRUCTIONS The same operator or team should perform all of the analyses for a given parameter, in a short time interval, specified for each compound below. These analyses should be considered independent tests: all of the operations were to be repeated, from sampling in the bottles to expression of the final result. 10.1.1 Total mercury in permanganate medium An absorption solution was prepared according to the stipulations of standard EN 13211, then was used as flushing solution on the INERIS test block where combustion gases were generated, in order to create a matrix as close as possible (presence of interferents) to samples usually analyzed. This absorption solution, made up of 2% of 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 13211. Two measurements were requested per bottle provided, or a total of 4 measurements expressed in µg Hg/L with zero decimals. It was strongly recommended to analyze these solutions within a maximum of 15 days (Cf EN 13211), the stability not being verified beyond that period. 10.1.2 Total mercury in dichromate medium 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 13211. Two measurements were requested per bottle provided, or a total of 4 measurements expressed in µg Hg/L with zero decimals. It was strongly recommended to analyze these solutions within a maximum of 15 days (Cf EN 13211), the stability not being verified beyond that period. DRC-11-119507-08855B Page 12 sur 171
10.1.3 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 1911. Two measurements were requested per bottle provided, or a total of 4 measurements expressed in mg HCl/L with one decimal. 10.1.4 Fluorhydric acid 10.1.4.1 Solution An absorption solution was prepared according to the stipulations of standard NF X 43-304, then was used as flushing solution on the INERIS test block where combustion gases were generated, in order to create a matrix as close as possible (presence of interferents) to samples usually analyzed. This absorption solution made up NaOH 0.1 N was analyzed, then spiked to make up the test material referenced 11/119507_HF solution. Two samples (X and Y) were taken out to be sent to each participant in order to determine the so-called HF gas content. The measurements have been done using standard laboratory methods. Two measurements were requested per bottle provided, or a total of 4 measurements expressed in mg HF/L with one decimal. 10.1.4.2 Dusts Dusts coming from a household waste incineration unit, previously analyzed, were dried and shredded to be spiked with fluorinated salts (NaF, CaF and 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-11-119507-08855B Page 13 sur 171
10.1.5 Metals (and metalloids) 10.1.5.1 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 14385. Two measurements were requested per bottle provided, or a total of 4 measurements expressed in µg/l with zero decimals. 10.1.5.2 Dusts Dusts coming from a glassworks manufacturing plant, previously analyzed, were dried and shredded to be spiked with oxides, also dried and shredded. The whole was homogenized in order to make up the final test material referenced 11/119507_Metaux Poussières. Two samples (X and Y) were taken out to be sent to each participant in order to determine the content level in As, Cd, Cr, Co, Cu, Mn, Ni, Pb, Sb, Tl and V expressed in µg /g with one decimal. The laboratories were asked to respect the following two protocols: free protocol: Usual practice of the laboratory in measuring particulate metals (EN 14385), imposed protocol: Free protocol with the requirement of not filtering the mineral residues before analysis. 10.1.6 Sulfur dioxide 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 14791. Two measurements were requested per bottle provided, or a total of 4 measurements expressed in mg SO 2 /L with one decimal. DRC-11-119507-08855B Page 14 sur 171
10.1.7 Ammonia An absorption solution was prepared according to the stipulations of standard NF X 43-303, then was used as flushing solution on the INERIS test block where combustion gases were generated. This absorption solution made up of H 2 SO 4 0.1 N was analyzed, then spiked to make up the test material referenced 11/119507_NH3. Two samples (X and Y) were taken out to be sent to each participant in order to determine the 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 43-303, of errors in the description of the colorimetric method using indophenol blue and that it was preferable to refer to other standards (For example: NF T 90-015-2 and EN ISO 11732). 11 SHIPPING A first shipment was done on May 17, 2011. For reasons inherent to our service provider, this first shipment was cancelled, requiring the production of new lots of test materials for the sensitive parameters (Hg). A second shipment was done on May 24, 2011. 12 HOMOGENEITY AND STABILITY OF THE SAMPLES 12.1 HOMOGENEITY OF THE MATERIALS The homogeneity of the materials was verified at the time of their distribution, according to the methodology explained in annex 1. DRC-11-119507-08855B Page 15 sur 171
Test materials Homogeneity of the test materials Homogeneity according to ISO 13528 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 - 12.2 STABILITY OF THE TEST MATERIALS For each lot of test materials, 9 samples were randomly taken so as to establish the stability of the materials at the time of their distribution and during the analysis period by the participants. Three samples were analyzed once per week for three weeks in double determination. The stability of the materials was verified according to the methodology presented in annex 1. Note: Because of internal analytical problem, the stability study of HCl has not been validated. Nevertheless, the study of the distribution of laboratory measures by time showed no significant trend due to a time effect. DRC-11-119507-08855B Page 16 sur 171
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 13.1.1 General information The details of the statistical processing are recalled in annex 1. In the context of this test, the assigned values were defined as follows: the value assigned to the average is taken to be equal to the robust average of the results provided by the participants in the inter-laboratory comparison, the reference value of the standard deviation for assessing the aptitude is taken to be equal to the robust standard deviation. The statistical processing applied to the data made it possible to determine: - the reference value (or assigned value) of each parameter for each test and its associated uncertainty, - each participant s performance relative to the reference values via the z score indicator, - suspicious or absurd results, - the repeatability and reproducibility confidence intervals for each compound and each test material. 13.1.2 Presentation of the results In this section, the results obtained before and after statistical processing, averages, repeatability standard deviations and performance of each laboratory (z score) are presented for each test material. A distribution diagram of the z scores making it possible to situate each laboratory globally relative to the other laboratories is also provided. DRC-11-119507-08855B Page 17 sur 171
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-11-119507-08855B Page 18 sur 171
13.1.3 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 12 9.8 4.0 40.5% 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-11-119507-08855B Page 19 sur 171
Averages, standard deviations and z scores for the laboratories Laboratory Identification x µg/l s r µg/l Mercury s r % Z scores 11201 8.5 1.0 11.7% -1.50 11207 Not analyzed 11209 10.2 1.5 14.6% -0.64 11210 Not analyzed 11212 Not analyzed 11236 13.2 2.2 16.7% 0.85 11249 12.0 0.0 0.0% 0.23 11250 Not analyzed 11255 10.5 0.6 5.5% -0.51 11262 < 1.0 0.0 0.0% (-5.22)* 11273 Not analyzed 11275 < 5.0 0.0 0.0% (-3.24)* 11279 12.5 0.6 4.6% 0.48 11281 13.0 0.0 0.0% 0.73 11283 11.8 0.5 4.3% 0.11 11285 Not analyzed 11288 Not analyzed 11291 Not analyzed ()*: Z score calculated relative to the threshold value rendered. NB: the absolute value is bounded from below. Remarks and comments : Laboratories 11262 and 11275 delivered results in the form of measurement thresholds respectively of < 1 and < 5 µg/l. They were excluded from the robust statistical processing by expert opinion. DRC-11-119507-08855B Page 20 sur 171
Laboratory 11236 was marked as abnormal by the Mandel k test due to its intralaboratory dispersion. 13.1.4 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 (%) 1.8 15.6% 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-11-119507-08855B Page 21 sur 171
Averages, standard deviations and z scores for the laboratories Laboratory Identification x µg/l s r µg/l Mercury 11201 Not analyzed s r % Z Scores 11207 12.50 1.29 10.33 0.69 11209 Not analyzed 11210 11.48 0.13 1.10 0.27 11212 < 10.00 0.00 0.00 (-0.71)* 11236 9.25 0.50 5.41-1.14 11249 9.75 0.50 5.13-0.86 11250 12.25 0.06 0.51 0.41 11255 11.50 0.58 5.02 0.13 11262 10.00 0.00 0.00-0.71 11273 10.50 0.58 5.50-0.43 11275 15.75 0.50 3.17 2.51 11279 Not analyzed 11281 Not analyzed 11283 11.25 0.50 4.44-0.01 11285 13.00 0.00 0.00 0.97 11288 9.30 0.08 0.88-1.28 11291 12.25 0.50 4.08 0.55 ()*: Z score calculated relative to the threshold value rendered. NB: the absolute value is bounded from below. Remarks and comments : Laboratory 11275 obtained a z score between 2 and 3. Laboratory 11212 rendered a threshold value of 10 µg/l. It was excluded from the robust statistical processing by expert opinion. DRC-11-119507-08855B Page 22 sur 171
Laboratory 11207 has a higher intra-laboratory dispersion than the rest of the population. 13.1.5 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 19.31 Population Standard Deviation CV R (%) CV rep (%) 0.99 5.13% 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* 19.27 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-11-119507-08855B Page 23 sur 171
Averages, standard deviations and z scores for the laboratories Laboratory Identification x mg/l Hydrochloric_Acid s r mg/l s r % Z Scores 11207 18.65 0.13 0.69% -0.60 11210 21.15 0.41 1.95% 1.84 11212 18.48 0.05 0.27% -0.77 11222 19.60 0.08 0.42% 0.33 11226 19.25 0.06 0.30% -0.01 11236 19.40 0.47 2.42% 0.13 11249 19.20 0.00 0.00% -0.06 11251 19.58 0.10 0.49% 0.30 11255 20.78 1.47 7.09% 1.48 11259 19.40 0.00 0.00% 0.13 11262 18.15 0.53 2.93% -1.09 11273 18.08 0.57 3.17% -1.16 11275 18.40 0.08 0.44% -0.85 11279 19.78 0.10 0.48% 0.50 11281 17.98 0.34 1.89% -1.26 11283 21.28 0.46 2.15% 1.96 11288 18.88 0.22 1.17% -0.38 11291 19.60 0.00 0.00% 0.33 Remarks and comments : Laboratory 11255 has a higher intra-laboratory dispersion than the rest of the population. DRC-11-119507-08855B Page 24 sur 171
13.1.6 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 (%) 0.10 5.04% 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-11-119507-08855B Page 25 sur 171
Averages, standard deviations and z scores for the laboratories Laboratory Identification x mg/l Fluorhydric Acid s r mg/l s r % Z Scores 11209 1.81 0.03 1.47% -0.77 11210 1.88 0.10 5.34% -0.04 11212 1.75 0.01 0.57% -1.35 11214 1.93 0.03 1.77% 0.42 11226 1.75 0.07 3.81% -1.33 11236 1.87 0.02 1.19% -0.16 11249 1.83 0.02 1.30% -0.57 11250 1.95 0.03 1.48% 0.59 11255 2.01 0.09 4.71% 1.18 11262 1.83 0.03 1.75% -0.50 11273 1.88 0.05 2.39% -0.01 11275 1.91 0.01 0.50% 0.28 11279 1.98 0.01 0.25% 0.96 11283 1.96 0.04 1.82% 0.74 11285 1.75 0.01 0.29% -1.33 11288 2.08 0.06 3.10% 1.88 11291 1.93 0.03 1.50% 0.40 DRC-11-119507-08855B Page 26 sur 171
Remarks and comments : Laboratories 11255 and 11210 have a higher intra-laboratory dispersion than the other laboratories. 13.1.7 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 10.25 Population Standard Deviation CV R (%)%) CV rep (%)%) 5.16 50.4% 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 4.96 5.02 0.83 Relative IC R (%) 108.0% Relative IC r (%) 17.8% DRC-11-119507-08855B Page 27 sur 171
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 11209 14.03 1.05 7.46% 0.83 11210 21.88 1.93 8.80% 2.40 11212 9.30 0.68 7.29% -0.12 11214 12.75 0.97 7.59% 0.57 11226 Not analyzed 11236 6.25 0.17 2.77% -0.74 11249 12.00 0.42 3.54% 0.42 11250 11.70 0.16 1.40% 0.36 11255 4.48 0.21 4.61% -1.09 11262 3.63 0.24 6.52% -1.26 11273 14.13 1.63 11.51% 0.85 11275 13.25 0.54 4.11% 0.67 11279 1.00 0.10 10.00% -1.79 11283 9.40 0.52 5.51% -0.10 11285 9.60 0.35 3.61% -0.06 11288 5.17 1.28 24.76% -0.95 11291 13.10 0.55 4.18% 0.64 DRC-11-119507-08855B Page 28 sur 171
