Proficiency Test SYKE 8/2012

REPORTS OF FINNISH ENVIRONMENT INSTITUTE 0 Proficiency Test SYKE 8/0 Volatile organic compounds in water and soil Kaija Korhonen-Ylönen, Jari Nuutinen, Mirja Leivuori and Markku Ilmakunnas Finnish Environment Institute

REPORTS OF FINNISH ENVIRONMENT INSTITUTE 0 Proficiency Test SYKE 8/0 Volatile organic compounds in water and soil Kaija Korhonen-Ylönen, Jari Nuutinen, Mirja Leivuori and Markku Ilmakunnas Helsinki 0 Finnish Environment Institute

REPORTS OF FINNISH ENVIRONMENT INSTITUTE 0 Finnish Environment Institute SYKE The proficiency test provider: Proftest SYKE, Finnish Environment Institute (SYKE), Centre Hakuninmaantie, 000 Helsinki phone +8 0, fax + 9 9 Publication is available only in the internet : www.environment.fi/publications ISBN 98-9--- (PDF) ISSN 9- (online)

CONTENT ALKUSANAT / PREFACE INTRODUCTION ORGANIZING OF THE POFICIENCY TEST. Responsibilities. Participants. Samples and their delivery. Homogeneity and stability studies. Feedback from the pro ciency test. Prosessing of the data.. Pretesting of the data.. Assigned value.. Standard deviation for pro ciency assessment and z score RESULTS AND CONCLUSIONS 8. Results 8. Analytical methods and status to the results. Uncertainties of the results EVALUATION OF PERFORMANCE SUMMARY YHTEENVETO REFERENCES APPENDIXES Participants Preparation of the samples Testing of homogeneity 9 Testing of stability Feedback from the pro ciency test Assigned values and their uncertainties Terms in the result tables 8 Results of each participant 9 Results and their measurement uncertainties 0 Summary of the z scores. Analytical methods 8. Results grouped according to the measurement methods 9 Examples of the reported measurement uncertainties reported by the laboratories 8 DOCUMENTATION PAGE KUVAILULEHTI PRESENTATIONBLAD

ALKUSANAT Suomen ympäristökeskus (SYKE) on toiminut ympäristöalan kansallisena vertailulaboratoriona vuodesta 00 lähtien. Toiminta perustuu ympäristöministeriön määräykseen, mikä on annettu ympäristönsuojelulain (8/000) nojalla. Vertailulaboratorion tarjoamista palveluista yksi tärkeimmistä on pätevyyskokeiden ja muiden vertailumittausten järjestäminen. SYKEn laboratoriot on FINAS-akkreditointipalvelun akkreditoima testauslaboratorio T00 ja kalibrointilaboratorio K0 (SFS-EN ISO/IEC 0) sekä vertailumittausten järjestäjä Pro!est SYKE PT0 (SFS-EN ISO/IEC 0, www. nas. ). Tämä pätevyyskoe on toteutettu SYKEn vertailulaboratorion pätevyysalueella ja se antaa tietoa osallistujien pätevyyden lisäksi tulosten vertailukelpoisuudesta myös yleisemmällä tasolla. Pätevyyskokeen onnistumisen edellytys on järjestäjän ja osallistujien välinen luottamuksellinen yhteistyö. Parhaat kiitokset yhteistyöstä kaikille osallistujille PREFACE Finnish Environment Institute (SYKE) is appointed National Reference in the environmental sector by the Ministry of the Environment according to section of the Environment Protection Act (8/000) since 00. "e duties of the reference laboratory service include providing pro ciency tests and other interlaboratory comparisons for analytical laboratories and other producers of environmental information. SYKE laboratories has been accredited by the Finnish Accreditation service as the testing laboratory T00 and the calibration laboratory K0 (EN ISO/IEC 0) and as the pro ciency testing provider Pro!est SYKE PT0 (EN ISO/IEC 0, www. nas. ). "is pro ciency test has been carried out under the scope of the SYKE reference laboratory and it provides information about performance of the participants as well as comparability of the results at a more general level. "e success of the pro ciency test requires con dential co-operation between the provider and participants. "ank you for your co-operation Helsingissä. helmikuuta 0 / Helsinki February 0 Laboratorionjohtaja / Chief of

INTRODUCTION In October 0 Pro!est SYKE carried out the pro ciency test (PT) for the analysis of volatile organic compounds (VOC) in water and soil. "e test was carried out in accordance with the international standards, ISO/IEC 0 [] and ISO 8 [] as well as IUPAC technical report []. "e SYKE laboratory has been accredited by the Finnish Accreditation Service as a pro ciency testing provider Pro!est SYKE PT0 on the eld of the present PT (www. nas. ). ORGANIZING OF THE PROFICIENCY TEST. Responsibilities Organizing laboratory: Pro!est SYKE, Finnish Environment Institute (SYKE), Centre, Hakuninmaantie, 000 Helsinki, Finland Phone: +8 0 # Fax: + 8 0 "e responsibilities in organizing the PT were as follows: Kaija Korhonen-Ylönen, coordinator Jari Nuutinen, analytical expert and substitute of coordinator Helena Tanttu, technical assistant Markku Ilmakunnas, technical assistant, layout of the report Keijo Tervonen, technical assistant Sari Lanteri, technical assistant Ritva Väisänen, technical assistant. Participants In total, laboratories from Czech Republic, Denmark, Finland, Hungary, Norway and Sweden participated in this PT (Appendix ). One laboratory reported two results measured by di$erent analytical methods. About % of the participating laboratories used accredited analytical methods for at least a part of the measurements. "e organizing laboratory (SYKE) has the code 8 in the result tables.. Samples and their delivery "e synthetic solution AV and the addition standard solutions for the water sample NV and the soil sample MV was prepared gravimetrically from individual compounds by diluting to the nal concentration (Appendix ). Both the soil sample MV and the water sample NV were spiked with a known amount of the addition solution. "e preparation of the samples is shown more detail in Appendix. "e concentrations of the aromatic and chlorinated hydrocarbons in the samples AV and NV were checked against the NIST-traceable certi ed calibration solution (Supelco Organics Calibration Mix). "e samples were delivered October 0. "ey were requested to be analysed before 9 October 0. All participants reported their results at the latest 9 October 0 and the preliminary results were reported to the participants November 0.

. Homogeneity and stability studies Homogeneities of the sample NV and the sample of MV were tested by analysing all VOC compounds in four replicate determinations from six sub samples (Appendix ). Although homogenous criteria ful lled for most VOC compounds in the water sample NV, the concentration of many VOC compounds decreased during the sample preparation a!er the sample number and the results of these compounds were not assessed. In the concentrations of,-dichloroethane, dichloromethane, chloroform and oxygenates were not observed any remarkable decrease and these results could be evaluated. According to the homogenous test the sample MV was considered to be homogenous. Homogeneity of the arti cial sample AV was tested by analysing VOC compounds as duplicates from three samples, because the arti cal samples are known to be homogenous according to literature and previous experience. Also according to the homogenous test the between-subsamples standard deviation was insigni cant compared to the analytical standard deviation. "e stabilities of the samples AV and MV were checked during the sample transport to the participants. "e sample vials were weighed at SYKE before the delivering and reweighed at the participating laboratory a!er the receiving. "e di$erences of these two measurements should be < 0. %. One sample AV and three samples MV were sent again due to evaporation of solvent during the transport. "e stability test was carried out for all samples AV, NV and MV. One part of the samples was stored at the room temperature and the other part at the temperature C over night. "e samples were analysed 9 October (Appendix ). "e stability of the samples during the transport was mainly adequately good. According to the test the concentration of tetrachloroethene in the sample AV could increase. "is was taken into account in performance evaluation and the results of tetrachloroethene were not assessed. According to the test the concentration of carbontetrachloride and dichloromethane in the sample MV could increase, if the temperature incresed to 0 C during the transport. Nine laboratories reported the temperature of the receaved samples to be higher than C. "is was taken into account in performance evaluation (Chapter ). Only the results of,-dichloroethane, dichloromethane, chloroform and oxygenates from the water sample NV was assessed and according to the test these compound were stable.. Feedback from the pro ciency test Appendix contains the comments sent by the participants as well as the provider s comments to some participants.. Processing of the data.. Pretesting of the data Before the statistical treatment, the data was tested according to the Kolmogorov-Smirnov normality test and the possible extreme values were rejected as the outliers according to the Hampel test (H in the results sheets). Also before the robust calculation some extreme outliers were rejected in case that the results deviated from the robust mean more than 0 % or in the case that the results was reported erroneously (e.g. wrong unit). "e replicate results were tested using the Cochran test (C in the result sheets). In case that the result had been reported to be lower than detection limit, it had not been included in the statistical calculation of the results (H in the results sheets). More detailed information of the testing and

