Analytische Qualitätssicherung Baden-Württemberg

Analytische Qualitätssicherung Baden-Württemberg Proficiency Test UKWIR SS 17 PAH in surface water with suspended solids Anthracene, Fluoranthene, Naphtalene, Benzo[a]pyrene, Benzo[b]fluoranthene, Benzo[k]fluoranthene, Benzo[g,h,i]perylene, Indeno[1,2,3-cd]pyrene Stuttgart, August 2017 provided by AQS Baden-Württemberg c/o Institute for Sanitary Engineering, Water Quality and Solid Waste Management, University of Stuttgart Bandtäle 2, 70569 Stuttgart-Büsnau, Germany

Responsibilities: Scientific director AQS: PT manager: Sample preparation: Dr.-Ing. Dipl.-Chem. Michael Koch Dr.-Ing. Frank Baumeister Matthias Mischo Release of the report (version 1) on 11 August 2017 by scientific director AQS AQS Baden-Württemberg at Institute of Sanitary Engineering, Water Quality and Solid Waste Management at University of Stuttgart Bandtäle 2 70569 Stuttgart-Büsnau Germany http://www.aqsbw.de Tel.: +49 (0)711 / 685-65446 Fax: +49 (0)711 / 685-63769 E-Mail: info@aqsbw.de This report is available in the internet on http://www.aqsbw.de/pdf/report_ukwir_ss_17.pdf.

UKWIR SS 17 Table of contents General... 1 PT design... 1 Analytical methods... 2 Evaluation procedure... 2 Results of evaluation... 3 Explanation of tables and graphs in the appendix... 4 Appendix A Anthracene A-1 Fluoranthene A-12 Naphtalene A-23 Benzo[a]pyrene A-34 Benzo[b]fluoranthene A-45 Benzo[k]fluoranthene A-56 Benzo[g,h,i]perylene A-67 Indeno[1,2,3-cd]perylene A-78

UKWIR SS 17 General This PT was provided by AQS Baden-Württemberg as a subcontractor for wca environment limited, Brunel House, Volunteer Way, Faringdon, Oxfordshire SN7 7YR, United Kingdom on behalf of United Kingdom Water Industry Research (UKWIR) to check the chemical analysis of priority and other substances in the context of chemical monitoring for the European Water Framework Directive, especially for compliance of surface waters with Environmental Quality Standards (EQS). The EQS directive 2008/105/EG requires that these substances are determined as total concentrations in the whole water sample, including the content at and in the suspended solids. In this round the following determinands were to be measured: Anthracene Fluoranthene Naphtalene Benzo[a]pyrene Benzo[b]fluoranthene Benzo[k]fluoranthene Benzo[g,h,i]perylene Indeno[1,2,3-cd]pyrene The PTs were executed and evaluated according to the requirements of ISO 13528: 2015. PT design Each participant received the following samples: 3 different surface water test samples at three concentration levels of the analytes in 1000 ml amber ground glass bottles. Two bottles of each sample were distributed for duplicate measurement. The samples were preserved by cooling. 3 different concentration levels/batches were produced. All participants received the same concentration levels. The concentrations of the analytes of the spiked samples were chosen according to the requirements of UKWIR based on the European Regulation for Environmental Quality Standard (Directive 2008/105/EG on environmental quality standards in the field of water policy). Sample preparation The samples were based on a real surface water. The suspended solids were isolated form the effluent of the waste water treatment plant Stuttgart- Büsnau with a high-speed centrifuge, freeze dried, grinded to a grain size of below 40 µm and analysed with GC-MS after Soxhlett extraction. For further use a stock solution of the suspended solids was produced. For the production of the batches/concentration levels, the surface water was filtered by using 5 µm and 1 µm filter cartridges to eliminate course particles. To reduce germs, the surface water was irradiated with ultraviolet light. page 1 of 5