Remarks and comments : Laboratory 11210 is beyond the monitoring limit and has a larger repeatability standard deviation than the rest of the population. Given the high inter-laboratory dispersion, the calculation of the z score does not make it possible to judge each laboratory s performance precisely. To situate their results, the laboratories are therefore advised to compare, for information, their averages values to the spiking value even if it is not the reference value for the exercise. Despite harmonization in the measuring of the particulate fluorinated compounds by quasi-systematic integration of alkali fusion, the inter-laboratory dispersion in the vicinity of 50% remains relatively significant for this analysis. The data collected via the online entry form does not make it possible to clearly explain this phenomenon. Nevertheless, it would be interesting to set certain parameters that can unbalance the robustness of the method, such as test-taking, for example. In fact, the impossibility of distributing filters to the laboratories on which a constant and homogenous quantity of dust is deposited leaves a broad choice in the initial test-taking. 13.1.8 Test material "11/119507_Metaux_solution" 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 (%) 450 130 20 190 220 230 210 220 480 20 190 455.5 132.3 20.9 189.9 215.0 224.8 214.2 212.4 488.9 20.2 185.5 22.2 8.9 4.6 20.5 24.3 23.5 26.5 24.3 17.5 3.2 20.4 4.87% 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 14 14 14 14 14 14 14 14 14 14 14 S L 22.1 8.8 4.6 20.5 24.3 23.4 26.4 24.2 17.3 3.2 20.3 S R 22.6 9.2 4.6 20.7 24.4 23.6 26.6 24.4 18.1 3.2 20.5 S r 4.9 2.8 0.4 2.9 2.5 2.9 2.5 3.5 5.2 0.7 2.4 DRC-11-119507-08855B Page 29 sur 171
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 450 130 20 190 220 230 210 220 480 20 190 x* 456.8 132.3 20.4 194.0 220.8 228.7 220.3 216.9 488.9 20.9 189.1 s* 22.1 10.1 0.9 8.3 8.4 15.3 7.2 12.6 19.9 1.2 11.8 u X* 7.4 3.4 0.3 2.8 2.8 5.1 2.4 4.2 6.6 0.4 3.9 w* 4.2 2.8 0.0 3.0 2.7 2.7 2.7 3.8 3.4 0.0 2.6 S L 22.0 10.0 0.9 8.2 8.3 15.2 7.0 12.5 19.8 1.2 11.7 S R 22.4 10.4 0.9 8.7 8.7 15.4 7.5 13.1 20.1 1.2 12.0 S r 4.2 2.8 0.0 3.0 2.7 2.7 2.7 3.8 3.4 0.0 2.6 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 11210 468.2 2.2 0.47% 0.49 125.5 1.3 1.03% -0.64 11212 467.2 1.5 0.32% 0.45 135.2 1.0 0.71% 0.28 11232 487.5 0.6 0.12% 1.32 118.8 5.6 4.73% -1.27 11236 458.0 3.6 0.78% 0.05 144.5 2.5 1.74% 1.15 11240 446.5 1.9 0.43% -0.44 126.8 0.5 0.39% -0.52 11249 490.0 2.2 0.44% 1.42 134.5 1.3 0.96% 0.21 11250 445.7 1.6 0.37% -0.47 125.3 1.7 1.32% -0.66 11255 438.0 5.7 1.29% -0.80 144.0 2.7 1.88% 1.10 11262 406.0 13.3 3.27% -2.18 127.5 1.0 0.78% -0.45 11273 465.8 6.4 1.37% 0.38 142.5 1.3 0.91% 0.96 11275 448.2 1.0 0.21% -0.37 117.5 0.6 0.49% -1.39 11279 458.0 6.9 1.51% 0.05 135.5 2.5 1.86% 0.30 11283 430.2 0.5 0.12% -1.14 134.2 4.2 3.12% 0.19 11288 467.8 2.5 0.53% 0.47 140.0 5.2 3.69% 0.73 DRC-11-119507-08855B Page 30 sur 171
Remarks and comments : Antimony : Laboratory 11262 obtained a z score between 2 and 3 and its intra-laboratory dispersion is higher than the rest of the population. DRC-11-119507-08855B Page 31 sur 171
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 11210 21.0 0.0 0.00% 0.65 197.5 1.3 0.65% 0.39 11212 21.0 0.0 0.00% 0.65 199.2 1.0 0.48% 0.59 11232 12.8 0.5 3.92% -8.28 122.2 3.5 2.86% -8.20 11236 21.0 0.0 0.00% 0.65 193.2 1.3 0.65% -0.09 11240 20.0 0.0 0.00% -0.43 194.0 1.6 0.84% -0.01 11249 21.0 0.0 0.00% 0.65 191.0 1.8 0.96% -0.35 11250 19.6 0.4 1.84% -0.70 190.1 0.6 0.34% -0.46 11255 20.0 0.0 0.00% -0.43 187.5 3.7 1.97% -0.75 11262 20.2 0.5 2.47% -0.16 193.8 1.5 0.77% -0.03 11273 19.5 0.6 2.96% -0.97 200.2 2.4 1.18% 0.71 11275 21.0 0.0 0.00% 0.65 181.2 0.5 0.28% -1.46 11279 35.0 0.0 0.00% 15.81 198.2 6.1 3.06% 0.48 11283 19.5 0.6 2.96% -0.97 207.2 3.2 1.54% 1.51 11288 20.8 1.0 4.61% 0.38 202.2 5.4 2.69% 0.94 DRC-11-119507-08855B Page 32 sur 171
Remarks and Comments : Cadmium : Laboratories 11232 and 11279 obtained z scores greater than 3. Laboratory 11288 has a higher intra-laboratory dispersion than the rest of the population. Chromium : Laboratory 11232 obtained a z score greater than 3. Laboratory 11288 has a higher intra-laboratory dispersion than the rest of the population. DRC-11-119507-08855B Page 33 sur 171
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 11210 225.0 1.4 0.63% 0.45 236.0 0.8 0.35% 0.45 11212 227.8 1.0 0.42% 0.74 243.5 1.3 0.53% 0.92 11232 135.0 4.2 3.14% -9.18 155.2 4.4 2.85% -4.57 11236 229.5 0.6 0.25% 0.93 244.8 1.0 0.39% 1.00 11240 216.0 1.4 0.65% -0.51 229.0 1.6 0.71% 0.02 11249 227.8 1.7 0.75% 0.74 241.2 1.9 0.78% 0.78 11250 215.2 1.2 0.55% -0.59 225.0 0.9 0.40% -0.21 11255 200.8 4.3 2.13% -2.15 208.2 7.1 3.43% -1.27 11262 218.5 1.9 0.88% -0.25 240.5 2.4 0.99% 0.73 11273 219.8 1.5 0.68% -0.11 233.0 3.6 1.53% 0.27 11275 215.0 0.0 0.00% -0.62 202.8 1.0 0.47% -1.61 11279 226.5 4.6 2.06% 0.61 231.0 0.8 0.35% 0.14 11283 225.2 0.5 0.22% 0.48 232.5 2.9 1.24% 0.24 11288 228.8 3.5 1.53% 0.85 225.2 3.0 1.33% -0.21 DRC-11-119507-08855B Page 34 sur 171
Remarks and Comments : Cobalt : Laboratory 11232 obtained a z score greater than 3. Laboratory 11255 obtained a z score between 2 and 3. Laboratory 11279 has a higher intra-laboratory dispersion than the rest of the population. Copper : Laboratory 11232 obtained a z score greater than 3. Laboratory 11255 has a higher intra-laboratory dispersion than the rest of the population. DRC-11-119507-08855B Page 35 sur 171
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 11210 224.0 0.8 0.36% 0.49 229.0 0.8 0.36% 0.90 11212 225.8 1.0 0.42% 0.72 227.8 1.0 0.42% 0.81 11232 124.2 4.0 3.24% -12.74 135.2 4.4 3.22% -6.12 11236 227.2 1.9 0.83% 0.92 227.8 1.0 0.42% 0.81 11240 212.5 1.3 0.61% -1.03 218.8 1.7 0.78% 0.14 11249 225.0 1.4 0.63% 0.62 219.0 2.2 0.99% 0.15 11250 216.2 1.6 0.76% -0.54 213.1 1.0 0.45% -0.26 11255 210.5 3.7 1.76% -1.30 199.8 5.9 2.96% -1.29 11262 218.8 2.8 1.26% -0.20 203.8 3.0 1.47% -0.99 11273 223.0 2.9 1.32% 0.36 217.0 3.8 1.76% 0.00 11275 216.8 1.0 0.44% -0.47 205.0 2.9 1.44% -0.90 11279 229.2 1.7 0.74% 1.19 226.2 5.5 2.43% 0.70 11283 222.5 2.9 1.30% 0.29 226.8 1.3 0.55% 0.74 11288 223.0 4.2 1.87% 0.36 225.0 6.4 2.83% 0.60 DRC-11-119507-08855B Page 36 sur 171
Remarks and Comments : Manganese : Laboratory 11232 obtained a z score greater than 3. Nickel : Laboratory 11232 obtained a z score greater than 3. DRC-11-119507-08855B Page 37 sur 171
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 11210 496.0 3.2 0.64% 0.32 22.0 0.0 0.00% 0.91 11212 496.8 1.0 0.19% 0.36 22.2 0.5 2.25% 1.11 11232 504.5 1.7 0.34% 0.71 <10.0 0.0 0.00% (-8.73)* 11236 499.8 2.9 0.57% 0.49 24.0 2.0 8.33% 2.52 11240 467.8 2.5 0.53% -0.96 20.0 0.0 0.00% -0.69 11249 502.5 3.1 0.62% 0.62 21.0 0.0 0.00% 0.11 11250 490.0 0.2 0.04% 0.05 20.3 0.2 0.76% -0.69 11255 467.5 1.9 0.41% -0.98 19.0 0.0 0.00% -1.50 11262 469.8 16.3 3.47% -0.87 20.8 1.0 4.61% -0.09 11273 491.5 4.1 0.84% 0.12 20.0 0.0 0.00% -0.69 11275 474.8 2.5 0.53% -0.65 20.0 0.0 0.00% -0.69 11279 517.5 2.4 0.46% 1.30 21.0 0.0 0.00% 0.11 11283 461.2 1.0 0.21% -1.26 21.0 1.2 5.50% 0.11 11288 505.5 6.0 1.18% 0.75 21.5 1.0 4.65% 0.51 ()* : Z score calculated relative to the threshold value rendered. NB: the absolute value is bounded from below. DRC-11-119507-08855B Page 38 sur 171
Remarks and comments : Lead : Laboratory 11262 has a higher intra-laboratory dispersion than the rest of the population. Thallium : Laboratory 11232 returned results in the form of a measurement threshold of < 10 µg/l. It was excluded from the robust statistical processing. Laboratory 11236 obtained a z score between 2 and 3. Furthermore, it is marked by the Cochran and Mandel k tests as having an excessively high intra-laboratory dispersion. DRC-11-119507-08855B Page 39 sur 171
Averages, standard deviations and z scores for the laboratories Laboratory Identification x µg/l Vanadium s r µg/l s r % Z Scores 11210 196.5 0.6 0.29% 0.59 11212 198.5 0.6 0.29% 0.76 11232 122.5 4.2 3.43% -5.34 11236 196.2 1.0 0.49% 0.57 11240 188.8 1.7 0.90% -0.03 11249 201.2 1.9 0.94% 0.98 11250 181.7 0.4 0.25% -0.59 11255 186.5 3.8 2.03% -0.21 11262 188.5 1.0 0.53% -0.05 11273 194.5 3.8 1.95% 0.43 11275 182.2 0.5 0.27% -0.55 11279 184.0 4.1 2.22% -0.41 11283 205.8 1.0 0.47% 1.34 11288 170.2 2.5 1.47% -1.51 Remarks and comments : Laboratory 11232 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 11232 must undertake corrective actions for 73% of the analytes measured. DRC-11-119507-08855B Page 40 sur 171
13.1.9 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 * * 201 1564 1786 1906 1681 1804 * 255 1533 5760.7 1853.8 215.0 729.9 1755.4 1953.4 1617.7 1644.6 35461.6 235.2 1446.4 695.0 736.4 99.3 610.8 258.9 241.1 400.3 478.6 4883.7 90.2 222.1 12.1% 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 13 13 13 13 13 13 13 13 13 13 13 S L 635.7 728.6 99.8 611.3 234.5 211.6 395.3 480.2 4748.5 84.4 211.7 S R 715.9 733.6 100.0 617.3 254.3 225.9 407.0 487.4 4957.1 85.0 225.7 S r 329.3 85.7 7.6 85.7 98.2 79.0 97.1 83.2 1422.8 10.1 78.2 * Compounds for which it was not necessary to add a dopant. 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 * * 201 1564 1786 1906 1681 1804 * 255 1533 x* 5753.9 1720.0 190.2 708.5 1731.9 1943.0 1583.2 1558.5 34973.5 233.1 1433.5 s* 693.7 585.3 32.1 692.6 217.3 203.1 361.7 285.1 4997.1 53.4 251.1 u X* 240.5 202.9 11.1 240.1 75.3 70.4 125.4 98.8 1732.4 18.5 87.1 w* 181.4 57.8 8.0 45.9 102.1 58.9 103.5 46.6 1029.3 11.2 60.2 S L 687.5 584.5 31.9 692.2 211.0 200.9 357.8 284.1 4969.4 53.1 249.2 S R 711.0 587.4 32.9 693.7 234.4 209.4 372.5 287.9 5074.9 54.2 256.4 S r 181.4 57.8 8.0 45.9 102.1 58.9 103.5 46.6 1029.3 11.2 60.2 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-11-119507-08855B Page 41 sur 171
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 11210 5781.5 132.1 2.28% 0.04 1475.8 61.2 4.15% -0.38 11212 5988.0 164.9 2.75% 0.32 1449.8 34.9 2.40% -0.42 11232 5046.2 14.9 0.30% -0.96 1405.0 52.6 3.74% -0.49 11236 6702.8 166.9 2.49% 1.29 2443.0 66.9 2.74% 1.12 11240 6037.8 30.3 0.50% 0.39 1805.5 23.4 1.30% 0.13 11249 5615.8 105.5 1.88% -0.19 1335.5 26.4 1.98% -0.60 11250 Not analyzed Not analyzed 11255 5910.5 114.2 1.93% 0.21 1516.5 32.8 2.16% -0.32 11262 4406.0 200.4 4.55% -1.84 1342.8 14.9 1.11% -0.58 11273 6092.2 877.9 14.41% 0.46 1762.5 198.9 11.28% 0.07 11275 5603.8 4.4 0.08% -0.20 2850.0 47.6 1.67% 1.75 11279 4458.0 1080.5 24.24% -1.77 975.0 1.4 0.15% -1.15 11283 6385.5 149.7 2.34% 0.86 1653.5 31.9 1.93% -0.10 11288 6210.2 130.4 2.10% 0.62 3645.2 181.5 4.98% 2.98 DRC-11-119507-08855B Page 42 sur 171
Remarks and Comments : Antimony : Laboratories 11273 and 11279 have higher intra-laboratory dispersions than the rest of the population. Arsenic : Laboratory 11288 obtained a Z score between 2 and 3. Furthermore, according to the Cochran and Mandel k tests, it has a higher intra-laboratory dispersion than the rest of the population. This last observation is also valid for laboratory 11273. DRC-11-119507-08855B Page 43 sur 171
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 11210 209.0 14.5 6.93% 0.55 932.2 17.4 1.87% 0.31 11212 177.0 2.2 1.22% -0.39 1421.2 28.7 2.02% 0.97 11232 145.0 3.5 2.39% -1.33 32.5 3.0 9.23% -0.92 11236 205.8 8.6 4.17% 0.46 200.0 99.2 49.59% -0.69 11240 194.2 3.3 1.70% 0.12 1599.5 29.5 1.84% 1.22 11249 175.0 3.6 2.03% -0.45 1345.8 50.3 3.73% 0.87 11250 Not analyzed Not analyzed 11255 185.0 1.2 0.62% -0.15 673.0 11.9 1.77% -0.05 11262 196.2 3.3 1.68% 0.18 10.5 1.7 16.50% -0.95 11273 225.5 11.7 5.18% 1.04 970.2 267.1 27.52% 0.36 11275 172.2 2.1 1.20% -0.53 42.8 0.5 1.17% -0.91 11279 129.0 5.7 4.39% -1.80 173.0 55.2 31.88% -0.73 11283 530.2 13.2 2.49% 10.00 1470.0 53.1 3.61% 1.04 11288 207.5 7.0 3.40% 0.51 339.5 28.7 8.44% -0.50 DRC-11-119507-08855B Page 44 sur 171
Remarks and comments : Cadmium : Laboratory 11283 obtained a Z score greater than 3. Laboratory 11210 has a greater intra-laboratory dispersion than the rest of the population. Chromium : Laboratories 11236 and 11273 are marked by the Cochran test as having significant intra-laboratory dispersions relative to those of the rest of the population. DRC-11-119507-08855B Page 45 sur 171
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 11210 1651.5 136.9 8.29% -0.35 1846.2 33.9 1.83% -0.45 11212 1705.2 106.6 6.25% -0.12 1963.0 37.5 1.91% 0.09 11232 1502.5 62.0 4.13% -1.00 1662.5 36.6 2.20% -1.30 11236 2285.5 145.1 6.35% 2.41 2359.0 11.9 0.50% 1.93 11240 1828.5 21.2 1.16% 0.42 2077.2 44.1 2.12% 0.62 11249 1594.0 100.5 6.30% -0.60 1902.8 66.2 3.48% -0.19 11250 Not analyzed Not analyzed 11255 1674.0 91.5 5.47% -0.25 1844.0 48.4 2.62% -0.46 11262 1642.8 36.0 2.19% -0.39 1844.2 50.4 2.73% -0.46 11273 1986.8 188.2 9.47% 1.11 2139.2 233.6 10.92% 0.91 11275 1844.5 7.0 0.38% 0.49 2112.5 15.0 0.71% 0.79 11279 1212.5 36.1 2.97% -2.26 1371.0 91.9 6.70% -2.66 11283 1671.2 19.3 1.16% -0.26 1989.5 21.4 1.08% 0.22 11288 1949.8 86.2 4.42% 0.95 1991.5 60.7 3.05% 0.23 DRC-11-119507-08855B Page 46 sur 171
Remarks and comments : Cobalt : Laboratories 11236 and 11279 obtained z scores between 2 and 3. According to the Mandel test, laboratory 11273 has a higher intra-laboratory dispersion than the rest of the population. Copper : Laboratory 11279 obtained a z score between 2 and 3. Laboratory 11273 is marked by the Cochran test as having significant intra-laboratory dispersions relative to the rest of the population. DRC-11-119507-08855B Page 47 sur 171