statistical treatment of the PT data is available on the internet in the guide for participating laboratories in SYKE pro ciency testing schemes (www.environment. /syke/pro!est)... Assigned value "e assigned values and their uncertainties are presented in Appendix. "e calculated concentrations were used as the assigned values for the concentrations of all measurements in the arti cial sample AV and the water sample NV. "e expanded uncertainty of the assigned value (k = ) was estimated using standard uncertainties associated with individual operations involved in the preparation of the sample. In all cases the uncertainty was < %. "e main resource of the uncertainty was impurity of the stock solutions. "e means of the reported results were used as the assigned value for the measurements of the soil sample MV. "e uncertainty of the assigned value was calculated using the standard deviation of the reported results. It was assumed that the uncertainty of mean included the e$ects of sample inhomogeneity and short term stability. In the sample MV the uncertainties of the assigned values varied from % to 8 %. A!er reporting of the preliminary results no changes to the assigned values have been done... Standard deviation for pro ciency assessment and z score "e performance evaluation was based on z score, which was calculated using the estimated standard deviation for pro ciency assessment (s p ). "e standard deviation for pro ciency assessment was estimated on basis of the type of the sample, the concentration of the element, the results of homogeneity and stability testing, the uncertainties of the assigned values and the longterm variation in former pro ciency tests. A!er the preliminary performance evaluation the total standard deviations were changed as follows: Sample Analyte / Sample Change of s p Impact on performance evaluation AV TCBz 0 % % No effect on the number of satisfactory results. MV DCM 0 % 0 % No effect on the number of satisfactory results. AV NV TECEe TCBz, Bz, cdcee, CCl, ETBz, mpxyl, oxyl, tdcee, TCEe, TECTe, TOL s p could not be estimated reliable Performance evaluation was not carried out. MV tdcee

8 e reliability of the assigned value was statistically tested according to the IUPAC Technical report []. e criterion was u/s p! 0., where u is the standard uncertainty of the assigned value and s p the standard deviation for pro"ciency assessment. Due to low number of the participants the criterion was not met in every case, which is indicated that the following assigned values had high uncertainty: Sample MV Measurement Bz, TCBz, DCEa, cdcee, CHCl, DCM, ETBE, ETBz, mpxyl, MTBE, oxyl, TAME RESULTS AND CONCLUSIONS. Results e results and the performance of each laboratory are presented in Appendix 8 and the summary of the results in Table. e results and their uncertainties are presented graphically in Appendix 9. Explanations for the result sheets are presented in Appendix. e summary of the performance evaluation (z scores) is presented in Appendix.

9 Table. Summary of the pro ciency test SYKE 8/0. Ass. val. -the assigned value, Mean- the mean value, Mean rob- the robust mean, Md- the median value, SD rob- the robust standard deviation, SD rob % - the robust standard deviation as percents, Num of Labs- the number of the participants, *Targ. SD%- the total standard deviation for pro ciency assessment at the 9% con dence interval (=*s p ), Accepted z-val% - the amount of satisfactory z scores. "e robust deviations of the assessed results of aromatic compounds varied from % to % and of the assessed results of chlorinated compounds from 9 % to %. "e robust deviations of the results of oxygenates were between and % (Table ). In this PT the participants were requested to report duplicate results for all measurements. "e results of the replicate determinations based on the ANOVA statistical handling are presented in Table.

Table. Results of the replicate determinations (ANOVA statistics). "e within-laboratory standard deviation, s w, describes the repeatability of measurements. While the between-laboratory standard deviation, s b, describes the reproducibility of measurements. In this PT the reproducibility (s b ) was an average from to times higher than the repeatability (s w ). For the robust methods, the ratio s b /s w, should be between and.

. Analytical methods and status to the results "e analytical methods used by the participants are presented more detailed in Appendix.. VOC compounds in water VOC compound were determined using the methods based on several standards [-]. One laboratory extracted VOC compounds from water with pentan extraction. All other participants used either headspace or purge & trap technique without liquid-liquid extraction. Most participants used GC-MS technique. With the GC-MS technique at least toluene-d8 was used as internal standard (Appendix.). Analytical methods were coded by coordinator based on the measurement technique as follows: Code Measurement tecnique Number of participants Method GC-MS Method GC-FID+ECD Method GC-FID Method Not specified Statistical comparison between methods was not possible due to the low number of the results, but according to the graphical presentation the unsatisfactory results were not coused based on applied technique (Appendix.). VOC compounds in soil Determination of VOC compounds from soil sample mostly based on ISO standard []. Extraction was mostly done by shaking. Only one participant heated the sample in headspace vial and one participant used both shaking and ultrasonication. Most participants used headspace as injection technique and only one split-technique. Equipment technique was mostly GC-MS and only one participant used GC-FID. Analytical methods were coded by coordinator according teh measurement technique as follows: Code Measurement tecnique Number of participants Method GC-MS Method GC-FID+ECD - Method GC-FID Method Not specified Statistical comparison between GC-MS and GC-FID was not possible, but according to the graphical presentation the unsatisfactory results were not due to the applied technique (Appendix.).. Uncertainties of the results Most laboratories (8 %) reported the expanded uncertainties with their results (Appendix 9). "e reported uncertainties varied greatly, especially in the analysis of water samples (Table ). Most laboratories estimated uncertainties using the data of validation and internal quality control (Meth ). "e reported evaluation procedures of the uncertainties did not explain the high variation between the reported uncertainties (Appendix ). It is evident, that harmonization in the estimation of uncertainties should be continued.

Table. e range of the expanded measurement uncertainties (k=) reported with the results in the PT8/0. Analyte AV % NV % MV % Benzene 0 0 Ethylbenzene 0 0 0 Toluene 0 0 o-xylene 0 0 m/p-xylene 0 0,,-Trichlorobenzene 0 0 0 0 Carbontetrachloride 0 0 0 0 Chloroform 0 0 0,-Dichloroethane 0 0 0 9 cis-,-dichloroethane 0 0 trans-,-dichloroethane 0 0 9 Dichloromethane 0 0 Trichloroethene 0 0 0 Tetrachloroethene 0 0 0 ETBE 0 0 0 8 MTBE 0 0 0 TAME 0 0 0 0 EVALUATION OF PERFORMANCE e evaluation of the participants was based on z scores, which were calculated using the estimated standard deviation for pro!ciency assessment. e results were interpreted as follows: Criteria Performance z Satisfactory < z < Questionable z Unsatisfactory e calculated z scores are presented with the results of each participant (Appendix 8) and graphical presentation of the results with their uncertainties is shown in Appendix 9. e summary of z scores is presented in Appendix. In total, % of the total result data in this PT were satisfactory. ree quarters of the participants used accredited methods and % of these results were satisfactory (Appendix ). The summary of the performance evaluation is shown in Table.

