PROFICIENCY TESTING SCHEME REPORT

PROFICIENCY TESTING SCHEME REPORT PTWFD-SCCPs: Short chain chloroparaffins (C -C 13 Chloroalkanes) in surface waters Report issued on the th of May 11. Cancel and replace the report issued on the th of May 11, due to a mistake in the spiked and the participants mean uncertainties. Written by Ronan Charpentier Association A.G.L.A.E. 9, avenue de la République 59 Lille FRANCE +33 () 3 1 91 +33 () 3 1 91 1 @ contact@association-aglae.fr www.association-aglae.fr Proficiency testing scheme report PTWFD - SCCPs Written the th May 11 page 1/15

INTRODUCTION This proficiency testing was provided by A.G.L.A.E. as part of the PT-WFD (Proficiency Testing for the Water Framework Directive) network, in collaboration with the following proficiency testing providers: BSG HU Hamburg Germany www.hamburg.de/ringversuche karla.ludwig-baxter@hu.hamburg.de BIPEA, FRANCE www.bipea.org/en/index.htm contact@bipea.org Kemijski Institut Ljubljana Slovenija, Slovenia http://www.ki.si/en/ info@ki.si LGC Standards - Proficiency Testing, United Kingdom www.lgcpt.com customerservices@lgcpt.com QUALITYCONSULT srl, Italy /www.aqc.it/en/ Qualityconsult@aqc.it Proftest SYKE, Finnish Environment Institute, Laboratories, Finland www.environment.fi/syke/proftest proftest@environment.fi VITUKI Non-profit Ltd., HUNGARY www.vituki.hu/ mecs@vituki.hu For further information on PT-WFD, please see: http://www.pt-wfd.eu/index.shtml Proficiency testing scheme report PTWFD - SCCPs Written the th May 11 page /15

TABLE OF CONTENTS PRESENTATION OF THE PROFICIENCY TESTING... MATERIAL PREPARATION... DESIGN OF THE PROFICIENCY TESTING...5 SENDING OF THE SAMPLES... QUALITY OF THE MATERIALS...7 DATA PROCESSING AND ANALYTICAL PERFORMANCE EVALUATION...7 APPROACH OF THE TRUENESS... DEVIATIONS BETWEEN ANALYTICAL MODALITIES...1 COMMENTS AND CONCLUSION...1 DESIGN AND IMPLEMENTATION OF THE PROFICIENCY TESTING...15 ENCLOSED ANNEXES...15 ACKNOWLEDGMENTS...15 Proficiency testing scheme report PTWFD - SCCPs Written the th May 11 page 3/15

PRESENTATION OF THE PROFICIENCY TESTING Testing period: November January 11 Closing date: 1 January 11 Type of matrix used: surface water diluted with tap water Number of batches: 3 Analysed items: C -C 13 chloroalkanes (SCCPs) Number of participants: 31. The following table displays the detail of these participants: Registration via Number of participants BIPEA 1 BSG 11 SYKE 1 LGC 1 PTWFD network 15 AGLAE 17 TOTAL 31 MATERIAL PREPARATION The subcontractor laboratory in charge of the sample preparation was: IPL Santé, Environnement Durables Nord 1, rue du Professeur Calmette 59 LILLE CEDEX FRANCE Supervisor: Mr Eric PIQUE Proficiency testing scheme report PTWFD - SCCPs Written the th May 11 page /15

The material preparation modalities are detailed in the following table: Batch identification Batch 1 (Bottles labeled A and B) Batch (Bottles labeled C and D) Batch 3 (Bottles labeled E and F) Parameters C -C 13 Chloroalkanes C -C 13 Chloroalkanes C -C 13 Chloroalkanes Matrix Surface water (1L) + tap water (L) Treatment mm sieving of the surface water and sodium thiosulfate dechlorination of the tap water Matrix characterization Biochemical oxygen demand = 7. mg of O.L -1 ; Total suspended materials =. mg.l -1 Stabilization None Fractionation Continuous racking under mechanic stirring, bottle by bottle Spiking Standard used for the spiking Directly inside the bottles in C -C 13 chloroalkanes : 51.5% chlorine content D. Ehrenstorfer Ref : X35CY Directly inside the bottles in C -C 13 chloroalkanes : 55.5% chlorine content D. Ehrenstorfer Ref : X355CY Directly inside the bottles in C -C 13 chloroalkanes : 3% chlorine content D. Ehrenstorfer Ref : X33CY Packaging ml white glass bottles ml white glass bottles ml white glass bottles DESIGN OF THE PROFICIENCY TESTING Each participant received six bottles from 3 batches spiked at the same level but with different chlorine contents. One analysis was carried out on each bottle (design with one replicate on two samples issued from the same batch). Proficiency testing scheme report PTWFD - SCCPs Written the th May 11 page 5/15