UKWIR SS 17 For preparation of the samples, each bottle was filled with surface water, was spiked with the stock solution of the suspended solids and with a solution of the substances dissolved in a mixture of water and acetonitrile. The concentration of the suspended solids was ca. 20 mg/l per bottle. The samples contained ca. 0,2 µl/l acetonitrile. The concentrations of the analytes of the spiked samples were chosen according to the Environmental Quality Standard (Directive 2008/105/EG on environmental quality standards in the field of water policy). The samples were cooled directly after preparation and dispatched with freezer packs added to the packages. Samples distribution The samples were dispatched on 04 April 2017 by the express service TNT. The participants were requested to start with the analysis one day after receipt of the samples at the latest. Analytical methods The participants were free to choose a suitable method, but it was recommended to use EN 16691:2015 Water Quality Determination of selected polycylic aromatic hydrocarbons (PAH) in whole water samples Method using phase extraction (SPE) with SPE-disks combined with gas chromatography-mass spectrometry (GC-MS). It was required that the analytical method achieved the following limits of quantification: Parameter LOQ (µg/l) Anthracene 0,03 Fluoranthene 0,002 Naphtalene 0,03 Benzo[a]pyrene 0,0003 Benzo[b]fluoranthene 0,005 Benzo[k]fluoranthene 0,005 Benzo[g,h,i]perylene 0,0025 Indeno[1,2,3-cd]pyrene 0,0025 The samples had to be analysed in duplicate over the complete method (sample preparation and measurement). The participants were asked to submit the results as average values in µg/l with four significant digits. Submission of results The deadline for the submission of results was on 05 May 2017. Evaluation procedure The statistical evaluation was executed according to ISO 13528:2015 with the combined estimator Hampel/Q-method, a method of robust statistics. The assigned value x pt was derived from the formulation of the spiked samples including the concentration of the respective PAH in the suspended solids. The uncertainty of the spike was calculated from a complete uncertainty budget according to GUM. The standard deviation for proficiency assessment σ pt was calculated in accordance with the European QA/QC Directive: σ pt = 0,25 * x pt. page 2 of 5

UKWIR SS 17 A z-score was calculated for each measurement result derived from the assigned value x pt and the standard deviation for proficiency assessment σ pt: z = x x pt σ pt The assessment of the results was as follows: z 2.0 satisfactory 2.0 < z < 3.0 questionable z 3.0 unsatisfactory Results of evaluation Number of participants: 15 1 laboratory did not report any result. Number of reported values: 190 Number of accepted values: 129 (67,9 %) In the following figure the percentage of satisfactory, questionable, unsatisfactory and not submitted results are illustrated. page 3 of 5

UKWIR SS 17 Explanation of tables and graphs in the appendix The appendix contains the PT data for all parameters and all samples in tables and graphs. For each parameter the following illustrations are given: Parameter table In these tables the following values for each concentration level are listed: assigned value in µg/l expanded uncertainty of the assigned value in % standard deviation of the data set in µg/l, calculated using the Q-method (due to the often low number of participants this standard deviation estimate is not very reliable) standard deviation for proficiency assessment in µg/l for the calculation of z-scores (25 % of the assigned value) rel. standard deviation for proficiency assessment in % tolerance limits above and below in µg/l and % (limit for assessment as satisfactory ) number of values in this level number of not satisfactory values ( questionable or unsatisfactory ) below and above the assigned value and the percentage of these values in total Mean vs. spiked amount Here the assigned values are shown versus the spiked amount of determinant including the respective expanded uncertainties (k=2). Relative standard deviation The diagrams for the rel. standard deviation vs. the assigned value show the values compared to the fixed standard deviation for proficiency assessment (horizontal line at 25%) and the concentration dependence. Used methods The percentage of analytical techniques used is shown here. Sample table In this table all results of the participants are noted together with uncertainties (where reported). For these uncertainties -scores (zeta-scores) are calculated according to the formula x x pt ζ = u 2 lab + u 2 xpt With x = result of the participant x pt = assigned value u lab = participant s standard uncertainty u x,pt = standard uncertainty of the assigned value -scores can be used for the plausibility check of measurement uncertainties. The type of assessment is equivalent to that of z-scores, i.e. an absolute value of 2,0 can be regarded as satisfactory. -scores above this value indicate an underestimation of the measurement uncertainty. This table also contains the assigned value and its uncertainty as well as the tolerance limits (z = ± 2,0). Sample graphs of concentrations All participants results, sorted for values, are shown here versus the laboratory codes. The assigned value and its uncertainty as well as the tolerance limits are also included. page 4 of 5

UKWIR SS 17 z-score graphs In a similar way the z-scores attributed to the participants results are shown here versus the laboratory codes. Graphs of expanded uncertainty The expanded uncertainty is shown if laboratories reported uncertainties. ζ-score graphs If laboratories reported uncertainties, ζ-scores were calculated and are shown versus the laboratory codes. page 5 of 5