Table. Summary of the performance evaluation in the pro!ciency test 8/0. Analyte / Sample s p Satisfactory Remarks results, % Aromatics / AV A few of the results were questionable and % were unsatisfactory. Chlorinated hydrocarbons / AV The results of tetrachloroethene were not assessed because of a suspicion of instability of analyte. 0 % of the results were unsatisfactory and % questionable. The results of TeCEe were not assessed. Oxygenates / AV 0 % of the results were unsatisfactory and 8 % questionable. Difficulties especially in measurements of TAME. Aromatics / NV - - The results were not assessed by the provider because the decreasing trend in the concentration according to the sub sampling number. The participant can compare one s results to the assigned values, if the sample bottle number of the sample NV was <. Chlorinated hydrocarbons / NV 0 9 Only the results of,-dichloroethene, chloroform and dichloromethane were assessed and the performance was mainly good. There were two questionable results and no unsatisfactory result. Oxygenates / NV 0 % of the results were unsatisfactory and only one result was questionable. Aromatics / MV 0 8 Only few of the results were questionable and five result were unsatisfactory. Only informative assessment for Bz, TCBz, mpxyl, oxyl. Chlorinated hydrocarbons/ MV 0 0 9 The performance was mainly good. Only few of the results were questionable and one result was unsatisfactory. The results of tdcee were not assessed. Only informative assessment for DCEa, cdcee, TCEe, TECEe. Oxygenates / MV 0 8 Mainly good performance. % of the results were questionable and no unsatisfactory result. s p = standard deviation for pro!ciency assessment. Satisfactory results for the AV sample were surprisingly low. e method for the analyzing the AV sample were not asked from the participants. e sample AV should have been measured as the calibration standards. According to the stability test the concentration of carbontetrachloride and dichloromethane in the sample MV could decrease, if the temperature increased to 0 C during the transport. Ten laboratories reported the temperature of the samples between " C and!ve of these laboratories had measured carbontetrachloride and dichloromethane. e performance of these laboratories has been studied below: Analyte z scores Conclusions CCl Four satisfactory results, one z score was. Duplicate results were.9 and.8, which indicated large deviation in the measurement. DCM Four satisfactory results, one z score was -.8. According to the stability test the concentration of DCM in the sample MV could decrease, if the temperature increased during the transport.

For the priority substances of the European Union surface water directive 008//EC the amount of the accepted z-values of the participants results for NV sample were from % to 0 % (Tables and ). Environmental quality standard values (EQS) for the surface waters in the directive are higher than the assigned value in this pro!ciency test for, DCM and CCl, and lower than the assigned value for CHCl, TCBz, DCEa, Bz, TCEe and TECEe. e limit of quantitation for the priority substances should be / of the EQS values. Table. e environmental quality standard (EQS) values for the compounds in surface waters. Compound EQS EQS Compound µg/l µg/l Benzene Chloroform, Trichlorobenzenes 0, Carbontetrachloride Tetrachloroethene,-Dichloroethane Trichloroethene Dichloromethane 0 SUMMARY Pro#est SYKE carried out the pro!ciency test for the determinations of volatile organic compounds (VOC) in water and soil samples in October 0. In total, laboratories participated in the pro!ciency test, from which one laboratory sent two results. One arti!cial sample (AV), one river water sample (NV), and one soil sample (MV) were delivered to the laboratories. e calculated concentrations (samples AV and NV) or the means of the results reported by the participants (MV) were used as the assigned values for the measurements. e uncertainties of the calculated assigned values were less than %. Respectively the uncertainties of the consensus assigned values (the mean) were from. % to %. In total, % of the total results in this PT were satisfactory when the deviations of 0 % from the assigned values were accepted. YHTEENVETO Pro#est SYKE järjesti pätevyyskokeen haihtuvien orgaanisten yhdisteiden määrityksistä vesi- ja maanäytteistä lokakuussa 0. Vesi- ja maanäytteen lisäksi osallistujalle toimitettiin synteettinen näyte. Pätevyyskokeeseen osallistui yhteensä laboratoriota, joista yksi toimitti kahdet tulokset. Synteettisessä näytteessä AV ja vesinäytteessä NV mittaussuureen vertailuarvona käytettiin laskennallista pitoisuutta ja maanäytteessä MV osallistujien raportoimien tulosten keskiarvoa. VOCyhdisteiden laskennallisten vertailuarvojen laajennetut epävarmuudet olivat "8 %. Yhdisteestä ja raportoitujen tulosten hajonnasta riippuen maanäytteessä vertailuarvon laajennetut epävarmuudet olivat 8 % (liite ). Synteettisten näytteiden tuloksissa sallittiin %:n poikkeama vertailuarvosta, jolloin aromaattisten yhdisteiden tuloksista hyväksyttäviä oli %, öljyn lisäaineiden tuloksista (ETBE, MTBE ja TAME) % ja kloorattujen hiilivetyjen tuloksista %. Vuoden 0 vastaavassa vertailussa hyväksyttäviä tuloksia oli enemmän. Silloin aromaattisten hiilivetyjen tuloksista oli hyväksyttäviä, öljyn lisäaineiden tuloksista % ja kloorattujen hiilivetyjen tuloksista % [8].

Vesinäytteiden tuloksista arvioitiin ainoastaan dikloorimetaani-, kloroformi-,-dikloorietaani-, ETBE-, MTBE- ja TAME-tulokset. Tuloksissa sallittiin 0 %:n poikkeama vertailuarvosta, jolloin hyväksyttäviä tuloksia oli 8 %. Maanäytteen tulosten sallittiin poiketa vertailuarvosta 0&0 %, jolloin aromaattisten hiilivetyjen tuloksista oli hyväksyttäviä 8 %, öljyn lisäaineiden tuloksista 8 % ja sekä että kloorattujen hiilivetyjen tuloksia 9 %. Vuoden 0 vastaavassa vertailussa sekä aromaattisten yhdisteiden tuloksista oli hyväksyttäviä 88 %, öljyn lisäaineiden tuloksista 0 % sekä kloorattujen hiilivetyjen 8 % [8]. Tässä pätevyyskokeessa koko aineistossa hyväksyttäviä tuloksia oli yhteensä %. Osallistujista % käytti määrityksissä akkreditoituja menetelmiä. Heidän tuloksistaan oli hyväksyttäviä %. REFERENCES ISO/IEC 0, 0. Conformity assessment General requirements for pro ciency testing. ISO 8, 00. Statistical methods for use in pro ciency testing by interlaboratory comparisons. "ompson. M., Ellison. S.L. R., Wood. R., 00. "e International Harmonized Protocol for the Pro ciency Testing of Analytical Chemistry laboratories (IUPAC). International Union of Pure and Applied Chemistry. Analytical Applied and Clinical Chemistry Division. Interdivisional Working Party for Harmonization of Quality Assurance Schemes for Analytical Laboratories. ISO 0:99, Water quality Determination of highly volatile halogenated hydrocarbons Gas chromatographic methods. ISO -:99, Water quality - Determination of benzene and some derivatives - Part : Head-space gas chromatographic method ISO 80:00, Water quality Gas-chromatographic determination of number of monocyclic aromatic hydrocarbons, naphthalene and several chlorinated compounds using purge and trap and thermal desorption. ISO :00, Soil quality Gas chromatographic quantitative determination of volatile aromatic and halogenated hydrocarbons and selected ethers Static headspace method. 8 Korhonen-Ylönen, K., Nuutinen, J., Leivuori, M., and Ilmakunnas, M., 0, Pro ciency Test SYKE 8a / 0 Volatile organic compounds in water and soil. Reports of Finnish Environment Institute / 0. IBSN 98-9--8-- (pdf). www.environment. / publications.