SENDING OF THE SAMPLES The testing materials were prepared on 1 November and sent on 3 November. The following table shows the receipt dates of the parcels and the sample temperatures upon receipt (information given by the participants). Laboratory code Sample temperature at receipt ( C) Receipt date 1 7 /11/ /11/ 3 5 5/11/ 7 /11/ 5 5 /11/ 7.3 /11/ 7 5. /11/ 9.9 /11/ 11 7.5 /11/ 1 5.9 /11/ 1 /11/ 1 3 /11/ 17 9/11/ 1 5/11/ - /11/ 1 5.5 /1/ 7 /11/ 3 /11/ 5 /11/ 5 3 /11/.5 /11/ 7 /11/ /11/ 9 - /11/ 3 /11/ 31 /11/ Note: the laboratory 1 s parcel was sent on 7 December in consequence of a late subscription. Proficiency testing scheme report PTWFD - SCCPs Written the th May 11 page /15

QUALITY OF THE MATERIALS The quality of the materials was verified for all the analysed parameters. The materials stability was checked thanks to the study of the participants results distribution in function of the declared treatment starting dates. Additionally, a control was led on the second batch (bottles C and D) by the subcontractor laboratory, in order to complete the stability evaluation. The homogeneity of the batches was evaluated through the study of the participants results. Like for the stability study, a complementary monitoring was carried out by the subcontractor laboratory for the second batch. These verifications have shown that the batches were stable and homogeneous enough for the implementation of proficiency testing: indeed, more than 95% of the mean square of the laboratories results dispersion (mean results per batch) corresponds to the variance of the laboratory component of the bias (according to ISO 575) ; while only less than 5% of the dispersion of one laboratory s results to an other (in terms of mean square) is potentially attributable to a lack of stability or homogeneity of the batch. DATA PROCESSING AND ANALYTICAL PERFORMANCE EVALUATION The statistical evaluation of the data was performed according to the A and S algorithms described in the European standard ISO 135 (5) «Statistical methods for use in proficiency testing by interlaboratory comparisons». This data processing was carried out on all the participants results, besides the results such as «lower than the quantification limit». The analytical performances of the participants were evaluated according to the criteria specified within the PT-WFD, namely: - the assigned reference value to the item (m) is the mean of the results, calculated according to algorithm A from standard ISO 135; - the standard deviation for proficiency assessment is set in comparison to the assigned reference value: SDPA =.5 m. z-scores are calculated according to: In which: ( x m) z = SDPA x= mean result of the laboratory m = assigned reference value to the item (algorithm A) SDPA =.5 m The evaluation of the results depends on the following criteria: z. Satisfactory result. < z < 3. Questionable result z 3. Unsatisfactory result Proficiency testing scheme report PTWFD - SCCPs Written the th May 11 page 7/15

The following table and plot display the number and percentage of satisfactory, questionable and unsatisfactory results for each batch. Batch 1 (chlorine content: 51.5%) Batch (chlorine content: 55.5%) Batch 3 (chlorine content: 3%) Number of z. 1 (53%) 1 (7%) (7%) Number of. < z < 3. (7%) 5 (17%) 3 (%) Number of z 3. (%) (13%) 7 (3%) Z-scores distribution % 9% % 7% % 5% % 3% % % % Batch 1 Batch Batch 3 Number of z. Number of. < z < 3. Number of z 3. APPROACH OF THE TRUENESS The following table compares the spiked value with the mean value observed by the participants, accounting for the confidence interval of both quantities. Note: the uncertainty on the spiked value was calculated according to the standard ENV 135 : 1999 (Guide To The Expression Of Uncertainty In Measurement) with a coverage factor k =. The expanded uncertainty on the value observed by the participants is equal to: S Z U = ± t 1. 5 in which: 95%,( p 1) p - p is the number of laboratories who returned a result - t is the fractile of the Student s t-distribution, with α=5% and p-1 freedom degrees 95%,( p 1 ) - Sz is the standard deviation resulting from the algorithm A. Proficiency testing scheme report PTWFD - SCCPs Written the th May 11 page /15

Item Initial in the matrix C -C 13 Chloroalkanes (batch 1 chlorine content: 51.5%) C -C 13 Chloroalkanes (batch chlorine content: 55.5%) C -C 13 Chloroalkanes (batch 3 chlorine content: 3%) <. <. <..937.937.937 Uncertainty of spiked Value observed by the participants Uncertainty of the value observed by the participants Recovery rate % (= m/spiked x ) value found? Units in µg.l -1 ±.77 ±.77 ±.77.3 3.5.3 ±.59 ±. ± 1.33 57% 7% % NO NO YES The mean values observed by the participants are lower than the spiked s values, more particularly for the batch 1, spiked with a 51.5% chlorine content C -C 13 chloroalkanes mix. As a result, several laboratories that have assessed results close to the spiked s are showing unsatisfactory z-scores (see following table). Proficiency testing scheme report PTWFD - SCCPs Written the th May 11 page 9/15

