French Inter-laboratories campaigns Context and finality

Context Arrêté du 04 septembre 2000 (agrément des organismes de contrôle) “agréments” are issued to laboratories performing sampling that have been accredited (programme n°97 COFRAC or equivt) agree to participate to interlaboratory campaigns of 3 days organized at INERIS at least once every 3 years on the bench and every year for the analytical comparisons.

Finality of the tests on the bench To follow and improve the quality of implementation of SRM through the evolution of Confidence intervals of reproducibility, compared to those required by EN standards, information and training for new EN standards (comparisons of measuring devices, of results). Judgment of the capacity of the laboratories conformity of measuring devices and of the implementation through audits, test of knowledge of standards, comparison of results / Caverage... ==> - the results of these tests are evaluated by the commission in charge of delivering “agréments” to the laboratories. - the synthesis report which enlightens slips of each laboratory in implementation of the SRM may be audited by the accreditation body. Ces finalités ont été discutées en interne à l’INERIS avec notre direction. Elle a été exposée et défendue par Jacques Repussard ( DG adjoint de l’INERIS) lors d’une réunion réunissant les responsables du COFRAC, Guillaume Bailly du MEDD en 2000 ? Les finalités ont été réafirmées lors des réunions de la commission agrément.

The bench

Specificity of the tests on the bench The totality of the method is involved (sampling + analysis) Generation of real flue gases in order to be under real conditions of operation (matrix, temperature, moisture). Means: generation of combustion gases, doped by additions of pollutants ignorance of the generated exact concentration Advantages: Possibility to simulate different types of gases (LCP, WI) provide real data and uncertainties at different level of concentrations Drawbacks: true value unknown _ comparisons of the results with the average value given by the participants limited number of participants ==> use of statistics limited

Capacity criteria Respect of QA/QC procedures and associated criteria field blank Leak test absorption efficiency Respect of standardised procedures list of key points check of provisions (written procedures, forms) check of application

Inter-laboratories tests Approach in the field leads to determination of the fidelity of the method characterised by a standard deviation or a repeatability or reproducibility confidence interval ==> see ISO 5725-2 lab A Sampled gases Type uncertainty sr "repeatability" lab A lab A lab A Type uncertainty sR Sampled gases "reproducibility" lab B lab C

Inter-laboratories tests lab A - 2 lab A - 1 Flue gases lab D - 1 lab B - 1 lab D - 2 lab B - 2 lab C - 2 lab C - 1

Inter-laboratories tests Results of the 26 first campaigns obtained with accredited laboratories They relates to : automatic analysis of O2 (5-13%), CO2, CO (10 à 500 mg/m3), NOx (75 à 1000 mg/m3), SO2 (40 à 1000 mg/m3) et COVT (0 à 50 mgC/m3) and from the 7th campaign on manual methods for HCl, HF, Hg and at last on H2O. From the 9th campaign participants are accredited and consequently EN standards should be applied.

Inter-laboratories tests Maximum value of Target value for the confidence interval reproducibility confidence fixed by directives interval : t.s R O - ±6 % 2 CO ±10 % ±5 % SO ±20 % ±10 % * 2 NO ±20 % ±10 % x COVT ±30 % ±15 % HF and HCl ±40 % ±20 % Hg - 25% dust ±30 % ±15 % * impossible to reach due to the manual method

Analytical inter-laboratories tests compound concentration s r average % R % I CR HF 2,1 mg/m 3 n 2,7 26,5 53,0 4,7 mg/m 2,9 18,1 36,2 HCl 20,6 mg/m 1,1 6,5 13,0 102,3 mg/m 0,9 4,3 8,6 SO 2 75,7 mg/m 14,1 28,2 214,7 mg/m 1,0 3,5 7,0 Hg 43,3 µg/m 4,8 13,8 27,6 130,0 µg/m 2,5 12,7 25,4 s : repeatability standard deviation r s : reproducibility standard deviation R I CR : : reproducibility confidence interval

Analytical inter-laboratories tests

Analytical inter-laboratories tests

Analytical inter-laboratories tests Compounds Target value µg/g Average X (µg/g) Recovery rate % Arsenic 3020 2346 77,7 Cadmium 520 421 81,0 Cobalt 4480 4065 90,7 Chrome 2690 410 15,2 Copper 6310 5573 88,3 Manganese 4920 4425 89,9 Nickel 5390 4688 87,0 Lead 10150 8543 84,2 Antimony 9190 8102 88,2 Tin 7250 103 1,4 Thallium 690 451 65,4 Selenium 7009 2082 29,7 Tellurium 6205 1082 27,4 Zinc 27478 25316 92,1 Vanadium 4050 3623 89,5 Table 4 : statistics values– digestion efficiency