APPENDIX PARTICIPANTS ALS Czech Republic s.r.o., Prague, Czech Republic Ekokem Oy Ab, Riihimäki, Finland Eurofins Environment Testing Norway AS, Moss, Norway Eurofins Environment Sweden AB, Lidköping, Sweden Eurofins Scientific Finland Oy, Tampere, Finland Finnish Environment Institute, SYKE, Helsinki, Finland Højvang Miljølaboratorium A/S, Dianalund, Denmark ISD DUNAFER Co. Ltd. Directorate of Material Testing and Calibration Laboratories, Hungary IVL Svenska Miljöinstitutet Ab, Göteborg, Sweden Kokemäenjoen vesistön vesiensuojelu ry, Hämeenlinna, Finland MetropoliLab Oy, Helsinki, Finland NabLabs Ympäristöanalytiikka Oy, Oulu, Finland Novalab Oy, Karkkila, Finland Ramboll Finland Oy, Lahti, Finland SGS Inspection Services Oy, Kotka, Finland

PREPARATION OF THE SAMPLES APPENDIX / Each individual stock solution was prepared by weighting methanol ( ml) and from 0. to 0. g of the pure compound into a vial. The concentrations of the analytes in the individual stock solutions have been presented in the table. The ARMixtue was prepared by weighing from 0. to.0 ml of the individual stock solutions (compounds shown in the table ) into a vial. The final volume of the ARMixture was. ml. The CLMixture was prepared by weighing from 0. to.0 ml of the individual stock solution (compounds shown in the table ) into a vial. The final volume of the CLMixture was. ml. The OXMixture was prepared by weighing from. to.8 ml of the individual stock solution (compounds shown in the table ) into a vial. The final volume of the OXMixture was. ml. Table. Concentrations of the stock solutions and the mixtures. Compound Stock solution, ARMixture producer, purity mg/ml mg/ml Benzene Fluka, 99.9 %. 0. Ethylbenzene Fluka, 99.9%.99 0.9 Toluene Fluka, 99.9 %.. o-xylene Fluka, 99. %.. p-xylene Fluka, 99. %..0,,-Trichlorobenzene Fluka, 99. % CLMixture mg/ml 8.. Carbontetrachloride Ehrenstorfer, 99.9 %.0.0 Chloroform Fluka, 99.90% 0..,-Dichloroethane Ehrenstorfer, 99. %..90 cis-,-dichloroethene Fluka, 9 %.9 9. trans-,- Dichloroethene Fluka, 98.0 % Dichloromethane Aldrich, 99.9 Trichloroethene Riedel-de Haën, 99.9 %.98..9. Tetrachloroethene Fluka, 99.0 %..88 OXMixture mg/ml 9.0 9.9 ETBE Fluka, 9.0 %.. MTBE Sigma Aldrich, 99.8 %.. TAME Aldrich, 9.0 %.9.0

APPENDIX / PREPARATION OF THE SAMPLES 8 The addition solution for the sample AV was prepared by weighting ml of methanol,. ml of the ARMixture, 0. ml of the CLMixture and.0 ml of the OXMixture into a vial. The sample AV was prepared by diluting ml of the addition solution with 0 ml methanol (Table ). The addition solution for the sample NV was prepared by weighting ml of the ARMixture, ml of the CLMixture and ml of the OXMixture into a vial. Addition solution was diluted three times with methanol in ratio : (v/v) and the final methanol solution (90 ml) was diluted with 0 litre of surface water to produce the sample NV (Table ). The addition solution was prepared by weighting 0 ml of methanol, ml of the ARMixture, ml of the CLMixture and ml of the OXMixture. The sample MV was made by mixing 0 g of dry soil, ml of water, ml of the addition solution and 0 ml of methanol (Table ). Table. Concentrations of the addition solutions (,, ) and the samples (AV, NV, MV). Measurement Addition solution mg/ml Addition solution mg/ml Addition solution mg/ml AV µg/ml NV µg/l MV mg/kg Benzene 0.080 0.9 0.0 0.9.8. Ethylbenzene 0. 0.8 0.0.0.9. Toluene 0.0 0.989 0.0.0.80.0 o-xylene 0. 0. 0.0...8 p-xylene 0..9 0...8.,,- Trichlorobenzene 0.098 0.9 0.08 0.9..0 0.08 0. 0.08 0. 8.0.9 Chloroform 0..00 0.0.0.9. Carbontetrachloride,- Dichloroethane cis-,- Dichloroethene trans-,- Dichloroethene 0.9. 0....9 0..8 0.9.. 8.9 0.099 0.9 0.08 0.98.9. Dichloromethane 0.09 0.90 0.0 0.9 9.8. Trichloroethene 0.9.08 0..8..9 Tetrachloroethene.8.9 0.. 0.8.8 ETBE 0. 0. 0.0... MTBE 0..80 0.. 9..8 TAME 0.8 0.9 0.08.8.8.

TESTING OF HOMOGENEITY 9 APPENDIX / The homogeneities of the samples NV and MV were tested by analysing six sub samples. Measurement/ sample NV Concentration (µg l - ) s h % s p % s h s a s a /s h s a /s h <0.? s bb s bb c s bb <c? Benzene.. - 0. 0.0 0.0 YES 0.8 0.0 0.0 YES Ethylbenzene.. - 0. 0.0 0.0 YES 0. 0.0 0.0 YES Toluene 9. -. 0.0 0.0 YES 0. 0. 0.9 YES o-xylene. - 0.0 0.0 0.0 YES 0.8 0. 0. YES m+p-xylene. 8. -. 0.0 0.0 YES.08.. YES,,-Trichlorobenzene 8.0 0-8.0 0.8 0.0 YES 0. 0. 0. YES Carbontetrachloride. -.9 0.09 0.0 YES.9.8.9 YES Chloroform. 0.9 0. 0. YES 0. 0.0 0. YES,-Dichloroethane.0. 0.0 0.9 0.8 YES 0. 0.0 0. YES cis-,-dichloroethene.8. -. 0. 0.0 YES.9.8.9 YES trans-,-dichloroethene 8. -.8 0.8 0.0 YES 0.80 0. 0.9 YES Dichloromethane 9. 0. 0. 0. YES 0. 0.0 0.0 YES Trichloroethene.. -. 0. 0.0 YES..0. YES Tetrachloroethene.8 8 -. 0.0 0.0 YES.9.. YES ETBE.98 0. 0.0 0. YES 0. 0.0 0.0 YES MTBE 9. 0.9 0. 0. YES 0.0 0. 0. YES TAME 8. 0.8 0.0 0. YES 0. 0.0 0.08 YES Measurement/ sample MV Concentration (µg kg - ) s h % s p % s h s a s a /s h s a /s h <0.? s bb s bb c s bb <c? Benzene 0.90 8 0. 0.0 0. YES 0.09 0.008 0.008 YES Ethylbenzene.9 0. 0.0 0. YES 0.09 0.008 0.0 YES Toluene. 0. 0. 0.0 YES 0. 0. 0. YES o-xylene.9 9 0. 0.0 0. YES 0.0 0.00 0.00 YES m+p-xylene. 0. 0. 0. YES 0. 0.8 0. YES,,-Trichlorobenzene. 0. 0.0 0. YES 0.0 0.00 0.008 YES Carbontetrachloride. 0. 0.0 0. YES 0.0 0.00 0.0 YES Chloroform. 0. 0.09 0.0 YES 0. 0.0 0.0 YES,-Dichloroethane.0 0. 0. 0. YES 0. 0.0 0.0 YES cis-,-dichloroethene 8..0 0.0 0.9 YES 0. 0. 0. YES trans-,-dichloroethene.8-0. 0. 0. YES 0.8 0.8 0.08 YES Dichloromethane.. 0. 0. 0. YES 0. 0.0 0.0 YES Trichloroethene.. 0. 0. 0. YES.9.9 0.99 YES Tetrachloroethene.8 0.. 0. YES...9 YES ETBE. 0. 0.0 0. YES 0.0 0.00 0.00 YES MTBE.8. 0.8 0. 0. YES 0.9 0.0 0.9 YES TAME. 0. 0.08 0. YES 0.0 0.00 0.0 YES Criteria for homogeinity: s a /s h <0. and s bb <c, where s p % = standard deviation for proficiency assessment s h % = standard deviation for testing of homogeneity s a = analytical deviation, standard deviation of the results within sub samples s bb = between-sample deviation, standard deviation of the results between sub samples c = F x s all + F x s a, where s all = (0. x s p ) F =. and F =.9, when the number of sub samples is

APPENDIX / Although the homogenous criteria was reached for most measurements in the water sample NV, the concentration of most VOC compounds decreased during the sample preparation after the sample bottle number. However, no remarkable decrease in the concentration of, -dichloroethane, chloroform, dichloromethane and oxygenates was observed. Homogenous criteria was reached for most measurements in the soil sample MV. However, the standard deviation for testing of homogeneity (s h ) was high for the measurement of trans-,-dichloroethene. So, the results of trans-,-dichloroethene could not be assessed. Conclusion: The water sample NV could be regarded homogenous only for the analysis of, - dichloroethane, chloroform, dichloromethane and oxygenates (ETBE; MTBE; TAME). The soil sample MV could be regarded as homogenous except for the analysis of trans-,-dichloroethene. The results of trans-,-dichloroethene were not evaluated. 0