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 11210 1148.2 50.6 4.41% -1.14 1542.0 10.1 0.65% -0.05 11212 1623.2 37.4 2.30% 0.10 1589.5 23.6 1.48% 0.10 11232 1450.0 52.1 3.59% -0.35 1186.2 19.3 1.63% -1.23 11236 1993.5 128.0 6.42% 1.07 3020.0 57.1 1.89% 4.84 11240 2493.5 15.9 0.64% 2.38 1563.0 35.2 2.25% 0.01 11249 1585.8 172.9 10.91% 0.01 1463.0 37.1 2.53% -0.32 11250 Not analyzed Not analyzed 11255 1545.5 84.9 5.49% -0.10 1575.8 44.8 2.84% 0.06 11262 900.8 160.5 17.82% -1.78 1024.0 176.9 17.27% -1.77 11273 1797.5 169.2 9.41% 0.56 1848.5 205.9 11.14% 0.96 11275 1725.2 6.1 0.35% 0.37 1751.2 21.0 1.20% 0.64 11279 1175.0 25.5 2.17% -1.07 1260.5 9.2 0.73% -0.99 11283 1680.8 30.5 1.82% 0.25 1644.2 37.9 2.30% 0.28 11288 1690.2 15.2 0.90% 0.28 1719.8 28.9 1.68% 0.53 DRC-11-119507-08855B Page 48 sur 171
Remarks and comments : Manganese : Laboratory 11240 obtained a z score between 2 and 3. Nickel : Laboratory 11236 obtained a z score greater than 3. Laboratories 11262 and 11273 are marked by the Cochran and Mandel k tests as having higher intra-laboratory dispersions than the rest of the population. DRC-11-119507-08855B Page 49 sur 171
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 11210 33350.8 1080.6 3.24% -0.31 238.2 6.13 2.57% -0.07 11212 36977.5 1064.8 2.88% 0.38 78.6 3.24 4.12% -3.76 11232 33625.0 1532.7 4.56% -0.25 232.0 2.45 1.06% -0.21 11236 45203.2 1185.6 2.62% 1.93 258.8 15.44 5.97% 0.41 11240 35515.2 474.3 1.34% 0.10 245.2 2.22 0.90% 0.09 11249 34408.0 980.1 2.85% -0.11 218.2 13.00 5.96% -0.53 11250 Not analyzed Not analyzed 11255 31392.0 523.8 1.67% -0.68 244.8 10.72 4.38% 0.08 11262 35527.0 361.1 1.02% 0.10 249.8 6.29 2.52% 0.20 11273 27593.2 4065.2 14.73% -1.40 289.8 18.30 6.32% 1.12 11275 42825.0 250.0 0.58% 1.48 184.2 4.35 2.36% -1.31 11279 28951.0 455.4 1.57% -1.14 56.5 10.61 18.77% -4.27 11283 34649.5 258.5 0.75% -0.06 250.5 2.38 0.95% 0.22 11288 37728.2 771.5 2.05% 0.52 421.8 15.90 3.77% 4.17 DRC-11-119507-08855B Page 50 sur 171
Remarks and comments : Lead : Laboratory 11273 is marked by the Cochran and Mandel k tests as having a higher intralaboratory dispersion than the rest of the population. Thallium : Laboratories 11212, 11279 and 11288 obtained z scores greater than 3. Laboratory 11279 was excluded from the robust statistical tests by expert opinion for delivering 2 results, 1 in threshold form. DRC-11-119507-08855B Page 51 sur 171
Averages, standard deviations and z scores for the laboratories Laboratory Identification x µg/g Vanadium s r µg/g s r % Z Scores 11210 1463.8 66.7 4.56% 0.11 11212 1616.0 35.9 2.22% 0.69 11232 1052.5 17.6 1.67% -1.43 11236 1326.8 27.6 2.08% -0.40 11240 1768.2 10.8 0.61% 1.26 11249 1352.2 74.0 5.47% -0.31 11250 Not analyzed 11255 1398.5 27.3 1.95% -0.13 11262 1469.2 44.2 3.01% 0.13 11273 1604.8 217.8 13.57% 0.64 11275 1198.8 17.5 1.46% -0.88 11279 1102.5 44.6 4.04% -1.25 11283 1613.5 93.2 5.78% 0.68 11288 1664.5 56.9 3.42% 0.87 Remarks and comments : Laboratory 11273 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-11-119507-08855B Page 52 sur 171
13.1.10 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 * * 201 1564 1786 1906 1681 1804 * 255 1533 6138.0 1886.5 243.6 931.4 1831.7 2034.7 1837.5 1783.3 36066.4 272.4 1511.2 402.9 671.2 138.6 549.3 174.0 172.8 290.6 469.9 4549.1 74.2 169.2 6.6% 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 10 10 10 10 10 10 10 10 10 10 10 S L 343.7 676.4 141.2 543.3 170.8 163.6 291.2 479.7 4581.3 67.2 166.0 S R 463.1 685.5 141.4 585.2 195.9 194.7 309.0 486.3 4907.7 69.5 188.8 S r 310.4 111.7 6.8 217.5 95.9 105.6 103.6 79.9 1759.7 17.8 90.1 * 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 * * 201 1564 1786 1906 1681 1804 * 255 1533 x* 6173.4 1724.2 202.2 953.5 1811.6 2015.3 1752.4 1671.0 35922.3 263.0 1504.2 s* 456.9 386.4 33.5 622.9 157.3 171.2 143.7 179.1 2326.9 46.1 187.2 u X* 180.6 152.7 13.2 246.2 62.2 67.7 56.8 70.8 919.8 18.2 74.0 w* 173.1 92.2 7.2 144.1 96.9 84.4 104.5 54.7 1765.7 18.4 71.1 S L 448.1 383.5 33.3 618.5 149.2 165.6 133.3 176.9 2142.9 45.1 183.6 S R 480.4 394.4 34.1 635.0 177.9 185.9 169.3 185.2 2776.6 48.7 196.9 S r 173.1 92.2 7.2 144.1 96.9 84.4 104.5 54.7 1765.7 18.4 71.1 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-11-119507-08855B Page 53 sur 171
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 11210 6318.0 171.4 2.71% 0.29 1561.8 80.3 5.14% -0.36 11212 Not analyzed Not analyzed 11232 5535.0 97.1 1.75% -1.30 1482.5 64.0 4.31% -0.53 11236 6807.8 115.9 1.70% 1.29 2402.8 94.8 3.94% 1.50 11240 6044.0 55.8 0.92% -0.26 1828.5 51.0 2.79% 0.23 11249 5870.0 31.7 0.54% -0.62 1398.5 41.7 2.98% -0.72 11250 Not analyzed Not analyzed 11255 6063.8 109.8 1.81% -0.22 1512.8 15.7 1.04% -0.47 11262 Not analyzed Not analyzed 11273 6092.2 877.9 14.41% -0.17 1762.5 198.9 11.28% 0.08 11275 Not analyzed Not analyzed 11279 6844.5 354.3 5.18% 1.37 1370.5 20.5 1.50% -0.78 11283 5948.0 36.9 0.62% -0.46 1717.2 11.0 0.64% -0.02 11288 6210.2 130.4 2.10% 0.08 3570.2 229.2 6.42% 4.07 DRC-11-119507-08855B Page 54 sur 171
Remarks and comments : Antimony : Laboratory 11273 is marked by the Cochran and Mandel k tests as having a higher intralaboratory dispersion than the rest of the population. Arsenic : Laboratory 11288 obtained a z score greater than 3. Laboratories 11273 and 11288 are marked by the Cochran and Mandel k tests as having a higher intra-laboratory dispersion than the rest of the population. DRC-11-119507-08855B Page 55 sur 171
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 11210 231.2 8.6 3.73% 0.81 865.8 196.8 22.73% -0.13 11212 Not analyzed Not analyzed 11232 160.2 2.5 1.56% -1.16 32.8 1.5 4.58% -1.37 11236 212.0 8.1 3.83% 0.27 649.0 563.1 86.77% -0.45 11240 197.0 3.6 1.81% -0.14 1684.5 65.3 3.88% 1.09 11249 175.5 2.6 1.51% -0.74 1375.8 3.9 0.28% 0.63 11250 Not analyzed Not analyzed 11255 193.5 7.8 4.06% -0.24 650.8 32.3 4.97% -0.45 11262 Not analyzed Not analyzed 11273 225.5 11.7 5.18% 0.65 970.2 267.1 27.52% 0.03 11275 Not analyzed Not analyzed 11279 167.0 1.4 0.85% -0.98 1373.0 103.2 7.52% 0.63 11283 628.5 4.5 0.72% 11.84 1593.5 68.3 4.29% 0.96 11288 207.5 7.0 3.40% 0.15 339.5 28.7 8.44% -0.92 DRC-11-119507-08855B Page 56 sur 171
Remarks and comments : Cadmium : Laboratory 11283 has a z score greater than 3. Chromium : Laboratories 11210, 11236 and 11273 are marked by the Cochran test as having a higher intra-laboratory dispersion than the rest of the population. DRC-11-119507-08855B Page 57 sur 171
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 11210 1764.5 119.9 6.80% -0.28 2003.8 89.3 4.46% -0.06 11212 Not analyzed Not analyzed 11232 1760.0 22.0 1.25% -0.30 1907.5 29.9 1.57% -0.59 11236 2208.5 74.7 3.38% 2.35 2376.8 50.6 2.13% 1.96 11240 1832.5 97.4 5.31% 0.12 2207.5 170.0 7.70% 1.04 11249 1645.5 36.5 2.22% -0.98 1942.5 39.6 2.04% -0.40 11250 Not analyzed Not analyzed 11255 1654.8 59.9 3.62% -0.93 1807.2 23.1 1.28% -1.13 11262 Not analyzed Not analyzed 11273 1984.2 186.4 9.40% 1.02 2139.2 233.6 10.92% 0.67 11275 Not analyzed Not analyzed 11279 1752.0 49.5 2.83% -0.35 1854.5 2.1 0.11% -0.87 11283 1725.0 89.2 5.17% -0.51 2026.8 58.4 2.88% 0.06 11288 1949.8 86.2 4.42% 0.82 1991.5 60.7 3.05% -0.13 DRC-11-119507-08855B Page 58 sur 171
Remarks and comments : Cobalt : Laboratory 11236 obtained a Z score between 2 and 3. Laboratory 11273 is marked by the Mandel k test as having a higher intra-laboratory dispersion than the rest of the population. Copper : Laboratories 11240 and 11273 are marked by the Cochran test as having a higher intralaboratory dispersion than the rest of the population. DRC-11-119507-08855B Page 59 sur 171
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 11210 1791.5 113.2 6.32% 0.25 1698.0 68.6 4.04% 0.14 11212 Not analyzed Not analyzed 11232 1621.2 26.6 1.64% -0.85 1338.8 11.8 0.88% -1.72 11236 2197.0 71.2 3.24% 2.88 3051.8 92.1 3.02% 7.17 11240 2507.2 198.4 7.91% 4.89 1608.5 15.5 0.96% -0.32 11249 1653.8 27.2 1.65% -0.64 1550.5 35.3 2.28% -0.63 11250 Not analyzed Not analyzed 11255 1664.0 64.9 3.90% -0.57 1542.0 16.1 1.04% -0.67 11262 Not analyzed Not analyzed 11273 1797.5 169.2 9.41% 0.29 1848.5 205.9 11.14% 0.92 11275 Not analyzed Not analyzed 11279 1672.5 21.9 1.31% -0.52 1634.0 2.8 0.17% -0.19 11283 1697.8 91.1 5.37% -0.35 1766.5 35.1 1.99% 0.50 11288 1690.2 15.2 0.90% -0.40 1719.8 28.9 1.68% 0.25 DRC-11-119507-08855B Page 60 sur 171
Remarks and comments : Manganese : Laboratory 11236 obtained a Z score between 2 and 3. Laboratory 11240 obtained a z score greater than 3. Laboratory 11240 is marked by the Mandel k test as having a higher intra-laboratory dispersion than the rest of the population. Nickel : Laboratory 11236 obtained a z score greater than 3. Laboratory 11273 is marked by the Mandel k test as having a higher intra-laboratory dispersion than the rest of the population. DRC-11-119507-08855B Page 61 sur 171
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 11210 36311.5 2269.2 6.25% 0.16 282.8 6.1 2.15% 0.40 11212 Not analyzed Not analyzed 11232 36650.0 640.3 1.75% 0.29 271.2 10.3 3.80% 0.17 11236 46105.0 1348.4 2.92% 4.07 291.0 28.3 9.73% 0.57 11240 36359.2 372.7 1.02% 0.17 251.0 16.8 6.69% -0.24 11249 35136.8 697.5 1.99% -0.31 207.5 3.1 1.50% -1.12 11250 Not analyzed Not analyzed 11255 33351.2 537.4 1.61% -1.03 257.2 3.9 1.50% -0.12 11262 Not analyzed 11273 27593.2 4065.2 14.73% -3.33 289.8 18.3 6.32% 0.54 11275 Not analyzed Not analyzed 11279 36891.5 3165.7 8.58% 0.39 125.0 56.6 45.25% -2.79 11283 34899.5 124.5 0.36% -0.41 253.5 7.8 3.10% -0.19 11288 37778.2 852.4 2.26% 0.74 421.8 15.9 3.77% 3.20 DRC-11-119507-08855B Page 62 sur 171
Remarks and comments : Lead : Laboratories 11236 and 11273 obtained z scores greater than 3. Laboratories 11210, 11273 and 11279 are marked by the Cochran test as having a higher intra-laboratory dispersion than the rest of the population. Thallium : Laboratory 11288 obtained z scores greater than 3. Laboratory 11279 obtained a Z score between 2 and 3. Laboratory 11279 is marked by the Cochran and Mandel k tests as having a higher intralaboratory dispersion than the rest of the population. DRC-11-119507-08855B Page 63 sur 171
Averages, standard deviations and z scores for the laboratories Laboratory Identification x µg/g Vanadium s r µg/g s r % Z Scores 11210 1589.8 99.2 6.24% 0.43 11212 Not analyzed 11232 1300.0 0.0 0.00% -1.01 11236 1287.5 24.1 1.87% -1.08 11240 1806.2 85.5 4.73% 1.50 11249 1425.0 37.4 2.63% -0.39 11250 Not analyzed 11255 1386.5 18.3 1.32% -0.58 11262 Not analyzed 11273 1604.8 217.8 13.57% 0.50 11275 Not analyzed 11279 1414.5 7.8 0.55% -0.45 11283 1584.5 74.5 4.70% 0.40 11288 1664.5 56.9 3.42% 0.80 Remarks and comments : Laboratory 11273 is marked by the Cochran and Mandel k tests as having a higher intralaboratory dispersion than the rest of the population. DRC-11-119507-08855B Page 64 sur 171
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 201 1564 1786 1906 1681 1804 255 1533 Free protocol x* 190.2 708.5 1731.9 1943 1583.2 1558.5 233.1 1433.5 Recovery rate % 94.6% 45.3% 97.0% 101.9% 94.2% 86.4% 91.4% 93.5% Absolute S R 32.9 693.7 234.4 209.4 372.5 287.9 54.2 256.4 Relative S R 17.3% 97.9% 13.5% 10.8% 23.5% 18.5% 23.3% 17.9% Imposed protocol x* 202.2 953.5 1811.6 2015.3 1752.4 1671 263 1504.2 Recovery rate % 100.6% 61.0% 101.4% 105.7% 104.2% 92.6% 103.1% 98.1% Absolute S R 34.1 635 177.9 185.9 169.3 185.2 48.7 196.9 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-11-119507-08855B Page 65 sur 171
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-11-119507-08855B Page 66 sur 171
13.1.11 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 99.75 Population Standard Deviation CV R (%) CV rep (%) 11.29 11.32% 1.35% Population 17 S L 11.25 S R 11.43 S r 2.04 Values observed after application of statistical algorithms Parameter (mg/liter) Value targeted by spiking Sulfur_dioxide 96.1 x* 97.96 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-11-119507-08855B Page 67 sur 171
Averages, standard deviations and z scores for the laboratories Laboratory Identification x mg/l Sulfur dioxide s r mg/l s r % Z Scores 11207 94.23 0.72 0.76% -0.56 11210 104.15 0.61 0.59% 0.93 11212 100.05 0.24 0.24% 0.31 11222 91.80 0.29 0.32% -0.92 11226 93.78 0.59 0.62% -0.63 11236 91.25 0.79 0.87% -1.00 11249 91.75 0.79 0.87% -0.93 11255 104.20 5.27 5.06% 0.93 11259 93.55 0.13 0.14% -0.66 11262 104.78 4.04 3.85% 1.02 11273 98.60 1.69 1.71% 0.10 11275 106.50 4.07 3.82% 1.28 11279 96.40 0.26 0.27% -0.23 11281 138.45 1.37 0.99% 6.06 11283 101.73 0.96 0.94% 0.56 11288 91.70 1.15 1.26% -0.94 11291 92.88 0.56 0.60% -0.76 Remarks and comments : Laboratory 11281 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, 11262 and 11275 were shown, through the Cochran and Mandel k tests, as having a greater intra-laboratory dispersion than the rest of the population. DRC-11-119507-08855B Page 68 sur 171
13.1.12 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 55.18 Population Standard Deviation CV R (%) CV rep (%) 5.57 10.1% 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* 56.24 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-11-119507-08855B Page 69 sur 171