UKWIR SS 17 anthracene level assigned value [µg/l] expanded uncertainty of the assigned value [%] standard deviation, calculated using robust statistics [µg/l] standard deviation for proficiency assessment [µg/l] standard deviation for proficiency assessment [%] upper tolerance limit [µg/l] 1 0,1088 2,66 0,0318 0,0272 25,00 0,1632 0,0544 50,00-50,00 6 0 0 0,0 2 0,1690 2,82 0,0373 0,0422 25,00 0,2535 0,0845 50,00-50,00 6 0 0 0,0 3 0,2544 2,65 0,0771 0,0636 25,00 0,3816 0,1272 50,00-50,00 6 1 1 33,3 sum 18 1 1 11,1 lower tolerance limit [µg/l] upper tolerance limit [%] lower tolerance limit [%] number of results out below out above out [%] Mean vs. spiked amount page A-1 of A-88

Relative standard deviation 25 % is the value used as standard deviation for proficiency assessment. Used methods page A-2 of A-88

UKWIR SS 17 anthracene - 1 assigned value [µg/l]* 0,1088 ± 0,0029 upper tolerance limit [µg/l 0,1632 lower tolerance limit [µg/l 0,05438 lab code result [µg/l] ± -score z-score assessm.** 2 0,0814-1,0 s 3 0,06541 0,02-4,3-1,6 s 7 0,0596 30 0,0-1,8 s 9 0,08189-1,0 s 11 0,09611 0,029-0,9-0,5 s 19 0,102 0,012-1,1-0,2 s * The stated uncertainty of the assigned value is the expanded uncertainty with a coverage factor k=2 corresponding to a confidence level of about 95% ** s = satisfactory, q = questionable, u = unsatisfactory page A-3 of A-88

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UKWIR SS 17 anthracene - 2 assigned value [µg/l]* 0,169 ± 0,0048 upper tolerance limit [µg/l 0,2535 lower tolerance limit [µg/l 0,08449 lab code result [µg/l] ± -score z-score assessm.** 2 0,131-0,9 s 3 0,1056 0,032-3,9-1,5 s 7 0,0972 30 0,0-1,7 s 9 0,1259-1,0 s 11 0,1785 0,054 0,4 0,2 s 19 0,131 0,016-4,6-0,9 s * The stated uncertainty of the assigned value is the expanded uncertainty with a coverage factor k=2 corresponding to a confidence level of about 95% ** s = satisfactory, q = questionable, u = unsatisfactory page A-6 of A-88

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UKWIR SS 17 anthracene - 3 assigned value [µg/l]* 0,2544 ± 0,0067 upper tolerance limit [µg/l 0,3816 lower tolerance limit [µg/l 0,1272 lab code result [µg/l] ± -score z-score assessm.** 2 0,196-0,9 s 3 0,1532 0,046-4,4-1,6 s 7 0,1188 30 0,0-2,1 q 9 0,1753-1,2 s 11 0,5598 0,168 3,6 4,8 u 19 0,211 0,025-3,4-0,7 s * The stated uncertainty of the assigned value is the expanded uncertainty with a coverage factor k=2 corresponding to a confidence level of about 95% ** s = satisfactory, q = questionable, u = unsatisfactory page A-9 of A-88

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fluoranthene level assigned value [µg/l] expanded uncertainty of the assigned value [%] standard deviation, calculated using robust statistics [µg/l] standard deviation for proficiency assessment [µg/l] standard deviation for proficiency assessment [%] 1 0,0898 2,36 0,0138 0,0224 25,00 0,1347 0,0449 50,00-50,00 12 0 0 0,0 2 0,1602 2,25 0,0282 0,0400 25,00 0,2403 0,0801 50,00-50,00 11 0 0 0,0 3 0,2458 2,28 0,0526 0,0615 25,00 0,3687 0,1229 50,00-50,00 11 0 0 0,0 sum 34 0 0 0,0 upper tolerance limit [µg/l] lower tolerance limit [µg/l] upper tolerance limit [%] lower tolerance limit [%] number of results out below out above out [%] Mean vs. spiked amount page A-12 of A-88

Relative standard deviation 25 % is the value used as standard deviation for proficiency assessment. Used methods page A-13 of A-88

UKWIR SS 17 fluoranthene - 1 assigned value [µg/l]* 0,08978 ± 0,00212 upper tolerance limit [µg/l 0,1347 lower tolerance limit [µg/l 0,04489 lab code result [µg/l] ± -score z-score assessm.** 1 0,076-0,6 s 2 0,093 0,1 s 3 0,08169 0,025-0,6-0,4 s 5 0,08385-0,3 s 7 0,0782 20 0,0-0,5 s 8 0,06464-1,1 s 9 0,06524-1,1 s 11 0,0879 0,018-0,2-0,1 s 16 0,09695 0,3 s 19 0,0817 0,011-1,4-0,4 s 20 0,04857-1,8 s 23 0,06745-1,0 s * The stated uncertainty of the assigned value is the expanded uncertainty with a coverage factor k=2 corresponding to a confidence level of about 95% ** s = satisfactory, q = questionable, u = unsatisfactory page A-14 of A-88