APPENDIX / TESTING OF STABILITY The samples were distributed October 0 and they were asked to analyse before 9 October 0. Stability was tested from the samples AV, NN and MV. The results have been shown in tables, and. Criterio for stability: D < 0. s p, where D = the difference of results measured from the samples stored at the temperatures and 0 C s p = standard deviation for proficiency assessment Table. Stability of the sample AV / concentration µg/ml. Analyte Assigned value Oct 9 Oct C 9 Oct 0 C D 0. s p Test pasted? Benzene 0.9 0.9 0.9 0.8-0.0 0.0 yes Ethylbenzene.0.09.0. 0.0 0.0 yes Toluene.0..99.99 0.0 0.0 yes o-xylene..8.88.8-0.00 0.0 yes m/p-xylene...9.00 0.0 0. yes,,- Trichlorobenzene 0.9 0.9.08.0-0.00 0.0 yes 0. 0.8 0.8 0.8-0.0 0.009 yes Chloroform.0.8 0.80 0.88-0.00 0.0 yes Carbontetrachloride,- Dichloroethane cis-,- Dichloroethene trans-,- Dichloroethene...0. -0,0 0.0 no )..8..9-0.0 0.08 yes 0.98 0,9 0.8 0.880 0.0 0.0 yes Dichloromethane 0.9 0.9 0.8 0.80-0.0 0.0 no ) Trichloroethene.88 8. 8.0 8.0 0.09 0.8 yes Tetrachloroethene..9.0 8. 0. 0. no ETBE.. 0.999 0.9-0.0 0.0 no ) MTBE....99-0. 0. no ) TAME.8.0.0. -0.08 0.0 no ) ) However the difference between the difference temperatures was within the daily variation of the method and within the variation between the subsamples. Thus, the stability was concluded to be satisfactory. Conclusion: The stability of the samples during the transport was mainly good. According to the test the concentration of tetrachloroethene could increase, if the temperature increased to 0 C during the transport. This was taken into account in performance evaluation and the results of tetrachloroethene were not assessed.

APPENDIX / TESTING OF STABILITY Table. Stability of the sample NV / concentration µg/l. Analyte Assigned value Oct 9 Oct C 9 Oct 0 C D 0. s p Test pasted? Benzene.8.,.9-0. 0. Yes Ethylbenzene.9...0-0. 0.9 No Toluene,80 9.9 8.99 8.0-0.9 0. No o-xylene...90.0-0, 0. No m/p-xylene....8 -.0 0. No. 8.9 8. 8. -0.9 0.9 No 8.0.99.. -0.9 0.0 No Chloroform.9..00 9.0-0.0 0. Yes,,- Trichlorobenzene Carbontetrachloride,- Dichloroethane cis-,- Dichloroethene trans-,- Dichloroethene..0..9-0.0.00 Yes...8.0 -..0 Yes.9 8...9-0.8 0. Yes Dichloromethane 9.8 8.8.0.0-0.9 0. Yes Trichloroethene 9..9.9. -..08 No Tetrachloroethene 0...08.9 -.8. No ETBE.... -0. 0. Yes MTBE 9. 0...0-0.9 0.9 Yes TAME.8 8.9..8-0. 0. Yes Conclusion: Only the results of,-dichloroethane, chloroform, dichloromethane and oxygenates (ETBE, MTBE, TAME) were evaluated. The stability of these compounds was good.

APPENDIX / TESTING OF STABILITY Table. Stability of the sample MV / concentration mg/kg. Analyte Assigned value Oct 9 Oct C 9 Oct 0 C D 0. s p Test pasted? Benzene.00 0.9 0.9 0.9 0.0 0.0 Yes Ethylbenzene.8..8. -0.0 0.0 Yes Toluene..8.. -0.8 0.0 Yes o-xylene.8..0. -0.0 0. Yes m/p-xylene.8..08.9-0. 0. Yes,,- Trichlorobenzene Carbontetrachloride...9. 0.0 0. Yes..0.. -0.9 0.0 No Chloroform..9..98 0.0 0. Yes ),- Dichloroethane cis-,- Dichloroethene trans-,- Dichloroethene.... -0.8 0. Yes.. 8.09.0-0.0 0. Yes )...0. -0.09 0. Yes ) Dichloromethane.... -0. 0. No Trichloroethene.80..9.8-0.8 0.88 Yes Tetrachloroethene 9.9.8.. -.8. Yes ETBE.8.8.8.8-0.0 0.08 Yes MTBE.... -0. 0. Yes TAME...09.0-0.0 0. Yes ) D = the difference of results measured from the samples stored at the temperatures ( Oct) and 0 C Conclusion: According to the test concentration of carbontetrachloride and dichloromethane could decease, if the temperature increaced to 0 C during the transport. This was taken into consideration in performance evaluation.

APPENDIX FEEDBACK FROM THE PROFICIENCY TEST Feedback sent by the participants Lab Comment on the samples Action/Proftest The weight of the sample AV was decreased during the A new sample was sent. transport more than 0. %. The sample AV does not represent the real samples. The purpose of the sample AV was to check calibration. Usefulness of synthetic samples will be discussed in the Proftest steering group.,, The weight of the sample MV was decrease during the transport more than 0. %. A new sample was sent. All On the electrical result sheet was guided to add the method code, although no method codes were given. On the web page was added the information to leave method column empty in the result reporting step. The provider added the method codes in the data handling step. Lab Comment on the results Action/Proftest The laboratory reported the results of the sample AV in the unit µg/l instead of µg/ml. The laboratory had reported the incorrect TeCEe results for the sample MV. The correct results were. and. mg/kg. For calculation of the results in the soil sample MV was used: 0 g soil and ml of extraction solution (water + methanol). The results were handled as outliers in the statistical data treatment. If the results had been reported as the correct units, most of them should have been satisfactory. The results were handled as outliers in the statistical data treatment. If the results had been reported correctly, they should have been satisfactory. Calculation has been correctly. Feedback to the participants Lab Comments from the provider The participant reported all results as accredited, but without any information about the used methods. The method code could not be added by the provider.

ASSIGNED VALUES AND THEIR UNCERTAINTIES Analyte Abbreviation Benzene Bz Ethylbenzene ETBz Toluene TOL o-xylene oxyl m/p-xylene mpxyl,,-trichlorobenzene TCBz Carbontetrachloride CCl Chloroform CHCl,-Dichloroethane DCEa cis-,-dichloroethene cdcee trans-,-dichloroethene tdcee Dichloromethane DCM Trichloroethene TCEe Tetrachloroethene TECEe ETBE MTBE TAME APPENDIX Sample Assigned Evaluation of Uncertainty Unit value the assigned value (U = u c ), % AV 0.9 µg/ml Calculated < MV.00 mg/kg Mean AV.0 µg/ml Calculated < MV.8 mg/kg Mean AV.0 µg/ml Calculated < MV. mg/kg Mean 9. AV. µg/ml Calculated < MV.8 mg/kg Mean AV. µg/ml Calculated < MV.8 mg/kg Mean AV 0.9 µg/ml Calculated < MV. mg/kg Mean AV 0. µg/ml Calculated < MV. mg/kg Mean AV.0 µg/ml Calculated < NV.9- µg/l Calculated < MV. mg/kg Mean AV. µg/ml Calculated < NV. µg/l Calculated < MV. mg/kg Mean AV. µg/ml Calculated < MV. mg/kg Mean AV 0.98 µg/ml Calculated < MV. mg/kg Mean AV 0.9 µg/ml Calculated < NV 9.8 µg/l Calculated < MV. mg/kg Mean 8 AV.88 µg/ml Calculated < MV.8 mg/kg Mean 9 AV. µg/ml Calculated < MV 9.9 mg/kg Mean AV. µg/ml Calculated < NV. µg/l Calculated < MV.8 mg/kg Mean 8 AV. µg/ml Calculated < NV 9. µg/l Calculated < MV. mg/kg Mean AV.8 µg/ml Calculated < NV.8 µg/l Calculated < MV. mg/kg Mean