Inter-laboratories tests O2 and CO2 Ic reference Ic average Ic 2005 Ic avrIcref Ic2005/Icref O 2 0,9 4,2 1,7 5,0 2,0 CO 4,0 3,8 Target value for O2 and CO2 : 6% Target reached in 2005 for 4 campaigns out of 4 for O2: : 2,75 / 0,45 / 1,9 / 1.7 improvement Target reached Target reached in 2005 for 4 campaigns out of 4 for CO2 : 3,7 / 5,05 / 4,4 / 2,2 Stability 1 3 4 5 6 7 8 9 10 11 12 13 14 15 O2 4-13% IC % CO2 4-10% 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 Number of campaigns

Inter-laboratories tests NOx 50 45 40 35 30 Ic % 25 NOx 80-1000mg/m3 20 15 10 5 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 Number of campaigns Ic reference Ic average Ic Ic /Icref 2005 Ic ave/Icref 2005 NOx 80-1000mg/m 3 2 11,1 11,9 5,5 6,0 Target for NOx : 10 % Target reached in 2005 2 times : 10 / 11,2 / 19,3 / 7,2 Light improvement Target reached at 50% Improvements to be brought : respect warm up time of the analysers Leak tests Contrôle of drifts contrôle of converter (efft > 95 %) Losses of NO 2

Inter-laboratories tests CO and TOC Ic reference Ic average Ic 2005 Ic av/Icref /Icref CO 30-500mg/m 3 3,1 15,1 5,2 5,0 1,7 10-30mg/m 2,4 50,9 43,5 21,2 18,1 TOC 5-40mgC/m 36,2 36,8 Target for CO : 5% Target reached 2 timesout of 4 in 2005 : 7,9 / 5,7 / 4,3 / 2,7 Improvement Target reached at 50% Target for TOC : 15% Target not reached in 2005 : 20,9 / 46,4 / 42,9 / 37 Target not reached ) 200 180 160 CO 30-500mg/m3 140 120 TOC 5-40mgC/m3 Ic % 100 80 60 CO 10-30mg/m3 40 20 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 Number of campaigns

Inter-laboratories tests H2O 50 45 40 35 30 Ic % 25 H2O % 20 15 2 10 5 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 Number of campaigns Ic reference Ic average Ic 2005 Ic av/Icref Ic /Icref 2005 H O 2 % 20 23,6 19,1 1,2 1,0 Target for H O : 20 % 2 Target reached in 2005 1 time out of 4 : 12 / 20,2 / 20,6 / 23,4 Improvement Targetr reached at 25% Improvements to be brought : Leak test Global weighing of the whole water capture system with a balance of 0,1g precision Heating of the sampling line

Inter-laboratories tests SO2 , HCl and HF , Ic reference Ic average Ic 2005 Ic moy/Icref /Icref SO 2 70-300mg/m 3 10 41,5 32,1 4,1 3,2 HF 5mg/m 30 75,4 29,9 2,5 1,0 HCl 40mg/m 5 43,1 34,2 8,6 6,8 Target for SO : 20 % Target not reached in 2005 : 43,5 / 39,8 / 21,4 / 23,8 Improvement Target not reached Ic analytique 2002 : 29,8 % at 76 mg/m and11 % at 212 mg/m Target for HCl Target not reached in 2005 : 25 / 40 / 50 / 30 Light improvement Ic analytique 2002 at 20 mg/m : 13 % Target for HF pour 5 mg/m Target not reached in 2005 : 25 / nd / 52 / 29 4 110 100 90 HF 1-20mg/m3 80 HCl 40mg/m3 70 Ic 60 % SO2 70-300mg/m3 50 40 30 20 10 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 Number of campaigns

Inter-laboratories tests Hg Ic 100 in 90 % 80 70 60 50 Hg 40-100µg/m3 40 30 20 10 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 Number of campaigns Ic reference Ic average Ic 2005 Ic ave/ Icref Ic 2005 / Icref Hg 40-100µg/m 3 25 63,0 94,2 2,5 3,2 Target for Hg : 20 % Target not reached in 2005 : 90 / 52,6 / 140 / nd No improvement Ic analytique 2002 : 27,6 to 29,4%