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UKWIR SS 17 fluoranthene - 2 assigned value [µg/l]* 0,1602 ± 0,0036 upper tolerance limit [µg/l 0,2403 lower tolerance limit [µg/l 0,0801 lab code result [µg/l] ± -score z-score assessm.** 1 0,097-1,6 s 2 0,167 0,2 s 3 0,15 0,045-0,5-0,3 s 5 0,1272-0,8 s 7 0,1613 20 0,0 0,0 s 8 0,1434-0,4 s 9 0,11577-1,1 s 11 0,1555 0,031-0,3-0,1 s 16 0,17577 0,4 s 19 0,171 0,024 0,9 0,3 s 23 0,1238-0,9 s * The stated uncertainty of the assigned value is the expanded uncertainty with a coverage factor k=2 corresponding to a confidence level of about 95% ** s = satisfactory, q = questionable, u = unsatisfactory page A-17 of A-88

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UKWIR SS 17 fluoranthene - 3 assigned value [µg/l]* 0,2458 ± 0,0056 upper tolerance limit [µg/l 0,3687 lower tolerance limit [µg/l 0,1229 lab code result [µg/l] ± -score z-score assessm.** 1 0,125-2,0 s 2 0,258 0,2 s 3 0,2121 0,064-1,0-0,5 s 5 0,19255-0,9 s 7 0,2316 20 0,0-0,2 s 8 0,208-0,6 s 9 0,18255-1,0 s 11 0,2719 0,054 1,0 0,4 s 16 0,29364 0,8 s 19 0,254 0,035 0,5 0,1 s 23 0,1881-0,9 s * The stated uncertainty of the assigned value is the expanded uncertainty with a coverage factor k=2 corresponding to a confidence level of about 95% ** s = satisfactory, q = questionable, u = unsatisfactory page A-20 of A-88

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naphthalene level assigned value [µg/l] expanded uncertainty of the assigned value [%] standard deviation, calculated using robust statistics [µg/l] standard deviation for proficiency assessment [µg/l] standard deviation for proficiency assessment [%] upper tolerance limit [µg/l] 1 0,1255 2,36 0,0164 0,0314 25,00 0,1882 0,0627 50,00-50,00 6 0 0 0,0 2 0,2061 2,36 0,1086 0,0515 25,00 0,3092 0,1031 50,00-50,00 6 0 1 16,7 3 0,2984 2,54 0,1299 0,0746 25,00 0,4476 0,1492 50,00-50,00 6 0 1 16,7 sum 18 0 2 11,1 lower tolerance limit [µg/l] upper tolerance limit [%] lower tolerance limit [%] number of results out below out above out [%] Mean vs. spiked amount page A-23 of A-88

25 % is the value used as standard deviation for proficiency assessment. page A-24 of A-88

UKWIR SS 17 naphthalene - 1 assigned value [µg/l]* 0,1255 ± 0,003 upper tolerance limit [µg/l 0,1882 lower tolerance limit [µg/l 0,06273 lab code result [µg/l] ± -score z-score assessm.** 2 0,134 0,033 0,5 0,3 s 3 0,1394 0,042 0,7 0,4 s 7 0,0967 70 0,0-0,9 s 9 0,12072-0,2 s 11 0,1366 0,068 0,3 0,4 s 19 0,102 0,056-0,8-0,7 s * The stated uncertainty of the assigned value is the expanded uncertainty with a coverage factor k=2 corresponding to a confidence level of about 95% ** s = satisfactory, q = questionable, u = unsatisfactory page A-25 of A-88

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UKWIR SS 17 naphthalene - 2 assigned value [µg/l]* 0,2061 ± 0,0049 upper tolerance limit [µg/l 0,3092 lower tolerance limit [µg/l 0,1031 lab code result [µg/l] ± -score z-score assessm.** 2 0,242 0,059 1,2 0,7 s 3 0,2257 0,068 0,6 0,4 s 7 0,1054 70 0,0-2,0 s 9 0,18607-0,4 s 11 0,3306 0,165 1,5 2,4 q 19 0,152 0,084-1,3-1,1 s * The stated uncertainty of the assigned value is the expanded uncertainty with a coverage factor k=2 corresponding to a confidence level of about 95% ** s = satisfactory, q = questionable, u = unsatisfactory page A-28 of A-88