APPENDIX TERMS IN THE RESULT TABLES Results of each participants Sample the code of the sample z-graphics z score - the graphical presentation z value calculated as follows: z = (x i - X)/s p, where x i = the result of the individual laboratory X = the reference value (the assigned value) s p = the target value of the standard deviation for proficiency assessment Outl test OK yes - the result passed the outlier test H = Hampel test (test for the mean value) C = Cochran test (replicate test) Assigned value the reference value * Targ SD % the target value of total standard deviation for proficiency assessment (s p ) at the 9 % confidence level, equal s p Lab s result the result reported by the participant (the mean value of the replicates) Md. Median Mean Mean SD Standard deviation SD% Standard deviation, % Passed The results passed the outlier test Outl. failed The results not passed the outlier test Missing i.e. < DL Num of labs the total number of the participants Summary on the z scores S satisfactory ( - z ) Q questionable ( < z < ), positive error, the result deviates more than s p from the assigned value q questionable ( - > z< -), negative error, the result deviates more than s p from the assigned value U unsatisfactory (z ), positive error, the result deviates more than s p from the assigned value u unsatisfactory (z -), negative error, the result deviates more than s p from the assigned value Robust analysis The data items are sorted in increasing order: x, x,, x i,,x p. Initial values for x * and s * are calculated as follows: x* = median of x i (i =,,...,p) s* =,8 median of x i x* (i =,,...,p) The mean x* and s* are updated as follows: Calculate =. s*. A new value is then calculated for each result x i (i =, p): { x* -, if x i < x* - x i * = { x* +, if x i > x* + { x i otherwise The new values of x * and s * are calculated as follows: * x xi / p * s *. p i ( x * i x * ) /( p ) Ref: Statistical methods for use in proficiency testing by inter laboratory comparisons, Annex C [].

LIITE APPENDIX 8 / LIITE 8. RESULTS OF EACH PARTICIPANT APPENDIX 8. Analyte Unit Sample z-graphics - - - 0 + + + Z- value Outl Assigned test OK value * Targ SD% Lab's result Md. Mean SD SD% Passed Outl. failed Missing Num of labs TCBz µg/ml AV -,9 yes 0,9 0,8 0,9 0,9 0,9, 9 0-0, yes, 0,,8, 0,0, 0 0 yes,, 8, 8,,9,9 0 0 DCEa µg/ml AV -,09 yes,,0,, 0,98, 9 0-0, yes, 0,9,, 0,89, 0 0-0, yes, 0,,,,, Bz µg/ml AV -,09 yes 0,9 0, 0,8 0,9 0,, 0 0, yes 0,0 0,990 0,99 0,8 8, 0 yes,8,,9,99 0,,9 cdcee µg/ml AV -,8 yes,,8,, 0,90, 8 0 0,0 yes, 0,,,,, 9 0 0 9 yes, 9,,,8, 9,8 0 0 CCl µg/ml AV -, yes 0, 0, 0, 0,8 0,0,9 0,09 yes, 0,,, 0,9 9, yes 8,0,9,,88,8,8 CHCl µg/ml AV -0,880 yes,0 0,99,0,0 0,08 0, 9 0,9 yes, 0,,, 0,, 8 -,0 yes,9 0 9,0,,,00 8, DCM µg/ml AV -,9 yes 0,9 0, 0,8 0,88 0,89, 9 0 0,9 yes, 0,,,09 0,8, 8 -,9 yes 9,8 0,99,,98,,8 ETBE µg/ml AV,88 yes,,,9,98 0,0 8, 0 8 0, yes,8 0,,, 0,, 0 0-0,8 yes, 0,,,8 0,,0 0 8 ETBz µg/ml AV -,98 yes,0 0,9,0 0,09 0, 0 0,99 yes,8 0,9,, 0,09, 0 yes,9,,8, 0,8, 0 mpxyl µg/ml AV -0, yes,,,, 0,, 0 0,9 yes,8 0,,9,,0 9,0 0 yes,,,9,, 0,0 0 0 MTBE µg/ml AV 0,9 yes,,,8,,, 0 -,8 yes, 0 8,,,,8, 0 0-0,8 yes 9, 0,, 8,,0 9, 0 oxyl µg/ml AV -0,8 yes,,,,9 0, 8, 0 0,09 yes,8 0,9,, 0, 9, 0 yes,,8,,,8 8, 0 tdcee µg/ml AV -,8 yes 0,98 0,8 0,8 0,89 0,8, 0 yes,,9,, 0,9, 0 0 yes,9,9,8 8,98, 8, 0 TAME µg/ml AV, yes,8,,,80 0,, 9 0 0, yes, 0,,, 0,88, 0 0-0,80 yes,8 0,0,9,9,99,8 8 TCEe µg/ml AV -0, yes,88,,,,, 0 0, yes,8 0,,9,, 0 0 yes 9, 8,9 0,,0,9 0 TECEe µg/ml AV yes,,,0,9,9, 0-0,08 yes 9,9 0 9, 0, 9,8,,8 0 0 yes 0,8,, 8,9,, 0 0 TOL µg/ml AV -0,8 yes,0,8,0,00 0,8 8,9 0 0, yes, 0,,,8 0,, 0 0 yes,8,98 8,9 9,9,8, 0 0 Outlier test failed: C - Cohcran, G - Grubbs(-outlier algorithm), G - Grubbs(-outliers algorithm), H - Hampel, M - manual SYKE - Interlaboratory comparison test 8/0

LIITE 8 / 8 APPENDIX Analyte Unit Sample z-graphics - - - 0 + + + Z- value Outl Assigned test OK value * Targ SD% Lab's result Md. Mean SD SD% Passed Outl. failed Missing Num of labs Bz µg/ml AV 0, yes 0,9 0,80 0,8 0,9 0,, 0 yes,8,8,9,99 0,,9 CCl µg/ml AV -0, yes 0, 0,0 0, 0,8 0,0,9 yes 8,0,,,88,8,8 CHCl µg/ml AV -0,9 yes,0 0,98,0,0 0,08 0, 9-0, yes,9 0,,,,00 8, ETBE µg/ml AV 0,99 yes,,,9,98 0,0 8, 0 8 -, yes, 0,,,8 0,,0 0 8 ETBz µg/ml AV -, yes,0 0,8,0 0,09 0, 0 yes,9,,8, 0,8, 0 mpxyl µg/ml AV -,99 yes,,,, 0,, 0 yes,,,9,, 0,0 0 0 MTBE µg/ml AV 0,9 yes,,,8,,, 0-0, yes 9, 0 8,, 8,,0 9, 0 oxyl µg/ml AV -,8 yes,,,,9 0, 8, 0 yes,,,,,8 8, 0 TCEe µg/ml AV,08 yes,88 8,0,,,, 0 yes 9,, 8,9 0,,0,9 0 TECEe µg/ml AV yes,,0,0,9,9, 0 yes 0,8, 9, 8,9,, 0 0 TOL µg/ml AV -0,0 yes,0,00,0,00 0,8 8,9 0 yes,8,9 8,9 9,9,8, 0 0 TCBz µg/ml AV,0 H 0,9 0,9 0,9 0,9, 9 0, yes, 0,9,8, 0,0, 0 0 yes, 9,9 8, 8,,9,9 0 0 DCEa µg/ml AV 0,0 H,,, 0,98, 9 0 0, yes, 0,,, 0,89, 0 0-0,0 yes, 0,,,,, Bz µg/ml AV 00,0 H 0,9 8 0,8 0,9 0,, 0 0,9 yes 0, 0,990 0,99 0,8 8, 0 yes,8,,9,99 0,,9 cdcee µg/ml AV 90,0 H, 0,, 0,90, 8 0 0, yes, 0 8,0,,,, 9 0 0 9 yes,,,,8, 9,8 0 0 CCl µg/ml AV 0,0 H 0, 9, 0, 0,8 0,0,9 0,09 yes, 0,,, 0,9 9, yes 8,0,,,88,8,8 CHCl µg/ml AV 00,0 H,0 0,0,0 0,08 0, 9 0,8 yes, 0,,, 0,, 8-0, yes,9 0,,,,00 8, DCM µg/ml AV 0,0 H 0,9 8, 0,8 0,88 0,89, 9 0,008 yes, 0,98,,09 0,8, 8 -, yes 9,8 0 8,,,98,,8 ETBE µg/ml AV,0 H, 00,9,98 0,0 8, 0 8 0, yes,8 0,,, 0,, 0 0-0,09 yes, 0,,,8 0,,0 0 8 ETBz µg/ml AV 00,0 H,0 0,0 0,09 0, 0, yes,8 0,,, 0,09, 0 yes,9,,8, 0,8, 0 mpxyl µg/ml AV 0,0 H, 0,, 0,, 0,8 yes,8 0,80,9,,0 9,0 0 yes,,,9,, 0,0 0 0 MTBE µg/ml AV 0,0 H, 90,8,,, 0 0,00 yes, 0,,,,8, 0 0 0,0 yes 9, 0 9,9, 8,,0 9, 0 oxyl µg/ml AV 0,0 H, 98,,9 0, 8, 0,8 yes,8 0,,, 0, 9, 0 yes,,8,,,8 8, 0 tdcee µg/ml AV 800,0 H 0,98 9, 0,8 0,89 0,8, 0 yes,,8,, 0,9, 0 0 yes,9 8,,8 8,98, 8, 0 TAME µg/ml AV 090,0 H,8 9,,80 0,, 9 0 0, yes, 0,,, 0,88, 0 0 0,09 yes,8 0,89,9,9,99,8 8 TCEe µg/ml AV 88,00 H,88 0,,,, 0 -,8 yes,8 0 9,,9,, 0 0 Outlier test failed: C - Cohcran, G - Grubbs(-outlier algorithm), G - Grubbs(-outliers algorithm), H - Hampel, M - manual SYKE - Interlaboratory comparison test 8/0

