Proficiency Test SYKE 11/2011

Transkriptio

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

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

4 REPORTS OF FINNISH ENVIRONMENT INSTITUTE 0 Finnish Environment Institute SYKE The proficiency test provider: Proftest SYKE, Finnish Environment Institute (SYKE), Centre Hakuninmaantie, 00 Helsinki phone + 0, fax + Publication is available only in the internet : ISBN (PDF) ISSN - (online)

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

6 ALKUSANAT Suomen ympäristökeskus (SYKE) on toiminut ympäristöalan kansallisena vertailulaboratoriona vuodesta 00 lähtien. Toiminta perustuu ympäristöministeriön määräykseen, mikä on annettu ympäristönsuojelulain (/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 Proftest 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 (/000) since 00. The 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 Proftest SYKE PT0 (EN ISO/IEC 0, www. nas. ). This 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. The success of the pro ciency test requires con dential co-operation between the provider and participants. Thank you for your co-operation! Helsingissä. huhtikuuta 0 / Helsinki April 0 Laboratorionjohtaja / Chief of

7 INTRODUCTION Proftest SYKE carried out the pro ciency test (PT) for analysis of PCB compounds in soil in November 0 January 0. An arti cial sample (PCBs in isooctane) and a contaminated soil sample were distributed to the participants. In this PT the results of Finnish laboratories providing environmental data for Finnish environmental authorities were evaluated. Additionally, other water and environmental laboratories were welcomed in the pro ciency test. The test was carried out in accordance with the international guidelines, ISO/IEC 0 [], ISO [] and IUPAC Technical Report []. Proftest SYKE has been accredited by the Finnish Accreditation Service as a pro ciency testing provider PT0 (ISO/IEC 0, www. nas. ). Proftest SYKE is the accredited pro ciency test provider on the eld of the present test. ORGANIZING THE PROFICIENCY TEST. Responsibilities Organizing laboratory: Proftest SYKE, Finnish Environment Institute (SYKE), Centre Hakuninmaantie, 00 Helsinki, Finland Phone: + 0 Fax: + The responsibilities in organizing the PT were as follows: Kaija Korhonen-Ylönen, coordinator Jari Nuutinen, substitute of coordinator, analytical expert Anne Markkanen, technical assistant Markku Ilmakunnas, technical assistant, layout of the report Keijo Tervonen, technical assistant Ritva Väisänen, technical assistant Sari Lanteri, technical assistant. Participants In total, laboratories from Denmark, Finland, Sweden and Turkey participated in this pro ciency test (Appendix ). From the participants eight laboratories used an accredited method for most of PCB compounds. The organizing laboratory (SYKE) had the codes (ASE extraction) and (Ultrasonic extraction) in the result tables.. Samples and delivery The sample A was a synthetic sample prepared by diluting the certi cated reference PCB solutions (Dr. Ehrenstorfer) with isooctane. The preparation of the samples is presented in more detail in Appendix. The sample A contained also the PCB congeners,, and though these congeners were not requested to be analysed. The sample A did not contained PCB but it was requested to be analysed. The sample was the PCB contaminated soil containing sealant. The soil sample was dried at the room temperature and sieved through a 0. mm sieve before homogenization and subsampling. The same sample was distributed earlier also in the PT SYKE / 00 and PT SYKE / 00.

8 The samples were delivered November 0. They were requested to be analysed and reported at the latest January 0.. Homogeneity studies Homogeneity of the soil sample was tested by analyzing PCB-, PCB-, PCB-, PCB-, PCB- and PCB-0 as duplicate determinations from six sub samples (Appendix ). According to the homogeneity test results the sample was considered to be homogenous.. Feedback from the pro ciency test Appendix contains the comments sent by the participants and feedback from the provider to the 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 (marked as 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 %. The replicate results were tested using the Cochran test (marked as C in the results 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. 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 ( /syke/proftest)... Assigned values and their uncertainties The assigned values and their uncertainties are presented in Appendix. The calculated concentrations were used as the assigned values for the concentrations of all measurements in the arti cial sample A. The uncertainty of the assigned value given is the expanded combined uncertainty based on the combination of uncertainties associated with individual operations involved in the preparation of the sample. In all cases the uncertainty was less than % and the main individual resource of the uncertainty was the uncertainty of the impurity in the stock solution. The robust means of the reported results were used as the assigned value for the concentrations of the PCBs in the soil sample. The uncertainty of the assigned value was calculated using the robust standard deviation of the reported results. Depending of the PCB congener the uncertainties varied from to 0 % (Appendix ). After reporting of the preliminary results no signi cant correction of the assigned value has been done... Standard deviation for pro ciency assessment and z score The evaluation of the participants was based on z scores, which were calculated using the estimated standard deviation for pro ciency assessment. The estimation of the target standard deviation based on the type of sample, the concentration of the analyte in the sample, the results of homogeneity test and the uncertainty of the assigned value.