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UKWIR SS 17 naphthalene - 3 assigned value [µg/l]* 0,2984 ± 0,0076 upper tolerance limit [µg/l 0,4476 lower tolerance limit [µg/l 0,1492 lab code result [µg/l] ± -score z-score assessm.** 2 0,325 0,079 0,7 0,4 s 3 0,3101 0,093 0,3 0,2 s 7 0,1991 70 0,0-1,3 s 9 0,2709-0,4 s 11 0,6098 0,305 2,0 4,2 u 19 0,159 0,087-3,2-1,9 s * The stated uncertainty of the assigned value is the expanded uncertainty with a coverage factor k=2 corresponding to a confidence level of about 95% ** s = satisfactory, q = questionable, u = unsatisfactory page A-31 of A-88

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benzo[a]pyrene level assigned value [µg/l] expanded uncertainty of the assigned value [%] standard deviation, calculated using robust statistics [µg/l] standard deviation for proficiency assessment [µg/l] standard deviation for proficiency assessment [%] upper tolerance limit [µg/l] 1 0,0116 3,41 0,0059 0,0029 25,00 0,0174 0,0058 50,00-50,00 12 3 2 41,7 2 0,0574 2,76 0,0164 0,0143 25,00 0,0861 0,0287 50,00-50,00 12 7 1 66,7 3 0,1036 2,74 0,0322 0,0259 25,00 0,1554 0,0518 50,00-50,00 12 7 1 66,7 sum 36 17 4 58,3 lower tolerance limit [µg/l] upper tolerance limit [%] lower tolerance limit [%] number of results out below out above out [%] Mean vs. spiked amount page A-34 of A-88

Relative standard deviation 25 % is used as standard deviation for proficiency assessment. Used methods page A-35 of A-88

UKWIR SS 17 benzo[a]pyrene - 1 assigned value [µg/l]* 0,01157 ± 0,00039 upper tolerance limit [µg/l 0,01736 lower tolerance limit [µg/l 0,005785 lab code result [µg/l] ± -score z-score assessm.** 1 0,04 9,8 u 2 0,0116 0,003 0,0 0,0 s 3 0,01381 0,004 1,1 0,8 s 5 0,011155-0,1 s 7 0,0092 30 0,0-0,8 s 8 0,00555-2,1 q 9 0,00731-1,5 s 11 0,007126 0,001-6,0-1,5 s 16 0,00358-2,8 q 19 0,0275 0,003 10,5 5,5 u 20 0,00322-2,9 q 23 0,01162 0,0 s * The stated uncertainty of the assigned value is the expanded uncertainty with a coverage factor k=2 corresponding to a confidence level of about 95% ** s = satisfactory, q = questionable, u = unsatisfactory page A-36 of A-88

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UKWIR SS 17 benzo[a]pyrene - 2 assigned value [µg/l]* 0,05739 ± 0,00158 upper tolerance limit [µg/l 0,08608 lower tolerance limit [µg/l 0,02869 lab code result [µg/l] ± -score z-score assessm.** 1 0,008-3,4 u 2 0,0457 0,011-2,1-0,8 s 3 0,04695 0,014-1,5-0,7 s 5 0,015315-2,9 q 7 0,0426 30 0,0-1,0 s 8 0,01947-2,6 q 9 0,031455-1,8 s 11 0,0198 0,004-17,6-2,6 q 16 0,01298-3,1 u 19 0,138 0,014 11,4 5,6 u 20 0,01206-3,2 u 23 0,02303-2,4 q * The stated uncertainty of the assigned value is the expanded uncertainty with a coverage factor k=2 corresponding to a confidence level of about 95% ** s = satisfactory, q = questionable, u = unsatisfactory page A-39 of A-88

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UKWIR SS 17 benzo[a]pyrene - 3 assigned value [µg/l]* 0,1036 ± 0,0028 upper tolerance limit [µg/l 0,1554 lower tolerance limit [µg/l 0,0518 lab code result [µg/l] ± -score z-score assessm.** 1 0,016-3,4 u 2 0,0847 0,02-1,9-0,7 s 3 0,09043 0,027-1,0-0,5 s 5 0,03419-2,7 q 7 0,0759 30 0,0-1,1 s 8 0,03542-2,6 q 9 0,056018-1,8 s 11 0,03583 0,007-17,6-2,6 q 16 0,02615-3,0 u 19 0,238 0,024 11,1 5,2 u 20 0,02018-3,2 u 23 0,04471-2,3 q * The stated uncertainty of the assigned value is the expanded uncertainty with a coverage factor k=2 corresponding to a confidence level of about 95% ** s = satisfactory, q = questionable, u = unsatisfactory page A-42 of A-88