9 LIITE APPENDIX 8 / Analyte Unit Sample z-graphics - - - 0 + + + Z- value Outl Assigned test OK value * Targ SD% Lab's result Md. Mean SD SD% Passed Outl. failed Missing Num of labs yes 9,, 8,9 0,,0,9 0 TECEe µg/ml AV H, 0,0,9,9, 0 0, yes 9,9 0, 0, 9,8,,8 0 0 yes 0,8 9, 8,9,, 0 0 TOL µg/ml AV 0,0 H,0,0,00 0,8 8,9 0,0 yes, 0,9,,8 0,, 0 0 yes,8, 8,9 9,9,8, 0 0 TCBz µg/ml AV, yes 0,9, 0,9 0,9 0,9, 9 0, yes, 0,8,8, 0,0, 0 0 yes,,0 8, 8,,9,9 0 0 DCEa µg/ml AV 0,0 yes,,,, 0,98, 9 0 0, yes, 0,,, 0,89, 0 0 0, yes, 0,,,,, Bz µg/ml AV -0,9 yes 0,9 0, 0,8 0,9 0,, 0 0, yes 0,0 0,990 0,99 0,8 8, 0 yes,8,,9,99 0,,9 cdcee µg/ml AV,8 yes,,98,, 0,90, 8 0-0,0 yes, 0,,,,, 9 0 0 9 yes, 8,98,,8, 9,8 0 0 CCl µg/ml AV,99 yes 0, 0,8 0, 0,8 0,0,9-0,0 yes, 0,0,, 0,9 9, yes 8,0 8,0,,88,8,8 CHCl µg/ml AV,0 yes,0,,0,0 0,08 0, 9 0,08 yes, 0,,, 0,, 8, yes,9 0,98,,,00 8, DCM µg/ml AV 0, yes 0,9,00 0,8 0,88 0,89, 9 0-0, yes, 0,,,09 0,8, 8 0,0 yes 9,8 0,9,,98,,8 ETBz µg/ml AV 0, yes,0,,0 0,09 0, 0 0, yes,8 0,,, 0,09, 0 yes,9,,8, 0,8, 0 mpxyl µg/ml AV 0, yes,,,, 0,, 0 0, yes,8 0,,9,,0 9,0 0 yes,,8,9,, 0,0 0 0 MTBE µg/ml AV 8,98 yes, 8,9,8,,, 0,90 yes, 0,8,,,8, 0 0 8,8 H 9, 0,8, 8,,0 9, 0 oxyl µg/ml AV,0 yes,,9,,9 0, 8, 0 0, yes,8 0,9,, 0, 9, 0 yes,,,,,8 8, 0 tdcee µg/ml AV, yes 0,98,0 0,8 0,89 0,8, 0 yes,,,, 0,9, 0 0 yes,9 9,9,8 8,98, 8, 0 TCEe µg/ml AV -, yes,88,8,,,, 0-0,8 yes,8 0,,9,, 0 0 yes 9,,89 8,9 0,,0,9 0 TECEe µg/ml AV yes,,,0,9,9, 0,08 yes 9,9 0, 0, 9,8,,8 0 0 yes 0,, 9, 8,9,, 0 0 TOL µg/ml AV, yes,0,,0,00 0,8 8,9 0 0, yes, 0,,,8 0,, 0 0 yes,8, 8,9 9,9,8, 0 0 Outlier test failed: C - Cohcran, G - Grubbs(-outlier algorithm), G - Grubbs(-outliers algorithm), H - Hampel, M - manual SYKE - Interlaboratory comparison test 8/0

LIITE 8 / 0 APPENDIX Analyte Unit Sample z-graphics - - - 0 + + + Z- value Outl Assigned test OK value * Targ SD% Lab's result Md. Mean SD SD% Passed Outl. failed Missing Num of labs Bz µg/ml AV 0, yes 0,9 0,80 0,8 0,9 0,, 0 -,00 yes 0 0, 0,990 0,99 0,8 8, 0 yes,8,,9,99 0,,9 cdcee µg/ml AV,8 H,,9,, 0,90, 8 0 yes,,,,8, 9,8 0 0 CCl µg/ml AV, yes 0, 0,9 0, 0,8 0,0,9 yes 8,0,,,88,8,8 CHCl µg/ml AV,8 yes,0,0,0,0 0,08 0, 9,0 yes,9 0,8,,,00 8, DCM µg/ml AV 0,800 yes 0,9,00 0,8 0,88 0,89, 9 0 -,09 yes 9,8 0 8,,,98,,8 ETBz µg/ml AV -0,0 yes,0,08,0 0,09 0, 0 -, yes,8 0,,, 0,09, 0 yes,9,9,8, 0,8, 0 mpxyl µg/ml AV 0,8 yes,,8,, 0,, 0 -, yes,8 0,,9,,0 9,0 0 yes,,,9,, 0,0 0 0 MTBE µg/ml AV -, yes,,,8,,, 0-0, yes 9, 0 8,, 8,,0 9, 0 oxyl µg/ml AV 0,8 yes,,8,,9 0, 8, 0 -,9 yes,8 0,9,, 0, 9, 0 yes,,9,,,8 8, 0 tdcee µg/ml AV,90 yes 0,98, 0,8 0,89 0,8, 0 yes,9 8,89,8 8,98, 8, 0 TCEe µg/ml AV, yes,88 9,,,,, 0 yes 9,, 8,9 0,,0,9 0 TECEe µg/ml AV yes,,,0,9,9, 0 yes 0,8 8,9 9, 8,9,, 0 0 TOL µg/ml AV 0, yes,0,9,0,00 0,8 8,9 0 -, yes, 0,,,8 0,, 0 0 yes,,0 8,9 9,9,8, 0 0 Bz µg/ml AV -,90 H 0,9 0,099 0,8 0,9 0,, 0 -,0 yes 0 0, 0,990 0,99 0,8 8, 0 yes,8,9,9,99 0,,9 ETBz µg/ml AV -,80 yes,0 0,09,0 0,09 0, 0-0,0 yes,8 0,,, 0,09, 0 yes,9,9,8, 0,8, 0 mpxyl µg/ml AV -,80 H, 0,8,, 0,, 0-0,90 yes,8 0,9,9,,0 9,0 0 yes,,,9,, 0,0 0 0 oxyl µg/ml AV -, H, 0,,,9 0, 8, 0-0, yes,8 0,,, 0, 9, 0 yes,,,,,8 8, 0 TOL µg/ml AV -,00 H,0 0,,0,00 0,8 8,9 0 -,098 yes, 0,,,8 0,, 0 0 yes,8, 8,9 9,9,8, 0 0 Outlier test failed: C - Cohcran, G - Grubbs(-outlier algorithm), G - Grubbs(-outliers algorithm), H - Hampel, M - manual SYKE - Interlaboratory comparison test 8/0