Laboratory code C -C 13 chloroalkanes Batch 1 (51.5% chlorine content) Deviation from the spiked in % z-score C -C 13 chloroalkanes Batch (55.5% chlorine content) Deviation from the spiked in % z-score C -C 13 chloroalkanes Batch 3 (3% chlorine content) Deviation from the spiked in % z-score 1-7% +1. -% +.15-1% -.9 +1% +.9 -% +1.3-9% +.15 3-5% -1. -9% -.3-1% -1.9 +1% +3.5-9% -.5 -% -1.53 5-39% +.7 +7% +1.97 +17% +.1 -% +1.13 +17% +.55 +% +1.5 7 <+3% <+.1 <+3% <+7.3 <+3% <+5.5 - - - - - - 9-7% +.7 +33% +3.1 +1% +.3-51% -.1-17% +.3 +77% +.9 11-3% +.33 -% +1. +13% +1.1 1-1% +. -3% -.5-3% -.3 13 +153% +13.5 +5% +33.9 +% +. 1-79% -.53-73% -.7-53% -1.3 15-9% -1. -7% -1. +9% +.9 1 -% -1. -39% -. -% -1.5 17-7% +1.11 +1% +. +5% +.1 1-9% -3.73-7% -.7-5% -1.79 19-7% -.19-5% -1.5 +3% +.9 -% +. -% -.7 -% -1.3 1-91% -3. -9% -3.57-9% -3.55-1% +. -3% -.9 -% -3.5 3-1% +1. -% +.3 -% -.51-5% +1. -% -.7 -% -1.7 5 -% +.57 -% +1.5 +% +1. -5% -1.7 +3% +1.73 +% +. 7-1% +.9 -% +. -% -. -91% -3.37-7% -3.9-9% -3. 9-73% -.15-7% -1. -5% +.33 3 -% -.7-71% -.1 -% -.33 31-5% -1.55-3% -.1 +17% +1.37 The deviations from the spiked s higher than 5% and 75% are indicated with the following colours: >5% and >75%. In order to verify if there were any laboratories that have found the spiked in the 3 batches, we calculated the sum of squared z-scores determined in relation to the spiked (SSz). Proficiency testing scheme report PTWFD - SCCPs Written the th May 11 page /15

For each laboratory: SSz = (z sc1 )²+ (z sc )²+ (z sc3 )² In which: ( x sc) Z sc1 = 1 SDPA and: ( x sc) z sc = SDPA ( x sc) z sc3 = 3 SDPA x 1 : laboratory s mean result for batch 1 x : laboratory s mean result for batch x 3 : laboratory s mean result for batch 3 sc: spiked (identical for the 3 batches) SDPA =.5 m The SSz are following a chi-square distribution with 3 freedom degrees and can be interpreted in the following way: - if SSz 7.1 : satisfactory; - if 7.1< SSz 11.3 : questionable; - if SSz > 11.3 : unsatisfactory. The higher SSz is, the further the laboratory s results are from the spiked. The laboratory with the smallest deviation in comparison to the spiked s for the 3 batches is then the laboratory (see following table). Laboratory code SSz Laboratory code SSz 1. 17 1.1.5 1 7. 3 9. 19 13.3.7.3 5 5.1 1 39.9.7 1.91 7-3.5 -. 9 7. 5.7 1.3. 11. 7 1.1 1 11.5 3. 13 3.5 9 1. 1. 3 5.51 15 11.3 31.7 1 11.9 Proficiency testing scheme report PTWFD - SCCPs Written the th May 11 page 11/15

DEVIATIONS BETWEEN ANALYTICAL MODALITIES The data processing was not disrupted by potential deviations due to the analytical modalities (there were no multiple populations of results). For each batch, we studied the laboratories results distribution depending on the used analytical modalities (see enclosed plots). This study did not show deviations between analytical modalities. Let us remind that we must be very cautious towards the interpretation of the discrepancies we might observe on these plots. Indeed: - on the one hand, these disparities would be sporadic observations, that could not be reasonably generalised without confirmation; - on the other hand, interlaboratory proficiency testing are not expressly designed for analytical modalities effect measurement. As a result, the comparison statistical tests are not always powerful enough, and there is a high risk of confusion between the studied factor and another unidentified hidden factor (and then a risk to lend the effect erroneously). However, on this testing s data, we can observe that: - on the batch (spiked with a 55.5% chlorine content chloroalkanes mix), the results of the laboratories using a calibration with 3 different chlorine contents are distinguished from the other laboratories results by a visibly lesser dispersion; - the results obtained without purification appear more scattered than the ones acquired after purification. COMMENTS AND CONCLUSION The dispersion of the participants results is quite high, with reproducibilities stated in variation coefficients, going from 9.5% to %. As a result, there was a very high number of unsatisfactory z- scores, considering the mode of calculation of the standard deviation for the proficiency evaluation, which is equal to 5% of the assigned value to the item. It appears that this dispersion is less important for the sample batch spiked with a 55.5% chlorine content in C -C 13 chloroalkanes mix. We can also note that this chlorine content was the most used during calibrations (see the chlorine contents distribution plot). To note as well that the uncertainty on the consensus value is high due to the important dispersion of the results. Finally, Mr Matthew Whetton, from LGC, pointed out that the deviation from the spiked varied with the samples chlorine content. The general tendency being that the spiked is best found when the chlorine content increases. However, it seems that the recovery rates evolution varies depending on the participants. Some laboratories show a recovery rate independent from the chlorine content, or even find a closer result from the spiked when the chlorine content is lower. In order to clarify these observations we classified the laboratories depending on the deviations from the spiked s they obtained on the 3 batches. We then have been able to identify 5 categories of laboratories. Proficiency testing scheme report PTWFD - SCCPs Written the th May 11 page 1/15