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benzo[b]fluoranthene level assigned value [µg/l] expanded uncertainty of the assigned value [%] standard deviation, calculated using robust statistics [µg/l] standard deviation for proficiency assessment [µg/l] standard deviation for proficiency assessment [%] upper tolerance limit [µg/l] 1 0,0503 2,78 0,0190 0,0126 25,00 0,0754 0,0251 50,00-50,00 7 1 1 28,6 2 0,1141 2,96 0,0367 0,0285 25,00 0,1711 0,0570 50,00-50,00 7 2 1 42,9 3 0,2266 2,84 0,0686 0,0566 25,00 0,3399 0,1133 50,00-50,00 7 3 1 57,1 sum 21 6 3 42,9 lower tolerance limit [µg/l] upper tolerance limit [%] lower tolerance limit [%] number of results out below out above out [%] Mean vs. spiked amount page A-45 of A-88

Relative standard deviation 25 % is used as standard deviation for proficiency assessment. page A-46 of A-88

UKWIR SS 17 benzo[b]fluoranthene - 1 assigned value [µg/l]* 0,05027 ± 0,0014 upper tolerance limit [µg/l 0,0754 lower tolerance limit [µg/l 0,02513 lab code result [µg/l] ± -score z-score assessm.** 1 0,023-2,2 q 2 0,0449-0,4 s 3 0,04657 0,014-0,5-0,3 s 7 0,0478 30 0,0-0,2 s 9 0,02832-1,7 s 11 0,03608 0,007-3,9-1,1 s 19 0,102 0,013 7,9 4,1 u * The stated uncertainty of the assigned value is the expanded uncertainty with a coverage factor k=2 corresponding to a confidence level of about 95% ** s = satisfactory, q = questionable, u = unsatisfactory page A-47 of A-88

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UKWIR SS 17 benzo[b]fluoranthene - 2 assigned value [µg/l]* 0,1141 ± 0,0034 upper tolerance limit [µg/l 0,1711 lower tolerance limit [µg/l 0,05705 lab code result [µg/l] ± -score z-score assessm.** 1 0,051-2,2 q 2 0,108-0,2 s 3 0,0918 0,028-1,6-0,8 s 7 0,085 30 0,0-1,0 s 9 0,10164-0,4 s 11 0,0479 0,01-13,0-2,3 q 19 0,222 0,028 7,7 3,8 u * The stated uncertainty of the assigned value is the expanded uncertainty with a coverage factor k=2 corresponding to a confidence level of about 95% ** s = satisfactory, q = questionable, u = unsatisfactory page A-50 of A-88

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UKWIR SS 17 benzo[b]fluoranthene - 3 assigned value [µg/l]* 0,2266 ± 0,0064 upper tolerance limit [µg/l 0,3399 lower tolerance limit [µg/l 0,1133 lab code result [µg/l] ± -score z-score assessm.** 1 0,031-3,5 u 2 0,188-0,7 s 3 0,1719 0,052-2,1-1,0 s 7 0,1778 30 0,0-0,9 s 9 0,05648-3,0 u 11 0,06372 0,013-22,8-2,9 q 19 0,454 0,057 7,9 4,0 u * The stated uncertainty of the assigned value is the expanded uncertainty with a coverage factor k=2 corresponding to a confidence level of about 95% ** s = satisfactory, q = questionable, u = unsatisfactory page A-53 of A-88

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benzo[k]fluoranthene level assigned value [µg/l] expanded uncertainty of the assigned value [%] standard deviation, calculated using robust statistics [µg/l] standard deviation for proficiency assessment [µg/l] standard deviation for proficiency assessment [%] upper tolerance limit [µg/l] 1 0,0671 3,04 0,0568 0,0168 25,00 0,1006 0,0335 50,00-50,00 7 2 1 42,9 2 0,1628 3,17 0,1154 0,0407 25,00 0,2442 0,0814 50,00-50,00 7 2 1 42,9 3 0,2766 3,03 0,1348 0,0691 25,00 0,4149 0,1383 50,00-50,00 7 3 1 57,1 sum 21 7 3 47,6 lower tolerance limit [µg/l] upper tolerance limit [%] lower tolerance limit [%] number of results out below out above out [%] Mean vs. spiked amount page A-56 of A-88

Relative standard deviation 25 % is used as standard deviation for proficiency assessment. page A-57 of A-88