9 The reliability of the assigned value was tested according the criterion u / s p 0., where u is the standard uncertainty (U / ) of the assigned value and s p the target value (target value for total deviation / ). Due to low number of the participants and the large deviation of the results the criterion was not ful lled in every case, which indicated that the following assigned values in the soil sample had high uncertainty: PCB-, PCB-, PCB-0, PCB-, PCB-+, PCB-. The reliability of the standard deviation for pro ciency assessment (s p ) and correspondingly the z score were estimated by comparing the target value (s p ) with the robust standard deviation of the reported results (s rob ). Due to low number of the results the criterion s rob <. s p was not ful lled in every cases (PCB-, PCB-, PCB-, PCB-), which weakened the evaluation of performance. The performance evaluation was not carried out in the case where the assigned value based on the consensus value and the number of the participants was below. Due to low number of participants the results of PCB-, PCB-0 and PCB- in the soil sample were not evaluated. RESULTS. Results Explanations for the result sheets are presented in Appendix. The results and the performance of each laboratory are presented in Appendix and the summary of the results in Table. The results and their uncertainties are presented graphically in Appendix and the summary of z scores is presented in Appendix. The robust standard deviation of the results was lower than % for % of the results and lower than 0 % for 0 % of the results. Standard deviations higher than 0 % applied mainly to the congeners PCB-, PCB-, PCB-+ and PCB-. Table. Summary of the pro ciency test /0. Ass. Val.- the assigned value, Mean - the mean value, Mean rob - robust mean, Md - the median value, SD % - the standard deviation as percent, SD rob - the robust standard deviation, SD rob % - the robust standard deviation as percents, Num of Labs - the number of participants, Targ. SD% - the total standard deviation for pro ciency assessment at % con dence level ( s p ), Accepted z-val% - the satisfactory z scores: the results (%), where z.

10 In this PT the participants were requested to report duplicate results for all measurements. The participants reported the replicates with the exception of one laboratory (Lab ). The results of the replicate determinations based on the ANOVA statistical handling are presented in Table. The 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 0. to times higher than the repeatability (s w ). For the robust methods the ratio s b / s w, should not exceed.. Analytical methods The analytical methods used by the participants are presented in Appendix.. PCB compounds in soil Determination of PCB compounds from soil samples based on several standard methods or EPAs methods [ ]. Half of the methods were modi cations of the standard methods. Extraction was mostly done by shaking. Most participants used splitless-injection technique. Six laboratories used GC-MS technique and ve used GC-ECD technique. Method comparison for the sample A was done between measurement techniques and for the soil sample between extraction methods. Before method comparison the results were coded by coordinator as follows: Sample A - Method : GC-MS - Method : GC-ECD - Method : GC-HRMS

11 Sample - Method : Extraction with Shaking - Method : Soxhlet extraction - Method : Extraction with accelerated solvent extractor - Method : Extraction with ultrasonic No signi cant difference could be obtained between the methods. According to the graphical presentation the unsatisfactory results were not due to the applied technique (Appendix.).. Uncertainties of the results All laboratories reported the expanded uncertainties at least with some of their results (Appendix ). Several procedures were used for estimating of measurement uncertainty (Appendix ). The procedure based on data obtained in the method validation and the internal quality control (Meth ) was the most common. The other procedures were used by only one or two laboratories. Due to low number of the participants it is dif cult to draw conclusion from the relation of the uncertainty and the evaluation procedure. Table. The range of the expanded uncertainties (%) reported by the participants Analyte Sample A Sample PCB PCB PCB PCB- 0 PCB- PCB- 0 PCB- PCB- PCB- 0 0 PCB- 0 PCB- 0 PCB-0 0 PCB-0 EVALUATION OF PERFORMANCE The evaluation of the participants was based on z scores, which were calculated using the estimated standard deviation for pro ciency assessment. In the performance evaluation z scores were interpreted as follows: z satisfactory results < z < questionable results z unsatisfactory results The calculated z scores are presented with the results of each participant (Appendix ) and the summary of z scores is presented in Appendix. When accepting deviations of 0 % from the assigned values for synthetic sample A, % of the results were satisfactory. In this PT the number of satisfactory results was slightly lower than in the previous PT /00 []. The participants had most problems in correct analysis of PCB, which poorly separates from PCB-.