Laboratory Identification x mg/l s r mg/l Ammonia s r % Z Scores 11207 58.50 1.33 2.27% 0.64 11210 58.08 0.62 1.07% 0.52 11212 56.88 1.54 2.70% 0.18 11222 56.58 0.22 0.39% 0.10 11227 59.00 1.46 2.47% 0.78 11236 54.50 5.78 10.60% -0.49 11244 52.65 0.17 0.33% -1.01 11249 55.08 0.31 0.56% -0.33 11250 42.63 0.57 1.33% -3.82 11255 39.18 0.64 1.63% -4.79 11259 55.45 0.65 1.16% -0.22 11262 58.03 0.46 0.79% 0.50 11269 57.38 0.44 0.77% 0.32 11273 57.08 0.26 0.46% 0.24 11275 54.38 1.78 3.28% -0.52 11279 48.73 5.28 10.84% -2.11 11281 60.80 0.71 1.17% 1.28 11283 59.35 0.57 0.97% 0.87 11288 54.08 1.92 3.55% -0.61 11291 60.98 0.70 1.15% 1.33 11296 59.53 1.53 2.57% 0.92 Remarks and comments : Laboratories 11250 and 11255 obtained z scores beyond the admissible value of 3. Laboratory 11279 obtained a z score between 2 and 3. According to the Mandel k test, laboratories 11236 and 11279 have intra-laboratory dispersions that are distinguished as being higher than the rest of the population. DRC-11-119507-08855B Page 70 sur 171
The relative inter-laboratory dispersion of 6.6% is satisfactory given the diversity of the methods used. In fact, given the INERIS warning regarding the operating mode described in standard NF X 43-303, colorimetry part, the laboratories applied or drew inspiration from other standards or internal operating modes (EN ISO 11732, VDI 3496, methods of air sampling and analysis, distillation/titration). 14 LIST OF ANNEXES Reference Title Number of pages Annex 1 General organization, description of tests and algorithms 9 Annex 2 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 * ). 41 41 Annex 4 Histogram of z scores obtained by each laboratory for all analytes in a test 9 DRC-11-119507-08855B Page 71 sur 171
ANNEX 1 GENERAL ORGANIZATION, DESCRIPTION OF TESTS AND ALGORITHMS DRC-11-119507-08855B Page 72 sur 171
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 5725-1 ( 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 13528. 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-11-119507-08855B Page 73 sur 171
- 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 13528 according to the following procedure. DRC-11-119507-08855B Page 74 sur 171
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 13528 : 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 5725. The confirmation of the verification of the hypotheses formulated in the part (NF ISO 5725-1) 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-11-119507-08855B Page 75 sur 171
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 5725-5 ( 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-11-119507-08855B Page 76 sur 171
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 5725-2 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 5725-5, 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 13528 and ISO 5725-5. 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-11-119507-08855B Page 77 sur 171
s * 1.483 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* 1.134 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 13528 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 13528 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-11-119507-08855B Page 78 sur 171
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-11-119507-08855B Page 79 sur 171
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 ( 7.4.2 standard ISO 13528). DRC-11-119507-08855B Page 80 sur 171
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-11-119507-08855B Page 81 sur 171
TABLE 1-11 119507 HCL WATER HYDROCHLORIC ACID RAW DATA IN MG/LITER Laboratory Identification 1 2 3 4 Beginning of analysis End of analysis Standard Average of measurements Standard Deviation of s 11207 18,8 18,7 18,5 18,6 27/05/2011 30/05/2011 NF EN 1911 18,650 0,1291 0,7% OK CVrep by % EXPERT opinion Expert Opinion Comments 11210 21,5 21,5 20,9 20,7 10/06/2011 10/06/2011 NF EN 1911 21,150 0,4123 1,9% OK 11212 18,5 18,5 18,4 18,5 31/05/2011 31/05/2011 NF EN 1911 18,475 0,0500 0,3% OK 11222 19,6 19,7 19,6 19,5 06/06/2011 16/06/2011 NF EN 1911 19,600 0,0816 0,4% OK 11226 19,3 19,2 19,3 19,2 06/06/2011 10/06/2011 NF EN 1911 19,250 0,0577 0,3% OK 11236 19,8 19,1 18,9 19,8 10/06/2011 14/06/2011 NF EN 1911 19,400 0,4690 2,4% OK 11249 19,2 19,2 19,2 19,2 08/06/2011 08/06/2011 NF EN 1911 19,200 0,0000 0,0% OK 11251 19,7 19,5 19,5 19,6 09/06/2011 09/06/2011 NF EN 1911 19,575 0,0957 0,5% OK 11255 19,5 22,0 19,5 22,1 27/05/2011 31/05/2011 NF EN 1911 20,775 1,4728 7,1% OK 11259 19,4 19,4 19,4 19,4 15/06/2011 16/06/2011 Autre, à préciser (Observations) 19,400 0,0000 0,0% OK 11262 17,6 17,8 18,5 18,7 01/06/2011 01/06/2011 NF EN 1911 18,150 0,5323 2,9% OK 11273 18,4 18,6 18,0 17,3 10/06/2011 10/06/2011 NF EN 1911 18,075 0,5737 3,2% OK 11275 18,5 18,3 18,4 18,4 31/05/2011 06/06/2011 NF EN 1911 18,400 0,0816 0,4% OK 11279 19,7 19,9 19,7 19,8 27/05/2011 16/06/2011 NF EN 1911 19,775 0,0957 0,5% OK 11281 17,7 18,4 17,7 18,1 10/06/2011 10/06/2011 NF EN 1911 17,975 0,3403 1,9% OK 11283 21,5 20,8 21,8 21,0 01/06/2011 22/06/2011 NF EN 1911 21,275 0,4573 2,1% OK 11288 19,0 18,6 18,8 19,1 30/05/2011 31/05/2011 NF EN 1911 18,875 0,2217 1,2% OK 11291 19,6 19,6 19,6 19,6 07/06/2011 07/06/2011 NF EN 1911 19,600 0,0000 0,0% OK DRC-11-119507-08855B Page 82 sur 171
TABLE 2-11 119507 HF SODIUM HYDROXIDE (NAOH) FLUORHYDRIC ACID - RAW DATA IN MG/LITER Laboratory Identification 1 2 3 4 Beginning of analysis End of analysis Standard Average of measurements Standard Deviation of s CVrep by % EXPERT opinion Expert Opinion Comments 11209 1,77 1,80 1,82 1,83 14/06/2011 14/06/2011 NF X 43-304 Décembre 2007 1,805 0,0265 1,5% OK 11210 1,94 1,79 1,99 1,80 10/06/2011 10/06/2011 NF X 43-304 Décembre 2007 1,880 0,1003 5,3% OK 11212 1,74 1,76 1,74 1,74 31/05/2011 31/05/2011 NF X 43-304 Décembre 2007 1,745 0,0100 0,6% OK 11214 1,88 1,94 1,96 1,93 07/06/2011 07/06/2011 NF X 43-304 Décembre 2007 1,928 0,0340 1,8% OK 11226 1,69 1,81 1,80 1,69 06/06/2011 10/06/2011 NF X 43-304 Décembre 2007 1,748 0,0665 3,8% OK 11236 1,89 1,84 1,86 1,88 10/06/2011 14/06/2011 NF X 43-304 Décembre 2007 1,868 0,0222 1,2% OK 11249 1,85 1,84 1,80 1,81 07/06/2011 07/06/2011 NF X 43-304 Décembre 2007 1,825 0,0238 1,3% OK 11250 1,92 1,97 1,97 1,92 01/06/2011 01/06/2011 NF X 43-304 Décembre 2007 1,945 0,0289 1,5% OK 11255 1,87 2,03 2,03 2,09 27/05/2011 15/06/2011 NF X 43-304 Décembre 2007 2,005 0,0943 4,7% OK 11262 1,81 1,82 1,88 1,82 01/06/2011 01/06/2011 NF X 43-304 Décembre 2007 1,833 0,0320 1,7% OK 11273 1,91 1,82 1,88 1,92 10/06/2011 10/06/2011 NF X 43-304 Décembre 2007 1,883 0,0450 2,4% OK 11275 1,92 1,92 1,90 1,91 31/05/2011 31/05/2011 NF X 43-304 Décembre 2007 1,913 0,0096 0,5% OK 11279 1,98 1,98 1,98 1,99 27/05/2011 06/06/2011 NF X 43-304 Décembre 2007 1,983 0,0050 0,3% OK 11283 1,92 1,94 1,99 1,99 01/06/2011 22/06/2011 NF X 43-304 Décembre 2007 1,960 0,0356 1,8% OK 11285 1,74 1,75 1,75 1,75 06/06/2011 07/06/2011 NF X 43-304 Décembre 2007 1,748 0,0050 0,3% OK 11288 2,17 2,06 2,06 2,02 30/05/2011 06/06/2011 NF X 43-304 Décembre 2007 2,078 0,0645 3,1% OK 11291 1,90 1,90 1,95 1,95 16/06/2011 16/06/2011 NF X 43-304 Décembre 2007 1,925 0,0289 1,5% OK DRC-11-119507-08855B Page 83 sur 171
TABLE 3-11 119507 HF DUST FLUORHYDRIC ACID RAW DATA IN MG/G Laboratory Identification 1 2 3 4 Beginning of analysis End of analysis Standard Average of measurements Standard Deviation of s 11209 13,0 13,3 15,2 14,6 14/06/2011 15/06/2011 NF X 43-304 Décembre 2007 14,025 1,0468 7,5% OK CVrep by % EXPERT opinion Expert Opinion Comments 11210 21,1 22,5 19,7 24,2 09/06/2011 10/06/2011 NF X 43-304 Décembre 2007 21,875 1,9259 8,8% OK 11212 10,3 9,1 9,0 8,8 06/06/2011 20/06/2011 NF X 43-304 Décembre 2007 9,300 0,6782 7,3% OK 11214 12,0 12,1 14,1 12,8 07/06/2011 07/06/2011 NF X 43-304 Décembre 2007 12,750 0,9678 7,6% OK 11226 Faites votre choix Non analysé Non analysé Non analysé Exclus 11236 6,0 6,3 6,4 6,3 20/06/2011 21/06/2011 NF X 43-304 Décembre 2007 6,250 0,1732 2,8% OK 11249 12,6 11,9 11,6 11,9 17/06/2011 17/06/2011 NF X 43-304 Décembre 2007 12,000 0,4243 3,5% OK 11250 11,5 11,7 11,7 11,9 31/05/2011 31/05/2011 NF X 43-304 Décembre 2007 11,700 0,1633 1,4% OK 11255 4,7 4,6 4,3 4,3 27/05/2011 15/06/2011 NF X 43-304 Décembre 2007 4,475 0,2062 4,6% OK 11262 3,3 3,6 3,8 3,8 08/06/2011 08/06/2011 NF X 43-304 Décembre 2007 3,625 0,2363 6,5% OK 11273 15,9 12,9 15,1 12,6 14/06/2011 21/06/2011 NF X 43-304 Décembre 2007 14,125 1,6256 11,5% OK 11275 12,5 13,4 13,8 13,3 30/05/2011 01/06/2011 NF X 43-304 Décembre 2007 13,250 0,5447 4,1% OK 11279 0,9 1,0 1,1 15/06/2011 17/06/2011 NF X 43-304 Décembre 2007 1,000 0,1000 10,0% OK 11283 9,9 8,7 9,5 9,6 01/06/2011 22/06/2011 NF X 43-304 Décembre 2007 9,425 0,5123 5,4% OK 11285 9,3 9,3 9,9 9,9 14/06/2011 21/06/2011 NF X 43-304 Décembre 2007 9,600 0,3464 3,6% OK 11288 4,6 6,5 3,7 5,9 30/05/2011 06/06/2011 NF X 43-304 Décembre 2007 5,175 1,2633 24,4% OK 11291 13,7 12,4 13,0 13,3 16/06/2011 17/06/2011 Autre, à préciser (Observations) 13,100 0,5477 4,2% OK DRC-11-119507-08855B Page 84 sur 171
TABLE 4-11 119507 NH3 SULFURIC ACID - AMMONIA RAW DATA IN MG/LITER Laboratory Identification 1 2 3 4 Beginning of analysis End of analysis Standard Average of measurements Standard Deviation of s 11207 59,6 58,3 59,4 56,7 27/05/2011 30/05/2011 NF X 43-303 58,500 1,3292 2,3% OK CVrep by % EXPERT opinion Expert Opinion Comments 11210 57,9 58,1 57,4 58,9 06/06/2011 08/06/2011 Autre, à préciser (Observations) 58,075 0,6238 1,1% OK 11212 58,1 54,7 57,8 56,9 30/05/2011 30/05/2011 Autre, à préciser (Observations) 56,875 1,5370 2,7% OK 11222 56,3 56,8 56,7 56,5 06/06/2011 16/06/2011 NF X 43-303 56,575 0,2217 0,4% OK 11227 57,7 60,0 57,8 60,5 31/05/2011 07/06/2011 Autre, à préciser (Observations) 59,000 1,4583 2,5% OK 11236 59,8 59,2 49,6 49,4 10/06/2011 15/06/2011 NF X 43-303 54,500 5,7793 10,6% OK 11244 52,5 52,5 52,8 52,8 06/06/2011 16/06/2011 Autre, à préciser (Observations) 52,650 0,1732 0,3% OK 11249 54,8 54,9 55,5 55,1 08/06/2011 08/06/2011 NF X 43-303 55,075 0,3096 0,6% OK 11250 43,1 42,8 42,8 41,8 31/05/2011 31/05/2011 NF X 43-303 42,625 0,5679 1,3% OK 11255 40,0 39,3 38,9 38,5 27/05/2011 14/06/2011 Autre, à préciser (Observations) 39,175 0,6397 1,6% OK 11259 54,8 55,0 56,1 55,9 07/06/2011 08/06/2011 Autre, à préciser (Observations) 55,450 0,6455 1,2% OK 11262 58,6 57,9 58,1 57,5 31/05/2011 31/05/2011 NF X 43-303 58,025 0,4573 0,8% OK 11269 57,7 56,9 57,8 57,1 07/06/2011 09/06/2011 Autre, à préciser (Observations) 57,375 0,4425 0,8% OK 11273 57,1 56,7 57,3 57,2 21/06/2011 22/06/2011 NF X 43-303 57,075 0,2630 0,5% OK 11275 55,2 56,5 52,9 52,9 01/06/2011 16/06/2011 NF X 43-303 54,375 1,7840 3,3% OK 11279 44,2 44,1 53,3 53,3 01/06/2011 01/06/2011 NF X 43-303 48,725 5,2829 10,8% OK 11281 61,2 60,8 59,8 61,4 08/06/2011 10/06/2011 NF X 43-303 60,800 0,7118 1,2% OK 11283 60,1 59,5 58,9 58,9 01/06/2011 22/06/2011 NF X 43-303 59,350 0,5745 1,0% OK 11288 52,1 56,7 53,6 53,9 30/05/2011 31/05/2011 NF X 43-303 54,075 1,9190 3,5% OK 11291 60,9 60,2 60,9 61,9 31/05/2011 31/05/2011 NF X 43-303 60,975 0,6994 1,1% OK 11296 59,3 57,9 61,6 59,3 30/05/2011 30/05/2011 Autre, à préciser (Observations) 59,525 1,5327 2,6% OK DRC-11-119507-08855B Page 85 sur 171
TABLE 5-11 119507 SO2 HYDROPEROXIDE SULFUR DIOXIDE RAW DATA IN MG/LITER Laboratory Identification 1 2 3 4 Beginning of analysis End of analysis Standard Average of measurements Standard Deviation of s 11207 95,1 94,5 93,8 93,5 27/05/2011 30/05/2011 NF EN 14791 94,225 0,7182 0,8% OK CVrep by % EXPERT opinion Expert Opinion Comments 11210 104,7 103,9 104,6 103,4 10/06/2011 10/06/2011 NF EN 14791 104,150 0,6137 0,6% OK 11212 100,2 99,7 100,2 100,1 31/05/2011 31/05/2011 NF EN 14791 100,050 0,2380 0,2% OK 11222 91,9 92,1 91,4 91,8 06/06/2011 16/06/2011 NF EN 14791 91,800 0,2944 0,3% OK 11226 94,0 93,3 94,5 93,3 06/06/2011 16/06/2011 NF EN 14791 93,775 0,5852 0,6% OK 11236 90,6 90,9 92,4 91,1 10/06/2011 14/06/2011 NF EN 14791 91,250 0,7937 0,9% OK 11249 92,8 91,9 91,3 91,0 08/06/2011 08/06/2011 NF EN 14791 91,750 0,7937 0,9% OK 11255 112,1 101,5 101,4 101,8 26/05/2011 31/05/2011 NF EN 14791 104,200 5,2694 5,1% OK 11259 93,5 93,4 93,7 93,6 09/06/2011 10/06/2011 Autre, à préciser (Observations) 93,550 0,1291 0,1% OK 11262 103,4 109,8 100,2 105,7 27/05/2011 01/06/2011 NF EN 14791 104,775 4,0385 3,9% OK 11273 96,2 99,3 100,1 98,8 10/06/2011 20/06/2011 NF EN 14791 98,600 1,6872 1,7% OK 11275 110,3 109,7 103,5 102,5 31/05/2011 06/06/2011 NF EN 14791 106,500 4,0694 3,8% OK 11279 96,1 96,3 96,7 96,5 27/05/2011 06/06/2011 NF EN 14791 96,400 0,2582 0,3% OK 11281 139,2 139,1 139,1 136,4 10/06/2011 10/06/2011 NF EN 14791 138,450 1,3675 1,0% OK 11283 102,3 102,0 102,3 100,3 01/06/2011 22/06/2011 NF EN 14791 101,725 0,9605 0,9% OK 11288 90,7 90,7 92,7 92,7 30/05/2011 31/05/2011 NF EN 14791 91,700 1,1547 1,3% OK 11291 93,4 93,1 92,9 92,1 07/06/2011 08/06/2011 NF EN 14791 92,875 0,5560 0,6% OK DRC-11-119507-08855B Page 86 sur 171