The first class includes two laboratories that observe particularly high values on the third batch. The second class comprises the laboratories with much lower values than the spiked s, no matter the chlorine content. The third and fourth classes associate the laboratories that have a tendency to get closer from the spiked as the chlorine content increases. The laboratories from the class n 3 detect on average higher values; and the one from the class n find very close values from the spiked for the third batch (3% chlorine content). Finally, the fifth class brings together the laboratories that have an almost constant deviation from the spiked (deviation between % and -5%) on all of the three batches. Some of these laboratories show their apparent recovery decreasing on the third batch. Evolution of the deviations from the spiked s depending on the samples' chlorine content % Laboratory code 1 15% 3 Deviation from the spiked (%) % 5% % -5% 5 9 11 1 1 15 1 17 1 19 1 3 5 -% Batch 1-51.5% chlorine content Batch - 55.5% chlorine content Batch 3-3% chlorine content 7 9 Class n 1 Class n Class n 3 Class n Class n 5 3 31 Proficiency testing scheme report PTWFD - SCCPs Written the th May 11 page 13/15

We then verified if this laboratories classification could be explained by the analytical modalities used by the participants (analytical line and number of standards). It seems that this is not the case. Indeed, each class brings together laboratories that employed different analytical modalities, as seen in the following table. Class number Laboratory code Batch 1 Batch Batch 3 Analytical line 1 5-39% 7% 17% L/L extraction then GC/ECD analysis 1 1 9-7% 33% 1% L/L extraction then GC/ECNI-MS analysis 1 1-79% -73% -53% L/L extraction then GC/ECD analysis 1 1-9% -7% -5% L/L extraction then GC/ECNI-MS analysis - 1-91% -9% -9% S/L extraction then GC/MS analysis - -91% -7% -9% L/L extraction then GC/ECNI-MS analysis 3 -% -71% -% L/L extraction then GC/ECNI-MS analysis 1 3 -% 17% % L/L extraction then GC/ECD analysis 1 3-51% -17% 77% L/L extraction then GC/ECD analysis 3 3 11-3% -% 13% L/L extraction then GC/MS/MS analysis 1 3 17-7% 1% 5% L/L extraction then GC/MS/MS analysis 3 5 -% -% % L/L extraction then GC-MS (NCI) analysis 3 3-5% 3% % L/L extraction then GC/ECNI-MS analysis 3 15-9% -7% 9% L/L extraction then GC/ECNI-MS analysis 1 19-7% -5% 3% - 1 9-73% -7% -5% L/L extraction then GC/ECNI-MS analysis 3 31-5% -3% 17% L/L extraction then GC/ECNI-MS analysis 3 5 1-7% -% -1% L/L extraction then GC/MS analysis 1 5 1% -% -9% L/L extraction then GC/ECD analysis 3 5 3-5% -9% -1% L/L extraction then GC/ECNI-MS analysis 3 5 1% -9% -% L/L extraction then GC/IE-MS analysis 1 5 1-1% -3% -3% L/L extraction then GC/ECD analysis 3 5 1 -% -39% -% L/L extraction then GC/ECD analysis 1 5 -% -% -% S/L extraction then GC/MS analysis 3 5-1% -3% -% L/L extraction then GC/MS/MS analysis - 5 3-1% -% -% L/L extraction then GC/ECNI-MS analysis 5 5-5% -% -% L/L extraction then GC/ECNI-MS analysis 3 5 7-1% -% -% L/L extraction then GC/ECNI-MS analysis 3 Number of standards Lastly, we contacted Dr Sabine Geiß from Thüringer Landesanstalt für Umwelt und Geologie, convener of the ISO/TC17/SC/WG59 working group, which is currently developing the new ISO/DIS 1 standard Water quality Determination of short chain polychlorinated alkanes (SCCP) in water Method using gas chromatography / mass spectrometry (GC/MS) and electron capture negative ionisation (ECNI). Dr Geiß pointed out that during the tests made for the standard development they also observed higher results when the chlorine contents were higher. However, the increase of the C -C 13 chloroalkanes contents depending on the samples chlorine content stayed negligible considering the measurement error. Proficiency testing scheme report PTWFD - SCCPs Written the th May 11 page 1/15