UKWIR SS 17 benzo[k]fluoranthene - 1 assigned value [µg/l]* 0,06708 ± 0,00204 upper tolerance limit [µg/l 0,1006 lower tolerance limit [µg/l 0,03354 lab code result [µg/l] ± -score z-score assessm.** 1 0,025-2,5 q 2 0,065 0,015-0,3-0,1 s 3 0,06795 0,02 0,1 0,1 s 7 0,0476 30 0,0-1,2 s 9 0,098848 1,9 s 11 0,021 0,004-19,7-2,7 q 19 0,174 0,043 5,0 6,4 u * The stated uncertainty of the assigned value is the expanded uncertainty with a coverage factor k=2 corresponding to a confidence level of about 95% ** s = satisfactory, q = questionable, u = unsatisfactory page A-58 of A-88

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UKWIR SS 17 benzo[k]fluoranthene - 2 assigned value [µg/l]* 0,1628 ± 0,0052 upper tolerance limit [µg/l 0,2442 lower tolerance limit [µg/l 0,08141 lab code result [µg/l] ± -score z-score assessm.** 1 0,091-1,8 s 2 0,166 0,038 0,2 0,1 s 3 0,1846 0,055 0,8 0,5 s 7 0,13 30 0,0-0,8 s 9 0,03639-3,1 u 11 0,07539 0,015-11,0-2,1 q 19 0,373 0,092 4,6 5,2 u * The stated uncertainty of the assigned value is the expanded uncertainty with a coverage factor k=2 corresponding to a confidence level of about 95% ** s = satisfactory, q = questionable, u = unsatisfactory page A-61 of A-88

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UKWIR SS 17 benzo[k]fluoranthene - 3 assigned value [µg/l]* 0,2766 ± 0,0084 upper tolerance limit [µg/l 0,4149 lower tolerance limit [µg/l 0,1383 lab code result [µg/l] ± -score z-score assessm.** 1 0,058-3,2 u 2 0,211 0,048-2,7-0,9 s 3 0,2329 0,07-1,2-0,6 s 7 0,1669 30 0,0-1,6 s 9 0,12016-2,3 q 11 0,06359 0,013-28,0-3,1 u 19 0,555 0,136 4,1 4,0 u * The stated uncertainty of the assigned value is the expanded uncertainty with a coverage factor k=2 corresponding to a confidence level of about 95% ** s = satisfactory, q = questionable, u = unsatisfactory page A-64 of A-88

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benzo[ghi]perylene level assigned value [µg/l] expanded uncertainty of the assigned value [%] standard deviation, calculated using robust statistics [µg/l] standard deviation for proficiency assessment [µg/l] standard deviation for proficiency assessment [%] upper tolerance limit [µg/l] 1 0,0811 2,65 0,0478 0,0203 25,00 0,1217 0,0406 50,00-50,00 7 1 1 28,6 2 0,1487 2,82 0,0896 0,0372 25,00 0,2230 0,0743 50,00-50,00 7 1 2 42,9 3 0,2247 2,66 0,1824 0,0562 25,00 0,3370 0,1123 50,00-50,00 7 2 1 42,9 sum 21 4 4 38,1 lower tolerance limit [µg/l] upper tolerance limit [%] lower tolerance limit [%] number of results out below out above out [%] Mean vs. spiked amount page A-67 of A-88

Relative standard deviation 25 % is used as standard deviation for proficiency assessment. page A-68 of A-88

UKWIR SS 17 benzo[ghi]perylene - 1 assigned value [µg/l]* 0,08114 ± 0,00215 upper tolerance limit [µg/l 0,1217 lower tolerance limit [µg/l 0,04057 lab code result [µg/l] ± -score z-score assessm.** 1 0,01-3,5 u 2 0,0593 0,016-2,7-1,1 s 3 0,0875 0,026 0,5 0,3 s 7 0,0442 40 0,0-1,8 s 9 0,045009-1,8 s 11 0,06688 0,013-2,1-0,7 s 19 0,184 0,12 1,7 5,1 u * The stated uncertainty of the assigned value is the expanded uncertainty with a coverage factor k=2 corresponding to a confidence level of about 95% ** s = satisfactory, q = questionable, u = unsatisfactory page A-69 of A-88

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UKWIR SS 17 benzo[ghi]perylene - 2 assigned value [µg/l]* 0,1487 ± 0,0042 upper tolerance limit [µg/l 0,223 lower tolerance limit [µg/l 0,07433 lab code result [µg/l] ± -score z-score assessm.** 1 0,076-2,0 s 2 0,143 0,038-0,3-0,2 s 3 0,2266 0,068 2,3 2,1 q 7 0,1228 40 0,0-0,7 s 9 0,11196-1,0 s 11 0,07012 0,014-10,7-2,1 q 19 0,396 0,259 1,9 6,7 u * The stated uncertainty of the assigned value is the expanded uncertainty with a coverage factor k=2 corresponding to a confidence level of about 95% ** s = satisfactory, q = questionable, u = unsatisfactory page A-72 of A-88