TABLE 6-11 119507 HG_ K2CR2O7 NITRIC ACID - DICHROMATE (HNO3-K2CR2O7) - MERCURY RAW DATA IN µg/liter Laboratory Identification 1 2 3 4 Beginning of analysis End of analysis Standard Average of measurements Standard Deviation of s CVrep by % EXPERT opinion Expert Opinion Comments 11201 Faites votre choix Non analysé Non analysé Non analysé Exclus 11207 14 11 13 12 27/05/2011 30/05/2011 NF EN 13211 12,500 1,2910 10,3% OK 11209 Faites votre choix Non analysé Non analysé Non analysé Exclus 11210 11 12 12 12 09/06/2011 09/06/2011 NF EN 13211 + NF EN 1483 11,750 0,5000 4,3% OK 11212 10 10 10 10 20/06/2011 20/06/2011 NF EN 13211 10,000 0,0000 0,0% Exclus Valeur rendue <10 11236 9 9 10 9 10/06/2011 10/06/2011 NF EN 13211 9,250 0,5000 5,4% OK 11249 10 10 10 9 07/06/2011 07/06/2011 NF EN 13211 + NF EN 1483 9,750 0,5000 5,1% OK 11250 12 12 12 12 25/05/2011 03/06/2011 Autre, à préciser (Observations) 12,000 0,0000 0,0% OK 11255 12 11 12 11 27/05/2011 31/05/2011 NF EN 13211 11,500 0,5774 5,0% OK 11262 10 10 10 10 09/06/2011 10/06/2011 NF EN 13211 10,000 0,0000 0,0% OK 11273 10 11 11 10 09/06/2011 09/06/2011 NF EN 13211 10,500 0,5774 5,5% OK 11275 15 16 16 16 09/06/2011 09/06/2011 NF EN 13211 15,750 0,5000 3,2% OK 11279 Faites votre choix Non analysé Non analysé Non analysé Exclus 11281 Faites votre choix Non analysé Non analysé Non analysé Exclus 11283 12 11 11 11 01/06/2011 22/06/2011 NF EN 13211 11,250 0,5000 4,4% OK 11285 13 13 13 13 26/05/2011 26/05/2011 NF EN 1483 13,000 0,0000 0,0% OK 11288 9 9 9 9 30/05/2011 06/06/2011 NF EN 13211 9,000 0,0000 0,0% OK 11291 12 12 12 13 30/05/2011 30/05/2011 NF EN 13211 + NF EN 1483 12,250 0,5000 4,1% OK DRC-11-119507-08855B Page 87 sur 171
TABLE 7-11 119507 HG_KMNO4 SULFURIC ACID - PERMANGANATE (H2SO4-KMNO4) - MERCURY RAW DATA IN µg/liter Laboratory Identification 1 2 3 4 Beginning of analysis End of analysis Standard Average of measurements Standard Deviation of s CVrep by % EXPERT opinion Expert Opinion Comments 11201 9 9 7 9 09/06/2011 22/06/2011 NF EN 13211 8,500 1,0000 11,8% OK 11207 Faites votre choix Non analysé Non analysé Non analysé Exclus 11209 9 9 12 11 08/06/2011 09/06/2011 NF EN 13211 10,250 1,5000 14,6% OK 11210 Faites votre choix Non analysé Non analysé Non analysé Exclus 11212 Faites votre choix Non analysé Non analysé Non analysé Exclus 11236 11 12 14 16 10/06/2011 10/06/2011 NF EN 13211 13,250 2,2174 16,7% OK 11249 12 12 12 12 07/06/2011 07/06/2011 NF EN 13211 + NF EN 1483 12,000 0,0000 0,0% OK 11250 Faites votre choix Non analysé Non analysé Non analysé Exclus 11255 10 10 11 11 27/05/2011 31/05/2011 NF EN 13211 10,500 0,5774 5,5% OK 11262 1 1 1 1 06/06/2011 10/06/2011 NF EN 13211 1,000 0,0000 0,0% Exclus Valeur rendue <1 11273 Faites votre choix Non analysé Non analysé Non analysé Exclus 11275 5 5 5 5 09/06/2011 09/06/2011 NF EN 13211 5,000 0,0000 0,0% Exclus Valeur rendue <5 11279 13 13 12 12 30/05/2011 30/05/2011 NF EN 13211 12,500 0,5774 4,6% OK 11281 13 13 13 13 16/06/2011 16/06/2011 NF EN 13211 13,000 0,0000 0,0% OK 11283 11 12 12 12 01/06/2011 22/06/2011 NF EN 13211 11,750 0,5000 4,3% OK 11285 Faites votre choix Non analysé Non analysé Non analysé Exclus 11288 Faites votre choix Non analysé Non analysé Non analysé Exclus 11291 Faites votre choix Non analysé Non analysé Non analysé Exclus DRC-11-119507-08855B Page 88 sur 171
TABLES 8 TO 18-11 119507 METALS_SOLUTION RAW DATA IN µg/liter Table 8-11 119507 Metals_solution Nitric acid hydroperoxide Antimony Raw Data in µg/liter Laboratory Identification 1 2 3 4 Beginning of analysis End of analysis Standard Average of measurements Standard Deviation of s CVrep by % EXPERT opinion Expert Opinion Comments 11210 471 469 466 467 09/06/2011 10/06/2011 NF EN 14385 468,250 2,2174 0,5% OK 11212 468 469 466 466 30/05/2011 30/05/2011 NF EN 14385 467,250 1,5000 0,3% OK 11232 488 488 487 487 20/06/2011 20/06/2011 Autre, à préciser (Observations) 487,500 0,5774 0,1% OK 11236 461 458 460 453 10/06/2011 14/06/2011 NF EN 14385 458,000 3,5590 0,8% OK 11240 448 446 444 448 07/06/2011 NF EN 14385 446,500 1,9149 0,4% OK 11249 490 487 491 492 10/06/2011 10/06/2011 NF EN 14385 490,000 2,1602 0,4% OK 11250 447 447 444 445 15/06/2011 15/06/2011 NF EN 14385 445,750 1,5000 0,3% OK 11255 438 434 434 446 27/05/2011 07/06/2011 NF EN 14385 438,000 5,6569 1,3% OK 11262 407 400 424 393 06/06/2011 08/06/2011 Autre, à préciser (Observations) 406,000 13,2916 3,3% OK 11273 463 467 459 474 08/06/2011 08/06/2011 NF EN 14385 465,750 6,3966 1,4% OK 11275 449 448 449 447 09/06/2011 09/06/2011 NF EN 14385 448,250 0,9574 0,2% OK 11279 464 464 452 452 27/05/2011 30/05/2011 NF EN 14385 458,000 6,9282 1,5% OK 11283 430 431 430 430 01/06/2011 22/06/2011 NF EN 14385 430,250 0,5000 0,1% OK 11288 468 467 471 465 30/05/2011 30/05/2011 NF EN 14385 467,750 2,5000 0,5% OK DRC-11-119507-08855B Page 89 sur 171
Table 9-11 119507 Metals_solution Nitric acid hydroperoxide - Arsenic Raw data in µg/liter Laboratory Identification 1 2 3 4 Beginning of analysis End of analysis Standard Average of measurements Standard Deviation of s CVrep by % EXPERT opinion Expert Opinion Comments 11210 126 127 124 125 09/06/2011 10/06/2011 NF EN 14385 125,500 1,2910 1,0% OK 11212 135 136 134 136 30/05/2011 30/05/2011 NF EN 14385 135,250 0,9574 0,7% OK 11232 113 126 120 116 20/06/2011 20/06/2011 Autre, à préciser (Observations) 118,750 5,6199 4,7% OK 11236 145 147 145 141 10/06/2011 14/06/2011 NF EN 14385 144,500 2,5166 1,7% OK 11240 127 126 127 127 07/06/2011 NF EN 14385 126,750 0,5000 0,4% OK 11249 136 133 134 135 10/06/2011 10/06/2011 NF EN 14385 134,500 1,2910 1,0% OK 11250 127 126 123 125 15/06/2011 15/06/2011 NF EN 14385 125,250 1,7078 1,4% OK 11255 143 143 148 142 27/05/2011 07/06/2011 NF EN 14385 144,000 2,7080 1,9% OK 11262 128 128 126 128 06/06/2011 08/06/2011 Autre, à préciser (Observations) 127,500 1,0000 0,8% OK 11273 143 141 142 144 08/06/2011 08/06/2011 NF EN 14385 142,500 1,2910 0,9% OK 11275 117 118 118 117 09/06/2011 09/06/2011 NF EN 14385 117,500 0,5774 0,5% OK 11279 136 138 132 136 27/05/2011 30/05/2011 NF EN 14385 135,500 2,5166 1,9% OK 11283 133 140 134 130 01/06/2011 22/06/2011 NF EN 14385 134,250 4,1932 3,1% OK 11288 134 142 138 146 30/05/2011 30/05/2011 NF EN 14385 140,000 5,1640 3,7% OK DRC-11-119507-08855B Page 90 sur 171
Table 10-11 119507 Metals_solution Nitric acid hydroperoxide - Cadmium Raw data in µg/liter Laboratory Identification 1 2 3 4 Beginning of analysis End of analysis Standard Average of measurements Standard Deviation of s CVrep by % EXPERT opinion Expert Opinion Comments 11210 21 21 21 21 09/06/2011 10/06/2011 NF EN 14385 21,000 0,0000 0,0% OK 11212 21 21 21 21 30/05/2011 30/05/2011 NF EN 14385 21,000 0,0000 0,0% OK 11232 12 13 13 13 20/06/2011 20/06/2011 Autre, à préciser (Observations) 12,750 0,5000 3,9% OK 11236 21 21 21 21 10/06/2011 14/06/2011 NF EN 14385 21,000 0,0000 0,0% OK 11240 20 20 20 20 07/06/2011 NF EN 14385 20,000 0,0000 0,0% OK 11249 21 21 21 21 10/06/2011 10/06/2011 NF EN 14385 21,000 0,0000 0,0% OK 11250 20 20 19 20 15/06/2011 15/06/2011 NF EN 14385 19,750 0,5000 2,5% OK 11255 20 20 20 20 27/05/2011 07/06/2011 NF EN 14385 20,000 0,0000 0,0% OK 11262 20 20 21 20 06/06/2011 08/06/2011 Autre, à préciser (Observations) 20,250 0,5000 2,5% OK 11273 20 19 20 19 08/06/2011 08/06/2011 NF EN 14385 19,500 0,5774 3,0% OK 11275 21 21 21 21 15/06/2011 15/06/2011 NF EN 14385 21,000 0,0000 0,0% OK 11279 35 35 35 35 27/05/2011 30/05/2011 NF EN 14385 35,000 0,0000 0,0% OK 11283 19 20 19 20 01/06/2011 22/06/2011 NF EN 14385 19,500 0,5774 3,0% OK 11288 21 20 22 20 30/05/2011 30/05/2011 NF EN 14385 20,750 0,9574 4,6% OK DRC-11-119507-08855B Page 91 sur 171
Table 11-11 119507 Metals_solution Nitric acid hydroperoxide Chromium Raw data in µg/liter Laboratory Identification 1 2 3 4 Beginning of analysis End of analysis Standard Average of measurements Standard Deviation of s CVrep by % EXPERT opinion Expert Opinion Comments 11210 199 198 196 197 09/06/2011 10/06/2011 NF EN 14385 197,500 1,2910 0,7% OK 11212 200 200 198 199 30/05/2011 30/05/2011 NF EN 14385 199,250 0,9574 0,5% OK 11232 121 126 118 124 20/06/2011 20/06/2011 Autre, à préciser (Observations) 122,250 3,5000 2,9% OK 11236 195 193 193 192 10/06/2011 14/06/2011 NF EN 14385 193,250 1,2583 0,7% OK 11240 194 192 194 196 07/06/2011 NF EN 14385 194,000 1,6330 0,8% OK 11249 193 189 192 190 10/06/2011 10/06/2011 NF EN 14385 191,000 1,8257 1,0% OK 11250 190 190 191 189 15/06/2011 15/06/2011 NF EN 14385 190,000 0,8165 0,4% OK 11255 185 186 193 186 27/05/2011 07/06/2011 NF EN 14385 187,500 3,6968 2,0% OK 11262 193 195 192 195 06/06/2011 08/06/2011 Autre, à préciser (Observations) 193,750 1,5000 0,8% OK 11273 202 197 200 202 08/06/2011 08/06/2011 NF EN 14385 200,250 2,3629 1,2% OK 11275 181 181 182 181 09/06/2011 09/06/2011 NF EN 14385 181,250 0,5000 0,3% OK 11279 204 203 193 193 27/05/2011 30/05/2011 NF EN 14385 198,250 6,0759 3,1% OK 11283 204 210 205 210 01/06/2011 22/06/2011 NF EN 14385 207,250 3,2016 1,5% OK 11288 202 208 204 195 30/05/2011 30/05/2011 NF EN 14385 202,250 5,4391 2,7% OK DRC-11-119507-08855B Page 92 sur 171
Table 12-11 119507 Metals_solution Nitric acid hydroperoxide - Cobalt Raw Data in µg/liter in µg/liter Laboratory Identification 1 2 3 4 Beginning of analysis End of analysis Standard Average of measurements Standard Deviation of s CVrep by % EXPERT opinion Expert Opinion Comments 11210 226 226 223 225 09/06/2011 10/06/2011 NF EN 14385 225,000 1,4142 0,6% OK 11212 227 229 228 227 30/05/2011 30/05/2011 NF EN 14385 227,750 0,9574 0,4% OK 11232 132 140 131 137 20/06/2011 20/06/2011 Autre, à préciser (Observations) 135,000 4,2426 3,1% OK 11236 230 230 229 229 10/06/2011 14/06/2011 NF EN 14385 229,500 0,5774 0,3% OK 11240 216 215 215 218 07/06/2011 NF EN 14385 216,000 1,4142 0,7% OK 11249 230 226 227 228 10/06/2011 10/06/2011 NF EN 14385 227,750 1,7078 0,7% OK 11250 215 215 217 214 15/06/2011 15/06/2011 NF EN 14385 215,250 1,2583 0,6% OK 11255 198 198 207 200 27/05/2011 07/06/2011 NF EN 14385 200,750 4,2720 2,1% OK 11262 217 221 217 219 06/06/2011 08/06/2011 Autre, à préciser (Observations) 218,500 1,9149 0,9% OK 11273 221 218 219 221 08/06/2011 08/06/2011 NF EN 14385 219,750 1,5000 0,7% OK 11275 215 215 215 215 15/06/2011 15/06/2011 NF EN 14385 215,000 0,0000 0,0% OK 11279 231 230 223 222 27/05/2011 30/05/2011 NF EN 14385 226,500 4,6547 2,1% OK 11283 226 225 225 225 01/06/2011 22/06/2011 NF EN 14385 225,250 0,5000 0,2% OK 11288 230 227 233 225 30/05/2011 30/05/2011 NF EN 14385 228,750 3,5000 1,5% OK DRC-11-119507-08855B Page 93 sur 171
Table 13-11 119507 Metals_solution Nitric acid hydroperoxide Copper Raw data in µg/liter Laboratory Identification 1 2 3 4 Beginning of analysis End of analysis Standard Average of measurements Standard Deviation of s CVrep by % EXPERT opinion Expert Opinion Comments 11210 237 236 235 236 09/06/2011 10/06/2011 NF EN 14385 236,000 0,8165 0,3% OK 11212 245 244 243 242 30/05/2011 30/05/2011 NF EN 14385 243,500 1,2910 0,5% OK 11232 152 160 151 158 20/06/2011 20/06/2011 Autre, à préciser (Observations) 155,250 4,4253 2,9% OK 11236 245 246 244 244 10/06/2011 14/06/2011 NF EN 14385 244,750 0,9574 0,4% OK 11240 229 227 229 231 07/06/2011 NF EN 14385 229,000 1,6330 0,7% OK 11249 244 240 241 240 10/06/2011 10/06/2011 NF EN 14385 241,250 1,8930 0,8% OK 11250 226 226 225 224 15/06/2011 15/06/2011 NF EN 14385 225,250 0,9574 0,4% OK 11255 201 206 218 208 27/05/2011 07/06/2011 NF EN 14385 208,250 7,1356 3,4% OK 11262 243 238 239 242 06/06/2011 08/06/2011 Autre, à préciser (Observations) 240,500 2,3805 1,0% OK 11273 235 230 230 237 08/06/2011 08/06/2011 NF EN 14385 233,000 3,5590 1,5% OK 11275 202 204 203 202 15/06/2011 15/06/2011 NF EN 14385 202,750 0,9574 0,5% OK 11279 231 232 230 231 27/05/2011 30/05/2011 NF EN 14385 231,000 0,8165 0,4% OK 11283 230 235 230 235 01/06/2011 22/06/2011 NF EN 14385 232,500 2,8868 1,2% OK 11288 229 226 222 224 30/05/2011 30/05/2011 NF EN 14385 225,250 2,9861 1,3% OK DRC-11-119507-08855B Page 94 sur 171
Table 14-11 119507 Metals_solution Nitric acid hydroperoxide - Manganese Raw data in µg/liter Laboratory Identification 1 2 3 4 Beginning of analysis End of analysis Standard Average of measurements Standard Deviation of s CVrep by % EXPERT opinion Expert Opinion Comments 11210 225 224 223 224 09/06/2011 10/06/2011 NF EN 14385 224,000 0,8165 0,4% OK 11212 225 227 226 225 30/05/2011 30/05/2011 NF EN 14385 225,750 0,9574 0,4% OK 11232 122 129 120 126 20/06/2011 20/06/2011 Autre, à préciser (Observations) 124,250 4,0311 3,2% OK 11236 230 226 227 226 10/06/2011 14/06/2011 NF EN 14385 227,250 1,8930 0,8% OK 11240 213 211 212 214 07/06/2011 NF EN 14385 212,500 1,2910 0,6% OK 11249 227 224 224 225 10/06/2011 10/06/2011 NF EN 14385 225,000 1,4142 0,6% OK 11250 218 217 216 214 15/06/2011 15/06/2011 NF EN 14385 216,250 1,7078 0,8% OK 11255 209 214 206 213 27/05/2011 07/06/2011 NF EN 14385 210,500 3,6968 1,8% OK 11262 217 220 216 222 06/06/2011 08/06/2011 Autre, à préciser (Observations) 218,750 2,7538 1,3% OK 11273 225 220 221 226 08/06/2011 08/06/2011 NF EN 14385 223,000 2,9439 1,3% OK 11275 216 218 217 216 09/06/2011 09/06/2011 NF EN 14385 216,750 0,9574 0,4% OK 11279 231 229 227 230 27/05/2011 30/05/2011 NF EN 14385 229,250 1,7078 0,7% OK 11283 220 225 220 225 01/06/2011 22/06/2011 NF EN 14385 222,500 2,8868 1,3% OK 11288 218 222 224 228 30/05/2011 30/05/2011 NF EN 14385 223,000 4,1633 1,9% OK DRC-11-119507-08855B Page 95 sur 171