She also mentioned the very low recovery rate (about 5%) they obtained with the calibration standard Ehrenstorfer «SCCP C to C 13, 51.5% Chlorine content», standard that we also used to spike our samples and for which the mean recovery rate observed during the testing is 57%. For the next proficiency testing, we will then consider to spike our samples with different standards. Finally, we are also envisaging to target lower levels. DESIGN AND IMPLEMENTATION OF THE PROFICIENCY TESTING The following persons participated in the design and in the implementation of this proficiency test, under the supervision of Mr Delattre (President of the Association) and Mr Guarini (Director), in collaboration with Mr Hennequin (member of the Technical Committee and Honour Vice-President of the Association) and Mr Pointillard (President of the Technical Committee). Technical design Mrs Lacoste Miss Hoenner Statistical analysis Confidentiality management Supervision of Quality Mr Charpentier Mr Thieffry Mrs De Buchy In case of a divergence between the French and English versions of this document, the French version shall prevail. ENCLOSED ANNEXES Subject of the document Nature Number of pages Reference and precision values 1 table 1 z-scores summary 1 table 1 Contents in C -C 13 Chloroalkanes observed by the participants on the batch 1 (51.5% chlorine content) 1 table + 1 plot Contents in C -C 13 Chloroalkanes observed by the participants on the batch (55.5% chlorine content) 1 table + 1 plot Contents in C -C 13 Chloroalkanes observed by the participants on the batch 3 (3% chlorine content) 1 table + 1 plot Distribution of the standards chlorine contents used by the participants 1 table 1 Results distribution plots (in function of the analytical modalities) Plots 9 ACKNOWLEDGMENTS We would like to thank our partners from the PT-WFD network for their useful comments. We are also grateful to Dr Sabine Geiß for her advice and observations. Proficiency testing scheme report PTWFD - SCCPs Written the th May 11 page 15/15

ANNEXES

Consensus value C -C 13 Chloroalkanes Batch 1 (51.5% chlorine content) IC inf 1,97 Glossary : m,3 m : consensus value, resulting from the algorithm A IC sup 3,91 ICinf : lower bound of the confidence interval of m (with 5% risk) r =,5 ICsup : upper bound of the confidence interval of m (with 5% risk) Observed R = 5,13 r : repeatability limit precision CVr% =,5 R : reproducibility limit CVR% =, CVr% : repetability stated in variation coefficient (Sr/m)* R / r =, CVR% : reproducibility stated in variation coefficient (SR/m)* SDPA =,7 R/r : repeatability on reproductibily ratio sz = 1, SDPA : standard deviation for proficiency assesment (z-scores calculation) (.5*m) unit : µg.l -1 sz : standard deviation of the laboratories'results, resulting from algorithm A Consensus value C -C 13 Chloroalkanes Batch (55.5% chlorine content) IC inf,71 m 3,5 IC sup,3 r =,3 Observed R =,9 precision CVr% =, CVR% = 9,5 R / r =, SDPA =,5 sz = 1,733 unit : µg.l -1 Consensus value C -C 13 Chloroalkanes Batch 3 (3 % chlorine content) IC inf 3,1 m,3 IC sup 5,7 r =, Observed R = 7,7 precision CVr% = 7, CVR% = 3,5 R / r = 9,5 SDPA = 1,1 sz =,71 unit : µg.l -1 Reference and precision values A.G.L.A.E. - PTWFD - SCCPs - November / January 11

Laboratory Code C -C 13 chloroalkanes C -C 13 Chloroalkanes C -C 13 Chloroalkanes Laboratory Code Batch 1 (51.5% chlorine content) Batch (55.5% chlorine content) Batch 3 (3% chlorine content) 1 +1, +,15 -,9 1 +,9 +1,3 +,15 3-1, -,3-1,9 3 +3,5 -,5-1,53 5 +,7 +1,97 +,1 5 +1,13 +,55 +1,5 7 <+.1 <+7.3 <+5.5 7 - - - 9 +,7 +3,1 +,3 9 -,1 +,3 +,9 11 +,33 +1, +1,1 11 1 +, -,5 -,3 1 13 +13,5 +33,9 +, 13 1 -,53 -,7-1,3 1 15-1, -1, +,9 15 1-1, -, -1,5 1 17 +1,11 +, +,1 17 1-3,73 -,7-1,79 1 19 -,19-1,5 +,9 19 +, -,7-1,3 1-3, -3,57-3,55 1 +, -,9-3,5 3 +1, +,3 -,51 3 +1, -,7-1,7 5 +,57 +1,5 +1, 5-1,7 +1,73 +, 7 +,9 +, -, 7-3,37-3,9-3, 9 -,15-1, +,33 9 3 -,7 -,1 -,33 3 31-1,55 -,1 +1,37 31 z-scores summary A.G.L.A.E. - PTWFD - SCCPs - November / January 11