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UKWIR SS 17 benzo[ghi]perylene - 3 assigned value [µg/l]* 0,2247 ± 0,006 upper tolerance limit [µg/l 0,337 lower tolerance limit [µg/l 0,1123 lab code result [µg/l] ± -score z-score assessm.** 1 0,017-3,7 u 2 0,203 0,054-0,8-0,4 s 3 0,3337 0,1 2,2 1,9 s 7 0,1739 40 0,0-0,9 s 9 0,14493-1,4 s 11 0,1029 0,021-11,4-2,2 q 19 0,638 0,417 2,0 7,4 u * The stated uncertainty of the assigned value is the expanded uncertainty with a coverage factor k=2 corresponding to a confidence level of about 95% ** s = satisfactory, q = questionable, u = unsatisfactory page A-75 of A-88

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indeno[1,2,3-cd]pyrene level assigned value [µg/l] expanded uncertainty of the assigned value [%] standard deviation, calculated using robust statistics [µg/l] standard deviation for proficiency assessment [µg/l] standard deviation for proficiency assessment [%] upper tolerance limit [µg/l] 1 0,0595 2,73 0,0389 0,0149 25,00 0,0892 0,0297 50,00-50,00 7 2 1 42,9 2 0,1762 2,88 0,0543 0,0441 25,00 0,2643 0,0881 50,00-50,00 7 1 1 28,6 3 0,2400 2,73 0,0925 0,0600 25,00 0,3600 0,1200 50,00-50,00 7 3 1 57,1 sum 21 6 3 42,9 lower tolerance limit [µg/l] upper tolerance limit [%] lower tolerance limit [%] number of results out below out above out [%] Mean vs. spiked amount page A-78 of A-88

Relative standard deviation 25 % is used as standard deviation for proficiency assessment. page A-79 of A-88

UKWIR SS 17 indeno[1,2,3-cd]pyrene - 1 assigned value [µg/l]* 0,05946 ± 0,00162 upper tolerance limit [µg/l 0,08919 lower tolerance limit [µg/l 0,02973 lab code result [µg/l] ± -score z-score assessm.** 1 0,015-3,0 u 2 0,0536-0,4 s 3 0,06271 0,019 0,3 0,2 s 7 0,0467 30 0,0-0,9 s 9 0,035546-1,6 s 11 0,0102 0,002-37,8-3,3 u 19 0,108 0,026 3,7 3,3 u * The stated uncertainty of the assigned value is the expanded uncertainty with a coverage factor k=2 corresponding to a confidence level of about 95% ** s = satisfactory, q = questionable, u = unsatisfactory page A-80 of A-88

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page A-82 of A-88

UKWIR SS 17 indeno[1,2,3-cd]pyrene - 2 assigned value [µg/l]* 0,1762 ± 0,0051 upper tolerance limit [µg/l 0,2643 lower tolerance limit [µg/l 0,08811 lab code result [µg/l] ± -score z-score assessm.** 1 0,106-1,6 s 2 0,172-0,1 s 3 0,1526 0,046-1,0-0,5 s 7 0,1162 30 0,0-1,4 s 9 0,094989-1,8 s 11 0,08045 0,016-11,4-2,2 q 19 0,35 0,083 4,2 3,9 u * The stated uncertainty of the assigned value is the expanded uncertainty with a coverage factor k=2 corresponding to a confidence level of about 95% ** s = satisfactory, q = questionable, u = unsatisfactory page A-83 of A-88

page A-84 of A-88

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UKWIR SS 17 indeno[1,2,3-cd]pyrene - 3 assigned value [µg/l]* 0,24 ± 0,0065 upper tolerance limit [µg/l 0,36 lower tolerance limit [µg/l 0,12 lab code result [µg/l] ± -score z-score assessm.** 1 0,017-3,7 u 2 0,162-1,3 s 3 0,1565 0,047-3,5-1,4 s 7 0,1226 30 0,0-2,0 s 9 0,095052-2,4 q 11 0,05947 0,012-26,6-3,0 u 19 0,372 0,088 3,0 2,2 q * The stated uncertainty of the assigned value is the expanded uncertainty with a coverage factor k=2 corresponding to a confidence level of about 95% ** s = satisfactory, q = questionable, u = unsatisfactory page A-86 of A-88

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