Table 15-11 119507 Metals_solution Nitric acid hydroperoxide - Nickel Raw Data in µg/liter in µg/liter Laboratory Identification 1 2 3 4 Beginning of analysis End of analysis Standard Average of measurements Standard Deviation of s CVrep by % EXPERT opinion Expert Opinion Comments 11210 230 229 228 229 09/06/2011 10/06/2011 NF EN 14385 229,000 0,8165 0,4% OK 11212 229 228 227 227 30/05/2011 30/05/2011 NF EN 14385 227,750 0,9574 0,4% OK 11232 129 139 136 137 20/06/2011 20/06/2011 Autre, à préciser (Observations) 135,250 4,3493 3,2% OK 11236 228 229 227 227 10/06/2011 14/06/2011 NF EN 14385 227,750 0,9574 0,4% OK 11240 219 217 218 221 07/06/2011 NF EN 14385 218,750 1,7078 0,8% OK 11249 222 217 219 218 10/06/2011 10/06/2011 NF EN 14385 219,000 2,1602 1,0% OK 11250 213 213 215 213 15/06/2011 15/06/2011 NF EN 14385 213,500 1,0000 0,5% OK 11255 195 196 208 200 27/05/2011 07/06/2011 NF EN 14385 199,750 5,9090 3,0% OK 11262 203 208 201 203 06/06/2011 08/06/2011 Autre, à préciser (Observations) 203,750 2,9861 1,5% OK 11273 220 212 216 220 08/06/2011 08/06/2011 NF EN 14385 217,000 3,8297 1,8% OK 11275 205 208 201 206 09/06/2011 09/06/2011 NF EN 14385 205,000 2,9439 1,4% OK 11279 231 231 222 221 27/05/2011 30/05/2011 NF EN 14385 226,250 5,5000 2,4% OK 11283 225 228 227 227 01/06/2011 22/06/2011 NF EN 14385 226,750 1,2583 0,6% OK 11288 221 225 234 220 30/05/2011 30/05/2011 NF EN 14385 225,000 6,3770 2,8% OK DRC-11-119507-08855B Page 96 sur 171
Table 16-11 119507 Metals_solution Nitric acid hydroperoxide Lead Raw Data in µg/liter Laboratory Identification 1 2 3 4 Beginning of analysis End of analysis Standard Average of measurements Standard Deviation of s CVrep by % EXPERT opinion Expert Opinion Comments 11210 499 498 492 495 09/06/2011 10/06/2011 NF EN 14385 496,000 3,1623 0,6% OK 11212 497 498 496 496 30/05/2011 30/05/2011 NF EN 14385 496,750 0,9574 0,2% OK 11232 503 503 506 506 20/06/2011 20/06/2011 Autre, à préciser (Observations) 504,500 1,7321 0,3% OK 11236 500 503 500 496 10/06/2011 14/06/2011 NF EN 14385 499,750 2,8723 0,6% OK 11240 468 465 467 471 07/06/2011 NF EN 14385 467,750 2,5000 0,5% OK 11249 503 498 505 504 10/06/2011 10/06/2011 NF EN 14385 502,500 3,1091 0,6% OK 11250 490 490 490 490 15/06/2011 15/06/2011 NF EN 14385 490,000 0,0000 0,0% OK 11255 466 470 466 468 27/05/2011 07/06/2011 NF EN 14385 467,500 1,9149 0,4% OK 11262 469 460 493 457 06/06/2011 08/06/2011 Autre, à préciser (Observations) 469,750 16,3172 3,5% OK 11273 488 494 488 496 08/06/2011 08/06/2011 NF EN 14385 491,500 4,1231 0,8% OK 11275 474 472 478 475 09/06/2011 09/06/2011 NF EN 14385 474,750 2,5000 0,5% OK 11279 517 521 516 516 27/05/2011 30/05/2011 NF EN 14385 517,500 2,3805 0,5% OK 11283 460 462 461 462 01/06/2011 22/06/2011 NF EN 14385 461,250 0,9574 0,2% OK 11288 499 503 507 513 30/05/2011 30/05/2011 NF EN 14385 505,500 5,9722 1,2% OK DRC-11-119507-08855B Page 97 sur 171
Table 17-11 119507 Metals_solution Nitric acid hydroperoxide - Thallium Raw Data in µg/liter Laboratory Identification 1 2 3 4 Beginning of analysis End of analysis Standard Average of measurements Standard Deviation of s CVrep by % EXPERT opinion Expert Opinion Comments 11210 22 22 22 22 09/06/2011 10/06/2011 NF EN 14385 22,000 0,0000 0,0% OK 11212 23 22 22 22 30/05/2011 30/05/2011 NF EN 14385 22,250 0,5000 2,2% OK 11232 10 10 10 10 20/06/2011 20/06/2011 Autre, à préciser (Observations) 10,000 0,0000 0,0% Exclus Valeur rendue < 10 11236 23 27 23 23 10/06/2011 14/06/2011 NF EN 14385 24,000 2,0000 8,3% OK 11240 20 20 20 20 07/06/2011 NF EN 14385 20,000 0,0000 0,0% OK 11249 21 21 21 21 10/06/2011 10/06/2011 NF EN 14385 21,000 0,0000 0,0% OK 11250 20 20 20 20 15/06/2011 15/06/2011 NF EN 14385 20,000 0,0000 0,0% OK 11255 19 19 19 19 27/05/2011 07/06/2011 NF EN 14385 19,000 0,0000 0,0% OK 11262 21 20 22 20 06/06/2011 08/06/2011 Autre, à préciser (Observations) 20,750 0,9574 4,6% OK 11273 20 20 20 20 08/06/2011 08/06/2011 NF EN 14385 20,000 0,0000 0,0% OK 11275 20 20 20 20 09/06/2011 09/06/2011 NF EN 14385 20,000 0,0000 0,0% OK 11279 21 21 21 21 27/05/2011 30/05/2011 NF EN 14385 21,000 0,0000 0,0% OK 11283 20 22 20 22 01/06/2011 22/06/2011 NF EN 14385 21,000 1,1547 5,5% OK 11288 20 22 22 22 30/05/2011 30/05/2011 NF EN 14385 21,500 1,0000 4,7% OK DRC-11-119507-08855B Page 98 sur 171
Table 18-11 119507 Metals_solution Nitric acid hydroperoxide - Vanadium Raw Data in µg/liter Laboratory Identification 1 2 3 4 Beginning of analysis End of analysis Standard Average of measurements Standard Deviation of s CVrep by % EXPERT opinion Expert Opinion Comments 11210 197 197 196 196 09/06/2011 10/06/2011 NF EN 14385 196,500 0,5774 0,3% OK 11212 199 199 198 198 30/05/2011 30/05/2011 NF EN 14385 198,500 0,5774 0,3% OK 11232 121 128 118 123 20/06/2011 20/06/2011 Autre, à préciser (Observations) 122,500 4,2032 3,4% OK 11236 197 197 196 195 10/06/2011 14/06/2011 NF EN 14385 196,250 0,9574 0,5% OK 11240 188 187 189 191 07/06/2011 NF EN 14385 188,750 1,7078 0,9% OK 11249 204 200 201 200 10/06/2011 10/06/2011 NF EN 14385 201,250 1,8930 0,9% OK 11250 182 182 182 181 15/06/2011 15/06/2011 NF EN 14385 181,750 0,5000 0,3% OK 11255 184 184 192 186 27/05/2011 07/06/2011 NF EN 14385 186,500 3,7859 2,0% OK 11262 189 189 187 189 06/06/2011 08/06/2011 Autre, à préciser (Observations) 188,500 1,0000 0,5% OK 11273 195 189 197 197 08/06/2011 08/06/2011 NF EN 14385 194,500 3,7859 1,9% OK 11275 182 183 182 182 09/06/2011 09/06/2011 NF EN 14385 182,250 0,5000 0,3% OK 11279 187 188 181 180 27/05/2011 30/05/2011 NF EN 14385 184,000 4,0825 2,2% OK 11283 205 206 205 207 01/06/2011 22/06/2011 NF EN 14385 205,750 0,9574 0,5% OK 11288 171 167 170 173 30/05/2011 30/05/2011 NF EN 14385 170,250 2,5000 1,5% OK DRC-11-119507-08855B Page 99 sur 171
TABLES 19 TO 29-11 119507 METALS DUST FREE PROTOCOL RAW DATA IN µg/g Table 19-11 119507 Metals Dust Free protocol Antimony Raw Data in µg/g Laboratory Identification 1 2 3 4 Beginning of analysis End of analysis Standard Average of measurements Standard Deviation of s CVrep by % EXPERT opinion Expert Opinion Comments 11210 5712 5754 5975 5685 20/06/2011 20/06/2011 NF EN 14385 5781,500 132,0871 2,3% OK 11212 5849 6161 6097 5845 13/06/2011 15/06/2011 NF EN 14385 5988,000 164,9040 2,8% OK 11232 5025 5060 5050 5050 20/06/2011 20/06/2011 Autre, à préciser (Observations) 5046,250 14,9304 0,3% OK 11236 6893 6731 6487 6700 14/06/2011 17/06/2011 NF EN 14385 6702,750 166,8819 2,5% OK 11240 6038 6080 6022 6011 03/06/2011 13/06/2011 NF EN 14385 6037,750 30,2696 0,5% OK 11249 5625 5494 5594 5750 15/06/2011 17/06/2011 NF EN 14385 5615,750 105,5221 1,9% OK 11250 Faites votre choix Non analysé Non analysé Non analysé Exclus 11255 5847 5830 5887 6078 27/05/2011 06/06/2011 NF EN 14385 5910,500 114,1943 1,9% OK 11262 4618 4226 4244 4536 06/06/2011 22/06/2011 Autre, à préciser (Observations) 4406,000 200,4063 4,5% OK 11273 6634 7043 5325 5367 09/06/2011 17/06/2011 NF EN 14385 6092,250 877,8912 14,4% OK 11275 5610 5602 5603 5600 09/06/2011 10/06/2011 NF EN 14385 5603,750 4,3493 0,1% OK 11279 3694 5222 10/06/2011 17/06/2011 NF EN 14385 4458,000 1080,4592 24,2% OK 11283 6240 6303 6418 6581 01/06/2011 22/06/2011 NF EN 14385 6385,500 149,7253 2,3% OK 11288 6346 6152 6286 6057 30/05/2011 06/06/2011 NF EN 14385 6210,250 130,4412 2,1% OK DRC-11-119507-08855B Page 100 sur 171
Table 20-11 119507 Metals Dust Free protocol - Arsenic - Raw Data in µg/g Laboratory Identification 1 2 3 4 Beginning of analysis End of analysis Standard Average of measurements Standard Deviation of s CVrep by % EXPERT opinion Expert Opinion Comments 11210 1451 1409 1553 1490 20/06/2011 20/06/2011 NF EN 14385 1475,750 61,2066 4,1% OK 11212 1443 1436 1420 1500 13/06/2011 15/06/2011 NF EN 14385 1449,750 34,8557 2,4% OK 11232 1380 1400 1360 1480 20/06/2011 20/06/2011 Autre, à préciser (Observations) 1405,000 52,5991 3,7% OK 11236 2467 2434 2356 2515 14/06/2011 17/06/2011 NF EN 14385 2443,000 66,8581 2,7% OK 11240 1839 1785 1796 1802 03/06/2011 13/06/2011 NF EN 14385 1805,500 23,4165 1,3% OK 11249 1364 1352 1313 1313 15/06/2011 17/06/2011 NF EN 14385 1335,500 26,4386 2,0% OK 11250 Faites votre choix Non analysé Non analysé Non analysé Exclus 11255 1488 1521 1496 1561 27/05/2011 06/06/2011 NF EN 14385 1516,500 32,8278 2,2% OK 11262 1357 1336 1325 1353 06/06/2011 22/06/2011 Autre, à préciser (Observations) 1342,750 14,9304 1,1% OK 11273 1886 1977 1605 1582 09/06/2011 17/06/2011 NF EN 14385 1762,500 198,8710 11,3% OK 11275 2800 2900 2880 2820 09/06/2011 10/06/2011 NF EN 14385 2850,000 47,6095 1,7% OK 11279 974 976 10/06/2011 20/06/2011 NF EN 14385 975,000 1,4142 0,1% OK 11283 1670 1680 1608 1656 01/06/2011 22/06/2011 NF EN 14385 1653,500 31,8904 1,9% OK 11288 3660 3864 3637 3420 30/05/2011 06/06/2011 NF EN 14385 3645,250 181,5441 5,0% OK DRC-11-119507-08855B Page 101 sur 171
Table 21-11 119507 Metals Dust Free protocol - Cadmium - Raw Data in µg/g Laboratory Identification 1 2 3 4 Beginning of analysis End of analysis Standard Average of measurements Standard Deviation of s CVrep by % EXPERT opinion Expert Opinion Comments 11210 201 198 207 230 20/06/2011 20/06/2011 NF EN 14385 209,000 14,4914 6,9% OK 11212 174 179 178 177 13/06/2011 15/06/2011 NF EN 14385 177,000 2,1602 1,2% OK 11232 144 144 142 150 20/06/2011 20/06/2011 Autre, à préciser (Observations) 145,000 3,4641 2,4% OK 11236 195 206 216 206 14/06/2011 17/06/2011 NF EN 14385 205,750 8,5781 4,2% OK 11240 196 198 192 191 03/06/2011 13/06/2011 NF EN 14385 194,250 3,3040 1,7% OK 11249 180 172 175 173 15/06/2011 17/06/2011 NF EN 14385 175,000 3,5590 2,0% OK 11250 Faites votre choix Non analysé Non analysé Non analysé Exclus 11255 184 184 186 186 27/05/2011 06/06/2011 NF EN 14385 185,000 1,1547 0,6% OK 11262 194 193 198 200 06/06/2011 22/06/2011 Autre, à préciser (Observations) 196,250 3,3040 1,7% OK 11273 214 217 237 234 09/06/2011 17/06/2011 NF EN 14385 225,500 11,6762 5,2% OK 11275 170 175 172 172 09/06/2011 10/06/2011 NF EN 14385 172,250 2,0616 1,2% OK 11279 125 133 10/06/2011 20/06/2011 NF EN 14385 129,000 5,6569 4,4% OK 11283 521 530 549 521 01/06/2011 22/06/2011 NF EN 14385 530,250 13,2004 2,5% OK 11288 215 209 198 208 30/05/2011 06/06/2011 NF EN 14385 207,500 7,0475 3,4% OK DRC-11-119507-08855B Page 102 sur 171
Tableau 22-11 119507 Metals Dust Free protocol Chromium Raw Data in µg/g Laboratory Identification 1 2 3 4 Beginning of analysis End of analysis Standard Average of measurements Standard Deviation of s CVrep by % EXPERT opinion Expert Opinion Comments 11210 914 944 921 950 20/06/2011 20/06/2011 NF EN 14385 932,250 17,4428 1,9% OK 11212 1434 1452 1385 1414 13/06/2011 15/06/2011 NF EN 14385 1421,250 28,7214 2,0% OK 11232 30 34 30 36 20/06/2011 20/06/2011 Autre, à préciser (Observations) 32,500 3,0000 9,2% OK 11236 324 235 109 132 14/06/2011 17/06/2011 NF EN 14385 200,000 99,1732 49,6% OK 11240 1565 1637 1597 1599 03/06/2011 13/06/2011 NF EN 14385 1599,500 29,4562 1,8% OK 11249 1271 1363 1379 1370 15/06/2011 17/06/2011 NF EN 14385 1345,750 50,2618 3,7% OK 11250 Faites votre choix Non analysé Non analysé Non analysé Exclus 11255 688 674 671 659 27/05/2011 06/06/2011 NF EN 14385 673,000 11,9164 1,8% OK 11262 11 11 8 12 06/06/2011 22/06/2011 Autre, à préciser (Observations) 10,500 1,7321 16,5% OK 11273 1137 1258 749 737 09/06/2011 17/06/2011 NF EN 14385 970,250 267,0598 27,5% OK 11275 42 43 43 43 09/06/2011 10/06/2011 NF EN 14385 42,750 0,5000 1,2% OK 11279 134 212 10/06/2011 20/06/2011 NF EN 14385 173,000 55,1543 31,9% OK 11283 1445 1435 1451 1549 01/06/2011 22/06/2011 NF EN 14385 1470,000 53,0786 3,6% OK 11288 369 328 305 356 30/05/2011 06/06/2011 NF EN 14385 339,500 28,6647 8,4% OK DRC-11-119507-08855B Page 103 sur 171
Table 23-11 119507 Metals Dust Free protocol Cobalt Raw Data in µg/g Laboratory Identification 1 2 3 4 Beginning of analysis End of analysis Standard Average of measurements Standard Deviation of s CVrep by % EXPERT opinion Expert Opinion Comments 11210 1640 1816 1668 1482 20/06/2011 20/06/2011 NF EN 14385 1651,500 136,8637 8,3% OK 11212 1646 1764 1589 1822 13/06/2011 15/06/2011 NF EN 14385 1705,250 106,6251 6,3% OK 11232 1450 1525 1455 1580 20/06/2011 20/06/2011 Autre, à préciser (Observations) 1502,500 61,9812 4,1% OK 11236 2411 2190 2408 2133 14/06/2011 17/06/2011 NF EN 14385 2285,500 145,0667 6,3% OK 11240 1807 1814 1843 1850 03/06/2011 13/06/2011 NF EN 14385 1828,500 21,1739 1,2% OK 11249 1488 1586 1572 1730 15/06/2011 17/06/2011 NF EN 14385 1594,000 100,4656 6,3% OK 11250 Faites votre choix Non analysé Non analysé Non analysé Exclus 11255 1567 1648 1695 1786 27/05/2011 06/06/2011 NF EN 14385 1674,000 91,4877 5,5% OK 11262 1600 1635 1687 1649 06/06/2011 22/06/2011 Autre, à préciser (Observations) 1642,750 35,9850 2,2% OK 11273 2091 2197 1859 1800 09/06/2011 17/06/2011 NF EN 14385 1986,750 188,2098 9,5% OK 11275 1843 1837 1844 1854 09/06/2011 10/06/2011 NF EN 14385 1844,500 7,0475 0,4% OK 11279 1187 1238 10/06/2011 20/06/2011 NF EN 14385 1212,500 36,0624 3,0% OK 11283 1674 1646 1672 1693 01/06/2011 22/06/2011 NF EN 14385 1671,250 19,3111 1,2% OK 11288 2069 1934 1933 1863 30/05/2011 06/06/2011 NF EN 14385 1949,750 86,1680 4,4% OK DRC-11-119507-08855B Page 104 sur 171