RESULTS Assigned value (mean) =.3 Standard Deviation for Proficiency Assessment (,5*m) =.7 =.937 (unit in µg.l -1 ) Bottle A Bottle B Laboratory Code Replicate 1 Replicate 1 Mean z-score 1 3. 3.3 3.5 +1. 5.37. 5.75 +.9 3 1.1 9.9.5-1..97 5.1.99 +3.5 5 3.3 3. 3.5 +.7 3.1 3.5 3.3 +1.13 7 <. <. <. <+.1 - - - - 9.7..5 +.7.3.5. -.1 11.9 3.1 3.5 +.33 1.9.91.95 +. 13 1. 11. 1.5 +13.5 1 1.9.99 1. -.53 15 1. 1. 1.53-1. 1 1..5 1.95-1. 17 3.55 3.9 3. +1.11 1.19.19.19-3.73 19 1. 1.31 1.5 -.19 3..97.95 +. 1.1.3.3-3..3.3.5 +. 3 3.9 3. 3. +1. 3.1 3.7 3.5 +1. 5.79.5.55 +.57..13.75-1.7 7 5.3.39.75 +.9..3.5-3.37 9 1.5 1. 1.3 -.15 3..93.5 -.7 31 1.73 1.7 1.735-1.55 Short chain chloroparaffins - SCCPs (C -C 13 chloroalkanes) in surface water Parameter C -C 13 chloroalkanes (51.5% chlorine content) Unit µg.l -1 A.G.L.A.E. - PTWFD - SCCPs - November - January 11 Table 1/1

, C C 13 chloroalkanes Batch 1 (51.5% chlorine content) Content in µg.l 1 5,, 3,, 1, ICsup m ICinf 1 1 3 1 19 9 15 31 1 3 1 5 11 1 17 3 9 7 z = +3. 5 z = +. z =. z = 3.,,1,,3,,5,,7,,9 1 Accrued number of laboratories Laboratories' results Assigned reference value to the item A.G.L.A.E. PTWFD SCCPs November / January 11

RESULTS Assigned value (mean) = 3.5 Standard Deviation for Proficiency Assessment (,5*m) =.5 =.937 (unit in µg.l -1 ) Bottle C Bottle D Laboratory Code Replicate 1 Replicate 1 Mean z-score 1 3.79 3.55 3.7 +.15.9..75 +1.3 3 37 3.7 35 3.5 3.515 -.33 3.9 3.5 3.95 -.5 5 5. 5.51 5.5 +1.97 5..1 5. +.55 7 <. <. <. <+7.3 - - - - 9.9..555 +3.1. 3.. +.3 11.9.. +1. 1.5 3.5 3. -.5 13 31. 35. 33. +33.9 1 1.7 1. 1.355 -.7 15.1..35-1. 1 3..7.99 -. 17 5. 5.37 5.55 +. 1 1.3 1. 1.35 -.7 19.55.7.1-1.5.9..77 -.7 1.31.5.31-3.57 3. 3.3 3. -.9 3 3.7 3.7 3.7 +.3.99.91.95 -.7 5.77.7. +1.5.79 5.35 5.7 +1.73 7 3.99 3.7 3.93 +..5.1.3-3.9 9.7.. -1. 3 1.39 1.3 1. -.1 31 3.7 3. 3.35 -.1 Short chain chloroparaffins - SCCPs (C -C 13 chloroalkanes) in surface water Parameter C -C 13 chloroalkanes (55.5% chlorine content) Unit µg.l -1 A.G.L.A.E. - PTWFD - SCCPs - November - January 11 Table 1/1

7,, 5, C C 13 chloroalkanes Batch (55.5% chlorine content) 11 5 9 z= +3, 5 17 z= +, Content in µg.l 1, 3,, 1 1 3 19 9 15 1 1 31 3 1 7 3 IC sup m IC inf z=, 1, 1 z= 3,,,1,,3,,5,,7,,9 1 Accrued number of laboratories Laboratories' results Assigned reference value to the item A.G.L.A.E. PTWFD SCCPs November / January 11