LIITE APPENDIX 8 / Analyte Unit Sample z-graphics - - - 0 + + + Z- value Outl Assigned test OK value * Targ SD% Lab's result Md. Mean SD SD% Passed Outl. failed Missing Num of labs TCBz µg/ml AV -0,9 yes 0,9 0,9 0,9 0,9 0,9, 9 0-0,8 yes, 0,8,8, 0,0, 0 0 yes,, 8, 8,,9,9 0 0 DCEa µg/ml AV -, yes,,0,, 0,98, 9 0 -, yes, 0,8,, 0,89, 0 0 -, yes, 0 8,,,,, Bz µg/ml AV 0,8 yes 0,9 0,8 0,8 0,9 0,, 0-0, yes 0 0,9 0,990 0,99 0,8 8, 0 yes,8,0,9,99 0,,9 cdcee µg/ml AV -0,98 yes,,,, 0,90, 8 0 -, yes, 0,9,,,, 9 0 0 9 yes,,,,8, 9,8 0 0 CCl µg/ml AV -,8 yes 0, 0, 0, 0,8 0,0,9 -, H, 0 0,,, 0,9 9, yes 8,0,0,,88,8,8 CHCl µg/ml AV -0, yes,0,0,0,0 0,08 0, 9 -,9 yes, 0,8,, 0,, 8 -, yes,9 0 8,8,,,00 8, DCM µg/ml AV -,98 yes 0,9 0,8 0,8 0,88 0,89, 9 0 -, yes, 0,,,09 0,8, 8 -,909 yes 9,8 0,0,,98,,8 ETBE µg/ml AV -, yes,,08,9,98 0,0 8, 0 8 -,0 yes,8 0,9,, 0,, 0 0 -,0 yes, 0,,,8 0,,0 0 8 ETBz µg/ml AV -,80 yes,0 0,8,0 0,09 0, 0 -,8 yes,8 0 0,8,, 0,09, 0 yes,9,8,8, 0,8, 0 mpxyl µg/ml AV -,8 yes,,9,, 0,, 0 -,0 yes,8 0,,9,,0 9,0 0 yes,,8,9,, 0,0 0 0 MTBE µg/ml AV -,98 yes,,08,8,,, 0 -,0 yes, 0,,,,8, 0 0 -, yes 9, 0,, 8,,0 9, 0 oxyl µg/ml AV -,9 yes,,9,,9 0, 8, 0 -,9 yes,8 0,8,, 0, 9, 0 yes,,,,,8 8, 0 tdcee µg/ml AV -,0 yes 0,98 0, 0,8 0,89 0,8, 0 yes, 0,9,, 0,9, 0 0 yes,9,,8 8,98, 8, 0 TAME µg/ml AV -,0 yes,8,,,80 0,, 9 0 -,0 yes, 0,9,, 0,88, 0 0 -, yes,8 0,0,9,9,99,8 8 TCEe µg/ml AV -, yes,88,,,,, 0 -, yes,8 0 9,9,9,, 0 0 yes 9, 8,9 8,9 0,,0,9 0 TECEe µg/ml AV yes,,09,0,9,9, 0-0,9 yes 9,9 0, 0, 9,8,,8 0 0 yes 0,8, 9, 8,9,, 0 0 TOL µg/ml AV 0,08 yes,0,,0,00 0,8 8,9 0 0,9 yes, 0,,,8 0,, 0 0 yes,8 8,9 8,9 9,9,8, 0 0 Outlier test failed: C - Cohcran, G - Grubbs(-outlier algorithm), G - Grubbs(-outliers algorithm), H - Hampel, M - manual SYKE - Interlaboratory comparison test 8/0

LIITE 8 / APPENDIX Analyte Unit Sample z-graphics - - - 0 + + + Z- value Outl Assigned test OK value * Targ SD% Lab's result Md. Mean SD SD% Passed Outl. failed Missing Num of labs 8 TCBz µg/ml AV 0,8 yes 0,9,0 0,9 0,9 0,9, 9 0 0,0 yes, 0,,8, 0,0, 0 0 yes, 8, 8, 8,,9,9 0 0 DCEa µg/ml AV -0,0 yes,,,, 0,98, 9 0 0, yes, 0,,, 0,89, 0 0-0,89 yes, 0,,,,, Bz µg/ml AV 0,0 yes 0,9 0,9 0,8 0,9 0,, 0-0, yes 0 0,9 0,990 0,99 0,8 8, 0 yes,8,,9,99 0,,9 cdcee µg/ml AV -0,0 yes,,,, 0,90, 8 0 0,0 yes, 0 8,,,,, 9 0 0 9 yes,,,,8, 9,8 0 0 CCl µg/ml AV 0,9 yes 0, 0,80 0, 0,8 0,0,9-0,8 yes, 0,,, 0,9 9, yes 8,0,9,,88,8,8 CHCl µg/ml AV -,80 yes,0 0,89,0,0 0,08 0, 9-0,090 yes, 0,,, 0,, 8-0,80 yes,9 0 9,0,,,00 8, DCM µg/ml AV -, yes 0,9 0,8 0,8 0,88 0,89, 9 0-0, yes, 0,,,09 0,8, 8 -,0 yes 9,8 0,8,,98,,8 ETBE µg/ml AV -,0 yes, 0,999,9,98 0,0 8, 0 8 -,8 yes,8 0,8,, 0,, 0 0 -,8 yes, 0,,,8 0,,0 0 8 ETBz µg/ml AV 0, yes,0,,0 0,09 0, 0 0,8 yes,8 0,,, 0,09, 0 yes,9,9,8, 0,8, 0 mpxyl µg/ml AV -, yes,,98,, 0,, 0-0, yes,8 0,,9,,0 9,0 0 yes,,,9,, 0,0 0 0 MTBE µg/ml AV 0,000 yes,,,8,,, 0-0,8 yes, 0,,,,8, 0 0-0,8 yes 9, 0,, 8,,0 9, 0 oxyl µg/ml AV 0, yes,,9,,9 0, 8, 0 0,9 yes,8 0,8,, 0, 9, 0 yes,,09,,,8 8, 0 tdcee µg/ml AV -,9 yes 0,98 0,8 0,8 0,89 0,8, 0 yes,,0,, 0,9, 0 0 yes,9,8,8 8,98, 8, 0 TAME µg/ml AV -0,88 yes,8,,,80 0,, 9 0 -, yes, 0,,, 0,88, 0 0 0,99 yes,8 0,0,9,9,99,8 8 TCEe µg/ml AV 0,9 yes,88,99,,,, 0 0,89 yes,8 0,9,, 0 0 yes 9,, 8,9 0,,0,9 0 TECEe µg/ml AV yes,,,0,9,9, 0,8 yes 9,9 0, 0, 9,8,,8 0 0 yes 0,8, 9, 8,9,, 0 0 TOL µg/ml AV -0, yes,0,98,0,00 0,8 8,9 0 0,8 yes, 0,,,8 0,, 0 0 yes,8 8,9 8,9 9,9,8, 0 0 9 Bz -0,00 yes 0 0,99 0,990 0,99 0,8 8, 0 ETBz -0,8 yes,8 0,,, 0,09, 0 mpxyl -0,00 yes,8 0,,9,,0 9,0 0 oxyl -0, yes,8 0,,, 0, 9, 0 TOL -0,80 yes, 0,8,,8 0,, 0 0 Outlier test failed: C - Cohcran, G - Grubbs(-outlier algorithm), G - Grubbs(-outliers algorithm), H - Hampel, M - manual SYKE - Interlaboratory comparison test 8/0