Table 24-11 119507 Metals - Dust - Free protocol - Copper - Raw Data in µg/g Laboratory Identification 1 2 3 4 Beginning of analysis End of analysis Standard Average of measurements Standard Deviation of s CVrep by % Expert Opinion Expert Opinion Comments 11210 1854 1819 1891 1821 20/06/2011 20/06/2011 NF EN 14385 1846,250 33,8760 1,8% OK 11212 1969 2004 1966 1913 13/06/2011 15/06/2011 NF EN 14385 1963,000 37,5322 1,9% OK 11232 1670 1695 1610 1675 20/06/2011 20/06/2011 Autre, à préciser (Observations) 1662,500 36,6288 2,2% OK 11236 2345 2373 2355 2363 14/06/2011 17/06/2011 NF EN 14385 2359,000 11,8884 0,5% OK 11240 2057 2037 2139 2076 03/06/2011 13/06/2011 NF EN 14385 2077,250 44,1390 2,1% OK 11249 1922 1978 1819 1892 15/06/2011 17/06/2011 NF EN 14385 1902,750 66,2388 3,5% OK 11250 Faites votre choix Non analysé Non analysé Non analysé Exclus 11255 1808 1864 1801 1903 27/05/2011 06/06/2011 NF EN 14385 1844,000 48,3942 2,6% OK 11262 1916 1839 1822 1800 06/06/2011 22/06/2011 Autre, à préciser (Observations) 1844,250 50,4273 2,7% OK 11273 2280 2394 1962 1921 09/06/2011 17/06/2011 NF EN 14385 2139,250 233,6370 10,9% OK 11275 2100 2120 2100 2130 09/06/2011 10/06/2011 NF EN 14385 2112,500 15,0000 0,7% OK 11279 1436 1306 10/06/2011 20/06/2011 NF EN 14385 1371,000 91,9239 6,7% OK 11283 1997 1965 2015 1981 01/06/2011 22/06/2011 NF EN 14385 1989,500 21,4398 1,1% OK 11288 2051 2022 1911 1982 30/05/2011 06/06/2011 NF EN 14385 1991,500 60,6658 3,0% OK DRC-11-119507-08855B Page 105 sur 171
Table 25-11 119507 Metals - Dust - Free protocol - Manganese - Raw Data in µg/g Laboratory Identification 1 2 3 4 Beginning of analysis End of analysis Standard Average of measurements Standard Deviation of s CVrep by % EXPERT opinion Expert Opinion Comments 11210 1080 1191 1182 1140 20/06/2011 20/06/2011 NF EN 14385 1148,250 50,6384 4,4% OK 11212 1649 1657 1611 1576 13/06/2011 15/06/2011 NF EN 14385 1623,250 37,3486 2,3% OK 11232 1395 1435 1450 1520 20/06/2011 20/06/2011 Autre, à préciser (Observations) 1450,000 52,1217 3,6% OK 11236 1896 2032 2158 1888 14/06/2011 17/06/2011 NF EN 14385 1993,500 128,0352 6,4% OK 11240 2476 2484 2507 2507 03/06/2011 13/06/2011 NF EN 14385 2493,500 15,9269 0,6% OK 11249 1360 1541 1712 1730 15/06/2011 17/06/2011 NF EN 14385 1585,750 172,9285 10,9% OK 11250 Faites votre choix Non analysé Non analysé Non analysé Exclus 11255 1466 1594 1482 1640 27/05/2011 06/06/2011 NF EN 14385 1545,500 84,9215 5,5% OK 11262 868 813 786 1136 06/06/2011 22/06/2011 Autre, à préciser (Observations) 900,750 160,5021 17,8% OK 11273 1911 1973 1667 1639 09/06/2011 17/06/2011 NF EN 14385 1797,500 169,1498 9,4% OK 11275 1720 1730 1720 1731 09/06/2011 10/06/2011 NF EN 14385 1725,250 6,0759 0,4% OK 11279 1193 1157 10/06/2011 20/06/2011 NF EN 14385 1175,000 25,4558 2,2% OK 11283 1653 1669 1724 1677 01/06/2011 22/06/2011 NF EN 14385 1680,750 30,5109 1,8% OK 11288 1709 1692 1688 1672 30/05/2011 06/06/2011 NF EN 14385 1690,250 15,1959 0,9% OK DRC-11-119507-08855B Page 106 sur 171
Table 26-11 119507 Metals - Dust - Free protocol - Nickel - Raw Data in µg/g Laboratory Identification 1 2 3 4 Beginning of analysis End of analysis Standard Average of measurements Standard Deviation of s CVrep by % EXPERT opinion Expert Opinion Comments 11210 1548 1527 1548 1545 20/06/2011 20/06/2011 NF EN 14385 1542,000 10,0995 0,7% OK 11212 1582 1618 1596 1562 13/06/2011 15/06/2011 NF EN 14385 1589,500 23,5726 1,5% OK 11232 1185 1195 1160 1205 20/06/2011 20/06/2011 Autre, à préciser (Observations) 1186,250 19,3111 1,6% OK 11236 2991 2983 3105 3001 14/06/2011 17/06/2011 NF EN 14385 3020,000 57,1431 1,9% OK 11240 1571 1608 1547 1526 03/06/2011 13/06/2011 NF EN 14385 1563,000 35,1852 2,3% OK 11249 1440 1423 1497 1492 15/06/2011 17/06/2011 NF EN 14385 1463,000 37,0855 2,5% OK 11250 Faites votre choix Non analysé Non analysé Non analysé Exclus 11255 1522 1581 1569 1631 27/05/2011 06/06/2011 NF EN 14385 1575,750 44,7763 2,8% OK 11262 800 993 1080 1223 06/06/2011 22/06/2011 Autre, à préciser (Observations) 1024,000 176,8936 17,3% OK 11273 1965 2078 1699 1652 09/06/2011 17/06/2011 NF EN 14385 1848,500 205,9166 11,1% OK 11275 1750 1730 1745 1780 09/06/2011 10/06/2011 NF EN 14385 1751,250 20,9662 1,2% OK 11279 1267 1254 10/06/2011 20/06/2011 NF EN 14385 1260,500 9,1924 0,7% OK 11283 1652 1692 1602 1631 01/06/2011 22/06/2011 NF EN 14385 1644,250 37,8627 2,3% OK 11288 1750 1715 1732 1682 30/05/2011 06/06/2011 NF EN 14385 1719,750 28,9410 1,7% OK DRC-11-119507-08855B Page 107 sur 171
Table 27-11 119507 Metals - Dust - Free protocol - Lead - Raw Data in µg/g Laboratory Identification 1 2 3 4 Beginning of analysis End of analysis Standard Average of measurements Standard Deviation of s CVrep by % EXPERT opinion Expert Opinion Comments 11210 32285 32564 34149 34405 20/06/2011 20/06/2011 NF EN 14385 33350,750 1080,6549 3,2% OK 11212 37800 37990 36150 35970 13/06/2011 15/06/2011 NF EN 14385 36977,500 1064,8122 2,9% OK 11232 33600 35300 31600 34000 20/06/2011 20/06/2011 Autre, à préciser (Observations) 33625,000 1532,6991 4,6% OK 11236 46292 45449 43516 45556 14/06/2011 17/06/2011 NF EN 14385 45203,250 1185,6102 2,6% OK 11240 35082 35129 35891 35959 03/06/2011 13/06/2011 NF EN 14385 35515,250 474,3405 1,3% OK 11249 33000 34539 35229 34864 15/06/2011 17/06/2011 NF EN 14385 34408,000 980,0684 2,8% OK 11250 Faites votre choix Non analysé Non analysé Non analysé Exclus 11255 30804 31660 31131 31973 27/05/2011 06/06/2011 NF EN 14385 31392,000 523,8479 1,7% OK 11262 35035 35644 35895 35534 06/06/2011 22/06/2011 Autre, à préciser (Observations) 35527,000 361,1214 1,0% OK 11273 30250 31882 24174 24067 09/06/2011 17/06/2011 NF EN 14385 27593,250 4065,1940 14,7% OK 11275 42500 43100 42800 42900 09/06/2011 10/06/2011 NF EN 14385 42825,000 250,0000 0,6% OK 11279 29273 28629 10/06/2011 20/06/2011 NF EN 14385 28951,000 455,3768 1,6% OK 11283 34530 34611 34435 35022 01/06/2011 22/06/2011 NF EN 14385 34649,500 258,5401 0,7% OK 11288 38638 37952 37526 36797 30/05/2011 06/06/2011 NF EN 14385 37728,250 771,5441 2,0% OK DRC-11-119507-08855B Page 108 sur 171
Table 28-11 119507 Metals - Dust - Free protocol - Thallium - Raw Data in µg/g Laboratory Identification 1 2 3 4 Beginning of analysis End of analysis Standard Average of measurements Standard Deviation of s CVrep by % EXPERT opinion Expert Opinion Comments 11210 234 234 247 238 20/06/2011 20/06/2011 NF EN 14385 238,250 6,1305 2,6% OK 11212 76 76 79 83 13/06/2011 15/06/2011 NF EN 14385 78,500 3,3166 4,2% OK 11232 229 235 232 232 20/06/2011 20/06/2011 Autre, à préciser (Observations) 232,000 2,4495 1,1% OK 11236 252 244 259 280 14/06/2011 17/06/2011 NF EN 14385 258,750 15,4353 6,0% OK 11240 243 244 246 248 03/06/2011 13/06/2011 NF EN 14385 245,250 2,2174 0,9% OK 11249 222 225 199 227 15/06/2011 17/06/2011 NF EN 14385 218,250 12,9968 6,0% OK 11250 Faites votre choix Non analysé Non analysé Non analysé Exclus 11255 233 259 244 243 27/05/2011 06/06/2011 NF EN 14385 244,750 10,7199 4,4% OK 11262 253 244 245 257 06/06/2011 22/06/2011 Autre, à préciser (Observations) 249,750 6,2915 2,5% OK 11273 271 278 310 300 09/06/2011 17/06/2011 NF EN 14385 289,750 18,3007 6,3% OK 11275 180 185 182 190 09/06/2011 10/06/2011 NF EN 14385 184,250 4,3493 2,4% OK 11279 49 64 10/06/2011 20/06/2011 NF EN 14385 56,500 10,6066 18,8% Exclus 2 valeurs rendues dont 1 <49 11283 250 249 249 254 01/06/2011 22/06/2011 NF EN 14385 250,500 2,3805 1,0% OK 11288 441 427 415 404 30/05/2011 06/06/2011 NF EN 14385 421,750 15,9034 3,8% OK DRC-11-119507-08855B Page 109 sur 171
Table 29-11 119507 Metals - Dust - Free protocol - Vanadium - Raw Data in µg/g Laboratory Identification 1 2 3 4 Beginning of analysis End of analysis Standard Average of measurements Standard Deviation of s CVrep by % EXPERT opinion Expert Opinion Comments 11210 1504 1536 1417 1398 20/06/2011 20/06/2011 NF EN 14385 1463,750 66,7052 4,6% OK 11212 1617 1644 1638 1565 13/06/2011 15/06/2011 NF EN 14385 1616,000 35,9166 2,2% OK 11232 1035 1040 1065 1070 20/06/2011 20/06/2011 Autre, à préciser (Observations) 1052,500 17,5594 1,7% OK 11236 1338 1356 1322 1291 14/06/2011 17/06/2011 NF EN 14385 1326,750 27,5847 2,1% OK 11240 1760 1779 1758 1776 03/06/2011 13/06/2011 NF EN 14385 1768,250 10,7819 0,6% OK 11249 1418 1320 1263 1408 15/06/2011 17/06/2011 NF EN 14385 1352,250 74,0197 5,5% OK 11250 Faites votre choix Non analysé Non analysé Non analysé Exclus 11255 1374 1414 1377 1429 27/05/2011 06/06/2011 NF EN 14385 1398,500 27,2825 2,0% OK 11262 1427 1474 1529 1447 06/06/2011 22/06/2011 Autre, à préciser (Observations) 1469,250 44,2446 3,0% OK 11273 1740 1840 1426 1413 09/06/2011 17/06/2011 NF EN 14385 1604,750 217,8338 13,6% OK 11275 1220 1180 1190 1205 09/06/2011 10/06/2011 NF EN 14385 1198,750 17,5000 1,5% OK 11279 1134 1071 10/06/2011 20/06/2011 NF EN 14385 1102,500 44,5477 4,0% OK 11283 1695 1683 1578 1498 01/06/2011 22/06/2011 NF EN 14385 1613,500 93,2255 5,8% OK 11288 1632 1745 1663 1618 30/05/2011 06/06/2011 NF EN 14385 1664,500 56,8653 3,4% OK DRC-11-119507-08855B Page 110 sur 171
TABLE 30 À 40-11 119507 METALS DUST IMPOSED PROTOCOL- RAW DATA IN µg/g Table 30-11 119507 Metals - Dust - Imposed protocol - Antimony - Raw Data in µg/g Laboratory Identification 1 2 3 4 Beginning of analysis End of analysis Standard Average of measurements Standard Deviation of s CVrep by % EXPERT opinion Expert Opinion Comments 11210 6525 6263 6366 6118 01/06/2011 06/06/2011 NF EN 14385 6318,000 171,4429 2,7% OK 11212 Faites votre choix Non analysé Non analysé Non analysé Exclus 11232 5500 5680 5480 5480 20/06/2011 20/06/2011 Autre, à préciser (Observations) 5535,000 97,1253 1,8% OK 11236 6887 6639 6825 6880 14/06/2011 17/06/2011 NF EN 14385 6807,750 115,8659 1,7% OK 11240 6029 5972 6079 6096 03/06/2011 13/06/2011 NF EN 14385 6044,000 55,7913 0,9% OK 11249 5824 5883 5896 5877 15/06/2011 17/06/2011 NF EN 14385 5870,000 31,6754 0,5% OK 11250 Faites votre choix Non analysé Non analysé Non analysé Exclus 11255 5982 6221 5995 6057 27/05/2011 30/05/2011 NF EN 14385 6063,750 109,8222 1,8% OK 11262 Faites votre choix Non analysé Non analysé Non analysé Exclus 11273 6634 7043 5325 5367 09/06/2011 17/06/2011 NF EN 14385 6092,250 877,8912 14,4% OK 11275 Faites votre choix Non analysé Non analysé Non analysé Exclus 11279 6594 7095 10/06/2011 17/06/2011 NF EN 14385 6844,500 354,2605 5,2% OK 11283 5907 5927 5974 5984 01/06/2011 22/06/2011 NF EN 14385 5948,000 36,9414 0,6% OK 11288 6346 6152 6286 6057 30/05/2011 06/06/2011 NF EN 14385 6210,250 130,4412 2,1% OK DRC-11-119507-08855B Page 111 sur 171
Table 31-11 119507 Metals - Dust - Imposed protocol - Arsenic - Raw Data in µg/g Laboratory Identification 1 2 3 4 Beginning of analysis End of analysis Standard Average of measurements Standard Deviation of s CVrep by % EXPERT opinion Expert Opinion Comments 11210 1518 1471 1637 1621 01/06/2011 06/06/2011 NF EN 14385 1561,750 80,2553 5,1% OK 11212 Faites votre choix Non analysé Non analysé Non analysé Exclus 11232 1430 1510 1430 1560 20/06/2011 20/06/2011 Autre, à préciser (Observations) 1482,500 63,9661 4,3% OK 11236 2510 2344 2452 2305 14/06/2011 17/06/2011 NF EN 14385 2402,750 94,7536 3,9% OK 11240 1905 1803 1802 1804 03/06/2011 13/06/2011 NF EN 14385 1828,500 51,0065 2,8% OK 11249 1366 1459 1377 1392 15/06/2011 17/06/2011 NF EN 14385 1398,500 41,7173 3,0% OK 11250 Faites votre choix Non analysé Non analysé Non analysé Exclus 11255 1528 1510 1492 1521 27/05/2011 30/05/2011 NF EN 14385 1512,750 15,6924 1,0% OK 11262 Faites votre choix Non analysé Non analysé Non analysé Exclus 11273 1886 1977 1605 1582 09/06/2011 17/06/2011 NF EN 14385 1762,500 198,8710 11,3% OK 11275 Faites votre choix Non analysé Non analysé Non analysé Exclus 11279 1356 1385 10/06/2011 20/06/2011 NF EN 14385 1370,500 20,5061 1,5% OK 11283 1705 1711 1725 1728 01/06/2011 22/06/2011 NF EN 14385 1717,250 11,0265 0,6% OK 11288 3360 3864 3637 3420 30/05/2011 06/06/2011 NF EN 14385 3570,250 229,1468 6,4% OK DRC-11-119507-08855B Page 112 sur 171
Table 32-11 119507 Metals - Dust - Imposed protocol - Cadmium - Raw Data in µg/g Laboratory Identification 1 2 3 4 Beginning of analysis End of analysis Standard Average of measurements Standard Deviation of s CVrep by % EXPERT opinion Expert Opinion Comments 11210 232 232 241 220 01/06/2011 06/06/2011 NF EN 14385 231,250 8,6168 3,7% OK 11212 Faites votre choix Non analysé Non analysé Non analysé Exclus 11232 159 164 159 159 20/06/2011 20/06/2011 Autre, à préciser (Observations) 160,250 2,5000 1,6% OK 11236 205 205 220 218 14/06/2011 17/06/2011 NF EN 14385 212,000 8,1240 3,8% OK 11240 194 194 199 201 03/06/2011 13/06/2011 NF EN 14385 197,000 3,5590 1,8% OK 11249 173 176 174 179 15/06/2011 17/06/2011 NF EN 14385 175,500 2,6458 1,5% OK 11250 Faites votre choix Non analysé Non analysé Non analysé Exclus 11255 193 204 185 192 27/05/2011 30/05/2011 NF EN 14385 193,500 7,8528 4,1% OK 11262 Faites votre choix Non analysé Non analysé Non analysé Exclus 11273 214 217 237 234 09/06/2011 17/06/2011 NF EN 14385 225,500 11,6762 5,2% OK 11275 Faites votre choix Non analysé Non analysé Non analysé Exclus 11279 166 168 10/06/2011 20/06/2011 NF EN 14385 167,000 1,4142 0,8% OK 11283 629 628 634 623 01/06/2011 22/06/2011 NF EN 14385 628,500 4,5092 0,7% OK 11288 215 209 198 208 30/05/2011 06/06/2011 NF EN 14385 207,500 7,0475 3,4% OK DRC-11-119507-08855B Page 113 sur 171