RESULTS Assigned value (mean) =.3 Standard Deviation for Proficiency Assessment (,5*m) = 1.1 =.937 (unit in µg.l -1 ) Bottle E Bottle F Laboratory Code Replicate 1 Replicate 1 Mean z-score 1 3.9.51.5 -.9.55.3.9 +.15 3 7.7 9.9.95-1.9.5.1.5-1.53 5 13. 13.1 13.35 +.1.7 5.9.3 +1.5 7 <. <. <. <+5.5 - - - - 9.5 11.7 11.1 +.3 9..5.75 +.9 11 5. 5.55 5.55 +1.11 1 1. 1.9 1. -.3 13 19. 13. 1. +. 1.7..35-1.3 15 5.35 5. 5.35 +.9 1.75.57. -1.5 17.95 5. 5.5 +.1 1.37..3-1.79 19 5.1.95 5.5 +.9.55 3.1.55-1.3 1..59.91-3.55.3.79. -3.5 3 3.3 3.7 3.775 -.51.9.99.955-1.7 5 5.9 5.91 5.95 +1. 7.5. 7.5 +. 7 3.73. 3.75 -.... -3. 9 3.7 5.9.5 +.33 3 1.7 1. 1. -.33 31 5.9 5.7 5. +1.37 Short chain chloroparaffins - SCCPs (C -C 13 chloroalkanes) in surface water Parameter C -C 13 chloroalkanes (3% chlorine content) Unit µg.l -1 A.G.L.A.E. - PTWFD - SCCPs - November - January 11 Table 1/1

1, C C 13 chloroalkanes Batch 3 (3% chlorine content) 9,, z= +3. Content in µg.l 1,,,, z= +. 31 5 3 7 1 9 19 17 15 11 IC sup m 1 1 1 3 IC inf 3 1 1 z =. z = 3.,1,,3,,5,,7,,9 1 Accrued number of laboratories Laboratories' results Assigned reference value to the item A.G.L.A.E. PTWFD SCCPs November / January 11

Standard's chlorine content Laboratory code 9.% 9.9% 51.5% 55.% 55.5% 5.% 57.5% 1.% 3.% 7.%.7% 9.% 1 - - - - YES - - - - - - - - - YES - YES - - - YES - - - 3 - - YES - YES - - - YES - - - - - YES - - - - - - - - - 5 - - - - YES - - - - - - - - - - - YES - - - - - - - 7 - - - - YES - - - - - - - - - - - - - - - - - - - 9 - - YES - - - - - - - - - - - YES - YES - - - YES - - - 11 - - - YES - - - - - - - - 1 - - YES - YES - - - YES - - - 13 - - YES - YES - - - YES - - - 1 - - - - - - - - YES - - - 15 - - - - YES - - - - - - - 1 - - YES - - - - - - - - - 17 - - YES - - - - - YES - - - 1 - - - - - - - - YES - - - 19 - - - - YES - - - - - - - - - YES - YES - - - YES - - - 1 - - - - - - - - - - - - - - - - YES - - - - - - - 3 - - YES - YES - YES YES YES - - - - - YES - YES - - - YES - - - 5 - - YES - YES - - - YES - - - YES - - - - YES - - - - YES - 7 - - YES - YES - - - YES - - - - - YES - - YES - - - - - - 9 YES - - - - YES - - - - YES - 3 - - - - - - - - YES - - - 31 YES - - - - YES - - - - YES - Total : 3 15 1 17 1 1 1 3 Distribution of the chlorine contents of the standards used by the participants A.G.L.A.E. PTWFD SCCPs November / January 11

1 Number of standards with a different chlorine content? 1 Number of laboratories 1 3 5 C C13chloroalkanes content (µg.l 1 ) 1 1 1 1 Batch 1 (51.5% chlorine content) 1 3 5 Number of standard with different chlorine contents C C13 chloroalkanes content (µg.l 1 ) 1 1 1 1 Batch (55.5% chlorine content) 1 3 5 Number of standard with different chlorine contents C C13 chloroalkanes (µg.l 1 ) 1 1 1 1 Batch 3 (3% chlorine content) Mean laboratory 1 3 5 Number of standard with different chlorine contents A.G.L.A.E. PTWFD SCCPs November / january 11

Calibration type adopted Number of laboratories 9 7 5 3 1 One standard : 51.5% One standard : 55.5% One standard : 55% One Two Two Three Three standard : standards : standards : standards : standards : 3% 51.5% and 51.5% and 51.5%, 9%, 5% 3% 5% 55.5% and and.7% 3% Others C C13 chloroalkanes content (µg.l 1 ) 1 1 1 1 Batch 1 (51.5% chlorine content) 1 3 5 7 9 Calibration type Caption : Calibration type 1/ one standard : 51.5% / one standard : 55.5% 3/ one standard : 55% / one standard : 3% 5/ two standards : 51.5% and 3% / two standards : 51.5% and 5% 7/ three standards : 51.5%, 55.5% and 3% / three standards : 9%, 5% and.7% 9/ others Batch (55.5% chlorine content) C C13 chloroalkanes content (µg.l 1 ) 1 1 1 1 1 3 5 7 9 Calibration type Batch 3 (3% chlorine content) C C13 chloroalkanes content (µg.l 1 ) 1 1 1 1 1 3 5 7 9 Calibration type A.G.L.A.E. PTWFD SCCPs November / January 11

Number of laboratories 1 1 1 1 Utilization of an internal standard? yes no C C13 chloroalkanes content (µg.l 1 ) 1 1 1 1 Batch 1 (51.5% chlorine content) 1 3 Caption : Utilization of an internal standard? 1/ yes / no utilization of an internal standard? Batch (55.5% chlorine content) C C13 chloroalkanes content (µg.l 1 ) 1 1 1 1 1 3 utilization of an internal standard? Batch 3 (3% chlorine content) C C13 chloroalkanes content (µg.l 1 ) 1 1 1 1 1 3 utilization of an internal standard? A.G.L.A.E. PTWFD SCCPs November / January 11

1 Analytical line 1 Number of laboratories L/L extraction then GC/ECD analysis L/L extraction then GC/MS analysis L/L extraction L/L extraction then GC/MS/MS then GC/EI MS analysis analysis L/L extraction then GC/ECNI MS analysis S/L extraction then GC/MS analysis Other : L/L extraction then GC/MS (NCI) analysis Caption : 1 Analytical line adopted 1 1/ L/L extraction then GC/ECD analysis 1 1 / L/L extraction then GC/MS analysis 3/ L/L extraction then GC/MS/MS analysis / L/L extraction then GC/EI MS analysis 5/ L/L extraction then GC/EI MS/MS analysis / L/L extraction then GC/ECNI MS analysis 7/ S/L extraction then GC/ECD analysis / S/L extraction then GC/MS analysis s) 9/ S/L extraction then GC/MS/MS analysis / S/L extraction then GC/EI MS analysis 11/ S/L extraction then GC/EI MS/MS analysis 1 3 5 7 9 11 1 13 1 1/ S/L extraction then GC/ECNI MS analysis Analytical line 13/ other : L/L extraction then GC/MS (NCI) analysis C C13 chloroalkanes content (µg.l 1 ) Batch 1 (51.5% chlorine content) C C13 chloroalkanes content (µg.l 1 ) 1 1 1 1 Batch (55.5% chlorine content) 1 3 5 7 9 11 1 13 1 Analytical line C C13 chloroalkanes content (µg.l 1 ) 1 1 1 1 Batch 3 (3% chlorine content) 1 3 5 7 9 11 1 13 1 Analytical line A.G.L.A.E. PTWFD SCCPs November / January 11

1 Extraction type? 1 Number of laboratories directly in the bottle with rinsing of the bottle without rinsing of the bottle C C13 chloroalkanes content (µg.l 1 ) 1 1 1 1 Batch 1 (51.5% chlorine content) 1 3 Caption : Extraction modalities 1/ directly in the bottle / with rinsing of the bottle 3/ without rinsing of the bottle Extraction type Batch (55.5% chlorine content) C C13 chloroalkanes content (µg.l 1 ) 1 1 1 1 1 3 Extraction type Batch 3 (3% chlorine content) Teneur en chloroalcanes C C13 (en µg.l 1 ) 1 1 1 1 1 3 Extraction type A.G.L.A.E. PTWFD SCCPs November / January 11

Number of laboratories 1 Extraction solvent used C C13 chloroalkanes content (µg.l 1 ) 1 1 1 1 Batch 1 (51.5% chlorine content) 1 3 5 7 9 Caption : Extraction solvent 1/ n hexane / cyclohexane 3/ n heptane / dichloromethane 5/ dichloromethane / ethyl acetate / pentane 7/ hexane/dichloromethane / Isohexane/ Diethyl ether 9/ n hexane/dichloromethane Extraction solvent Batch (55.5% chlorine content) C C13 chloroalkanes content (µg.l 1 ) 1 1 1 1 1 3 5 7 9 Extraction solvent Batch 3 (3% chlorine content) C C13 chloroalkanes content (µg.l 1 ) 1 1 1 1 1 3 5 7 9 Extraction solvent A.G.L.A.E. PTWFD SCCPs November / January 11

5 Purification phase? Number of laboratories 15 5 yes no C C13 chloroalkanes content (µg.l 1 ) 1 1 1 1 Batch 1 (51.5% chlorine content) 1 3 Caption : Purification phase? 1/ yes / no Purification phase Batch (55.5% chlorine content) C C13 chloroalkanes content (µg.l 1 ) 1 1 1 1 1 3 Purification phase Batch 3 (3% chlorine content) C C13 chloroalkanes content (µg.l 1 ) 1 1 1 1 1 3 Purification phase A.G.L.A.E. PTWFD SCCPs November / January 11

3 Concentration phase? Number of laboratories 5 15 5 yes no C C13 chloroalkanes content (µg.l 1 ) 1 1 1 1 Batch 1 (51.5% chlorine content) 1 3 Caption : Concentration phase 1/ yes / no Concentration phase Batch (55.5% chlorine content) C C13 chloroalkanes content (µg.l 1 ) 1 1 1 1 1 3 Concentration phase Batch 3 (3% chlorine content) C C13 chloroalkanes content (µg.l 1 ) 1 1 1 1 1 3 Concentration phase A.G.L.A.E. PTWFD SCCPs November / January 11