Table 33-11 119507 Metals - Dust - Imposed protocol - Chromium - Raw Data in µg/g Laboratory Identification 1 2 3 4 Beginning of analysis End of analysis Standard Average of measurements Standard Deviation of s CVrep by % EXPERT opinion Expert Opinion Comments 11210 704 816 791 1152 01/06/2011 06/06/2011 NF EN 14385 865,750 196,7780 22,7% OK 11212 Faites votre choix Non analysé Non analysé Non analysé Exclus 11232 31 32 34 34 20/06/2011 20/06/2011 Autre, à préciser (Observations) 32,750 1,5000 4,6% OK 11236 354 349 400 1493 14/06/2011 17/06/2011 NF EN 14385 649,000 563,1347 86,8% OK 11240 1671 1626 1663 1778 03/06/2011 13/06/2011 NF EN 14385 1684,500 65,3427 3,9% OK 11249 1378 1378 1377 1370 15/06/2011 17/06/2011 NF EN 14385 1375,750 3,8622 0,3% OK 11250 Faites votre choix Non analysé Non analysé Non analysé Exclus 11255 694 657 626 626 27/05/2011 30/05/2011 NF EN 14385 650,750 32,3252 5,0% OK 11262 Faites votre choix Non analysé Non analysé Non analysé Exclus 11273 1137 1258 749 737 09/06/2011 17/06/2011 NF EN 14385 970,250 267,0598 27,5% OK 11275 Faites votre choix Non analysé Non analysé Non analysé Exclus 11279 1446 1300 10/06/2011 20/06/2011 NF EN 14385 1373,000 103,2376 7,5% OK 11283 1539 1530 1649 1656 01/06/2011 22/06/2011 NF EN 14385 1593,500 68,2862 4,3% OK 11288 369 328 305 356 30/05/2011 06/06/2011 NF EN 14385 339,500 28,6647 8,4% OK DRC-11-119507-08855B Page 114 sur 171
Table 34-11 119507 Metals - Dust - Imposed protocol - Cobalt - Raw Data in µg/g Laboratory Identification 1 2 3 4 Beginning of analysis End of analysis Standard Average of measurements Standard Deviation of s CVrep by % EXPERT opinion Expert Opinion Comments 11210 1589 1827 1853 1789 01/06/2011 06/06/2011 NF EN 14385 1764,500 119,9152 6,8% OK 11212 Faites votre choix Non analysé Non analysé Non analysé Exclus 11232 1735 1770 1750 1785 20/06/2011 20/06/2011 Autre, à préciser (Observations) 1760,000 21,9848 1,2% OK 11236 2254 2258 2223 2099 14/06/2011 17/06/2011 NF EN 14385 2208,500 74,6570 3,4% OK 11240 1950 1827 1841 1712 03/06/2011 13/06/2011 NF EN 14385 1832,500 97,3465 5,3% OK 11249 1698 1624 1618 1642 15/06/2011 17/06/2011 NF EN 14385 1645,500 36,4555 2,2% OK 11250 Faites votre choix Non analysé Non analysé Non analysé Exclus 11255 1591 1627 1671 1730 27/05/2011 30/05/2011 NF EN 14385 1654,750 59,8909 3,6% OK 11262 Faites votre choix Non analysé Non analysé Non analysé Exclus 11273 2081 2197 1859 1800 09/06/2011 17/06/2011 NF EN 14385 1984,250 186,4213 9,4% OK 11275 Faites votre choix Non analysé Non analysé Non analysé Exclus 11279 1717 1787 10/06/2011 20/06/2011 NF EN 14385 1752,000 49,4975 2,8% OK 11283 1650 1646 1810 1794 01/06/2011 22/06/2011 NF EN 14385 1725,000 89,1665 5,2% OK 11288 2069 1934 1933 1863 30/05/2011 06/06/2011 NF EN 14385 1949,750 86,1680 4,4% OK DRC-11-119507-08855B Page 115 sur 171
Table 35-11 119507 Metals - Dust - Imposed protocol - Copper - Raw Data in µg/g Laboratory Identification 1 2 3 4 Beginning of analysis End of analysis Standard Average of measurements Standard Deviation of s CVrep by % EXPERT opinion Expert Opinion Comments 11210 2043 1964 2106 1902 01/06/2011 06/06/2011 NF EN 14385 2003,750 89,3099 4,5% OK 11212 Faites votre choix Non analysé Non analysé Non analysé Exclus 11232 1865 1935 1915 1915 20/06/2011 20/06/2011 Autre, à préciser (Observations) 1907,500 29,8608 1,6% OK 11236 2358 2381 2444 2324 14/06/2011 17/06/2011 NF EN 14385 2376,750 50,5791 2,1% OK 11240 2198 2448 2060 2124 03/06/2011 13/06/2011 NF EN 14385 2207,500 169,9598 7,7% OK 11249 1998 1915 1913 1944 15/06/2011 17/06/2011 NF EN 14385 1942,500 39,6190 2,0% OK 11250 Faites votre choix Non analysé Non analysé Non analysé Exclus 11255 1823 1818 1773 1815 27/05/2011 30/05/2011 NF EN 14385 1807,250 23,0705 1,3% OK 11262 Faites votre choix Non analysé Non analysé Non analysé Exclus 11273 2280 2394 1962 1921 09/06/2011 17/06/2011 NF EN 14385 2139,250 233,6370 10,9% OK 11275 Faites votre choix Non analysé Non analysé Non analysé Exclus 11279 1853 1856 10/06/2011 20/06/2011 NF EN 14385 1854,500 2,1213 0,1% OK 11283 1973 1980 2070 2084 01/06/2011 22/06/2011 NF EN 14385 2026,750 58,3745 2,9% OK 11288 2051 2022 1911 1982 30/05/2011 06/06/2011 NF EN 14385 1991,500 60,6658 3,0% OK DRC-11-119507-08855B Page 116 sur 171
Table 36-11 119507 Metals - Dust - Imposed protocol - Manganese - Raw Data in µg/g Laboratory Identification 1 2 3 4 Beginning of analysis End of analysis Standard Average of measurements Standard Deviation of s CVrep by % EXPERT opinion Expert Opinion Comments 11210 1767 1952 1761 1686 01/06/2011 06/06/2011 NF EN 14385 1791,500 113,1680 6,3% OK 11212 Faites votre choix Non analysé Non analysé Non analysé Exclus 11232 1590 1655 1620 1620 20/06/2011 20/06/2011 Autre, à préciser (Observations) 1621,250 26,5754 1,6% OK 11236 2221 2136 2287 2144 14/06/2011 17/06/2011 NF EN 14385 2197,000 71,1946 3,2% OK 11240 2739 2256 2494 2540 03/06/2011 13/06/2011 NF EN 14385 2507,250 198,3959 7,9% OK 11249 1668 1665 1613 1669 15/06/2011 17/06/2011 NF EN 14385 1653,750 27,2198 1,6% OK 11250 Faites votre choix Non analysé Non analysé Non analysé Exclus 11255 1634 1704 1588 1730 27/05/2011 30/05/2011 NF EN 14385 1664,000 64,8896 3,9% OK 11262 Faites votre choix Non analysé Non analysé Non analysé Exclus 11273 1911 1973 1667 1639 09/06/2011 17/06/2011 NF EN 14385 1797,500 169,1498 9,4% OK 11275 Faites votre choix Non analysé Non analysé Non analysé Exclus 11279 1657 1688 10/06/2011 20/06/2011 NF EN 14385 1672,500 21,9203 1,3% OK 11283 1772 1781 1613 1625 01/06/2011 22/06/2011 NF EN 14385 1697,750 91,1386 5,4% OK 11288 1709 1692 1688 1672 30/05/2011 06/06/2011 NF EN 14385 1690,250 15,1959 0,9% OK DRC-11-119507-08855B Page 117 sur 171
Table 37-11 119507 Metals - Dust - Imposed protocol - Nickel - Raw Data in µg/g Laboratory Identification 1 2 3 4 Beginning of analysis End of analysis Standard Average of measurements Standard Deviation of s CVrep by % EXPERT opinion Expert Opinion Comments 11210 1653 1683 1799 1657 01/06/2011 06/06/2011 NF EN 14385 1698,000 68,6343 4,0% OK 11212 Faites votre choix Non analysé Non analysé Non analysé Exclus 11232 1340 1355 1330 1330 20/06/2011 20/06/2011 Autre, à préciser (Observations) 1338,750 11,8145 0,9% OK 11236 3029 2983 3187 3008 14/06/2011 17/06/2011 NF EN 14385 3051,750 92,1064 3,0% OK 11240 1622 1591 1621 1600 03/06/2011 13/06/2011 NF EN 14385 1608,500 15,4596 1,0% OK 11249 1520 1566 1523 1593 15/06/2011 17/06/2011 NF EN 14385 1550,500 35,2751 2,3% OK 11250 Faites votre choix Non analysé Non analysé Non analysé Exclus 11255 1536 1546 1524 1562 27/05/2011 30/05/2011 NF EN 14385 1542,000 16,0831 1,0% OK 11262 Faites votre choix Non analysé Non analysé Non analysé Exclus 11273 1965 2078 1699 1652 09/06/2011 17/06/2011 NF EN 14385 1848,500 205,9166 11,1% OK 11275 Faites votre choix Non analysé Non analysé Non analysé Exclus 11279 1636 1632 10/06/2011 20/06/2011 NF EN 14385 1634,000 2,8284 0,2% OK 11283 1732 1742 1787 1805 01/06/2011 22/06/2011 NF EN 14385 1766,500 35,0856 2,0% OK 11288 1750 1715 1732 1682 30/05/2011 06/06/2011 NF EN 14385 1719,750 28,9410 1,7% OK DRC-11-119507-08855B Page 118 sur 171
Table 38-11 119507 Metals - Dust - Imposed protocol - Lead - Raw Data in µg/g Laboratory Identification 1 2 3 4 Beginning of analysis End of analysis Standard Average of measurements Standard Deviation of s CVrep by % EXPERT opinion Expert Opinion Comments 11210 38526 33798 37907 35015 01/06/2011 06/06/2011 NF EN 14385 36311,500 2269,2308 6,2% OK 11212 Faites votre choix Non analysé Non analysé Non analysé Exclus 11232 37100 37300 36100 36100 20/06/2011 20/06/2011 Autre, à préciser (Observations) 36650,000 640,3124 1,7% OK 11236 46390 44154 46639 47237 14/06/2011 17/06/2011 NF EN 14385 46105,000 1348,3578 2,9% OK 11240 36110 36031 36848 36448 03/06/2011 13/06/2011 NF EN 14385 36359,250 372,6601 1,0% OK 11249 35313 35126 34213 35895 15/06/2011 17/06/2011 NF EN 14385 35136,750 697,4804 2,0% OK 11250 Faites votre choix Non analysé Non analysé Non analysé Exclus 11255 32824 34082 33120 33379 27/05/2011 30/05/2011 NF EN 14385 33351,250 537,3499 1,6% OK 11262 Faites votre choix Non analysé Non analysé Non analysé Exclus 11273 30250 31882 24174 24067 09/06/2011 17/06/2011 NF EN 14385 27593,250 4065,1940 14,7% OK 11275 Faites votre choix Non analysé Non analysé Non analysé Exclus 11279 34653 39130 10/06/2011 20/06/2011 NF EN 14385 36891,500 3165,7171 8,6% OK 11283 34805 34793 35055 34945 01/06/2011 22/06/2011 NF EN 14385 34899,500 124,5298 0,4% OK 11288 38838 37952 37526 36797 30/05/2011 06/06/2011 NF EN 14385 37778,250 852,3968 2,3% OK DRC-11-119507-08855B Page 119 sur 171
Table 39-11 119507 Metals - Dust - Imposed protocol - Thallium - Raw Data in µg/g Laboratory Identification 1 2 3 4 Beginning of analysis End of analysis Standard Average of measurements Standard Deviation of s CVrep by % EXPERT opinion Expert Opinion Comments 11210 288 285 274 284 01/06/2011 06/06/2011 NF EN 14385 282,750 6,0759 2,1% OK 11212 Faites votre choix Non analysé Non analysé Non analysé Exclus 11232 260 285 270 270 20/06/2011 20/06/2011 Autre, à préciser (Observations) 271,250 10,3078 3,8% OK 11236 304 254 320 286 14/06/2011 17/06/2011 NF EN 14385 291,000 28,3078 9,7% OK 11240 236 248 275 245 03/06/2011 13/06/2011 NF EN 14385 251,000 16,7929 6,7% OK 11249 212 205 206 207 15/06/2011 17/06/2011 NF EN 14385 207,500 3,1091 1,5% OK 11250 Faites votre choix Non analysé Non analysé Non analysé Exclus 11255 255 256 255 263 27/05/2011 30/05/2011 NF EN 14385 257,250 3,8622 1,5% OK 11262 Faites votre choix Non analysé Non analysé Non analysé Exclus 11273 271 278 310 300 09/06/2011 17/06/2011 NF EN 14385 289,750 18,3007 6,3% OK 11275 Faites votre choix Non analysé Non analysé Non analysé Exclus 11279 165 85 10/06/2011 20/06/2011 NF EN 14385 125,000 56,5685 45,3% OK 11283 258 262 245 249 01/06/2011 22/06/2011 NF EN 14385 253,500 7,8528 3,1% OK 11288 441 427 415 404 30/05/2011 06/06/2011 NF EN 14385 421,750 15,9034 3,8% OK DRC-11-119507-08855B Page 120 sur 171
Table 40-11 119507 Metals - Dust - Imposed protocol - Vanadium - Raw Data in µg/g Laboratory Identification 1 2 3 4 Beginning of analysis End of analysis Standard Average of measurements Standard Deviation of s CVrep by % EXPERT opinion Expert Opinion Comments 11210 1640 1503 1705 1511 01/06/2011 06/06/2011 NF EN 14385 1589,750 99,2216 6,2% OK 11212 Faites votre choix Non analysé Non analysé Non analysé Exclus 11232 1300 1300 1300 1300 20/06/2011 20/06/2011 Autre, à préciser (Observations) 1300,000 0,0000 0,0% OK 11236 1303 1252 1302 1293 14/06/2011 17/06/2011 NF EN 14385 1287,500 24,0901 1,9% OK 11240 1817 1688 1828 1892 03/06/2011 13/06/2011 NF EN 14385 1806,250 85,4883 4,7% OK 11249 1432 1460 1372 1436 15/06/2011 17/06/2011 NF EN 14385 1425,000 37,4344 2,6% OK 11250 Faites votre choix Non analysé Non analysé Non analysé Exclus 11255 1406 1397 1366 1377 27/05/2011 30/05/2011 NF EN 14385 1386,500 18,2665 1,3% OK 11262 Faites votre choix Non analysé Non analysé Non analysé Exclus 11273 1740 1840 1426 1413 09/06/2011 17/06/2011 NF EN 14385 1604,750 217,8338 13,6% OK 11275 Faites votre choix Non analysé Non analysé Non analysé Exclus 11279 1420 1409 10/06/2011 20/06/2011 NF EN 14385 1414,500 7,7782 0,5% OK 11283 1520 1520 1646 1652 01/06/2011 22/06/2011 NF EN 14385 1584,500 74,5185 4,7% OK 11288 1632 1745 1663 1618 30/05/2011 06/06/2011 NF EN 14385 1664,500 56,8653 3,4% OK DRC-11-119507-08855B Page 121 sur 171
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-11-119507-08855B Page 122 sur 171
11 119507 HCI ACIDE CHLORHYDRIQUE DRC-11-119507-08855B Page 123 sur 171
11 119507 HF ACIDE FLUORHYDRIQUE DRC-11-119507-08855B Page 124 sur 171
11 119507 HF POUSSIERE - ACIDE FLUORHYDRIQUE DRC-11-119507-08855B Page 125 sur 171
11 119507 NH3 AMMONIAC DRC-11-119507-08855B Page 126 sur 171
11 119507 SO2 DIOXYDE DE SOUFRE DRC-11-119507-08855B Page 127 sur 171
11 119507 HG K2CR2O7 - MERCURE DRC-11-119507-08855B Page 128 sur 171
11 119507 HG_KMNO4 - MERCURE DRC-11-119507-08855B Page 129 sur 171
11 119507 METAUX_SOLUTION (11 FIGURES) DRC-11-119507-08855B Page 130 sur 171
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11 119507 METAUX POUSSIERE PROTOCOLE LIBRE (11 FIGURES) DRC-11-119507-08855B Page 141 sur 171
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11 119507 METAUX POUSSIERE PROTOCOLE IMPOSE (11 FIGURES) DRC-11-119507-08855B Page 152 sur 171
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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-11-119507-07760B Page 163 sur 171
FIGURE 1 : 11/119507_METAUX SOLUTION (PART 1 TO 3) DRC-11-119507-07760B Page 164 sur 171
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FIGURE 2: 11/119507_METAUX POUSSIERE FREE PROTOCOL (PART 1 TO 3) DRC-11-119507-07760B Page 167 sur 171
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FIGURE 3: 11/119507_METAUX POUSSIERE IMPOSED PROTOCOLE (PART 1 TO 2) DRC-11-119507-07760B Page 170 sur 171
11/119507_METAUX POUSSIERE IMPOSED PROTOCOL (PART 2) DRC-11-119507-07760B Page 171 sur 171