12 Consequently, when accepting deviations of % from the assigned values for the soil sample, % of the results were satisfactory. The number of the satisfactory results in this PT was at the same level as in the PT /00 [], where the same soil sample was distributed and an average % of the results were satisfactory. In total, % of the total result data in this PT were satisfactory. Most participants used accredited methods and % of their results were satisfactory (Appendix ). SUMMARY Proftest SYKE carried out the pro ciency test for the determinations of PCB compounds in soil samples in the end of 0. In total, laboratories participated in the pro ciency test. One arti cial sample (A) and one soil sample () were delivered to the laboratories. The calculated concentrations (sample A) or the robust mean of the results reported by the participants (sample ) were used as the assigned values for the measurands. The uncertainties of the calculated assigned values were less than %. Respectively the uncertainties of the consensus assigned values (the robust mean) were from. % to %. In total, % of the total result data in this PT were satisfactory when the deviations of 0 % from the assigned values were accepted. Regardless of the several methods, extraction and instrument techniques used for the analysis of the soil sample the results were surprisingly similar. YHTEENVETO Proftest SYKE järjesti pätevyyskokeen PCB yhdisteiden määrityksestä maanäytteestä () loppuvuodesta 0. Maanäytteen lisäksi osallistujille toimitettiin synteettinen näyte (A). Pätevyyskokeeseen osallistui yhteensä laboratoriota Ruotsista, Suomesta, Tanskasta ja Turkista. Synteettisessä näytteessä (A) PCB-pitoisuuden vertailuarvona käytettiin laskennallista pitoisuutta (teoreettinen arvo). PCB-yhdisteiden laskennallisten vertailuarvojen laajennetut epävarmuudet olivat alle %. Maanäytteessä () PCB-pitoisuuden vertailuarvona käytettiin osallistujien raportoimien tulosten robustiakeskiarvoa (sopimusarvo). Yhdisteestä ja raportoitujen tulosten hajonnasta riippuen vertailuarvon laajennettu epävarmuus, %, kun vertailuarvona käytettiin sopimusarvoa. Synteettisten näytteiden tuloksissa sallittiin 0 %:n poikkeama vertailuarvosta, jolloin tuloksista oli hyväksyttäviä %. Vuoden 00 vastaavassa vertailussa PCB-yhdisteiden tuloksista oli hyväksyttäviä %, mutta silloin määritettäviä PCB-yhdisteitä synteettisessä näytteessä oli enemmän []. Maanäytteen tulosten sallittiin poiketa vertailuarvosta %, jolloin PCB-yhdisteiden tuloksista oli hyväksyttäviä %. Vuoden 00 vastaavassa vertailussa PCB-yhdisteiden tuloksista oli hyväksyttäviä %. Vaikka osallistujien käyttämät menetelmät, uutto- ja mittaustekniikat poikkesivat toisistaan huomattavasti, niin näytteen tulokset olivat yllättävän vertailukelpoisia. Tässä pätevyyskokeessa koko aineistossa hyväksyttäviä tuloksia oli yhteensä %. Akkreditoituna ilmoitetuista tuloksista hyväksyttäviä oli %.

13 REFERENCES ISO/IEC 0, 0. Conformity assessment General requirements for pro ciency testing. ISO, 00. Statistical methods for use in pro ciency testing by interlaboratory comparisons. Thompson, M., Ellison, S.L. R., Wood, R., 00. The International Harmonized Protocol for the Pro ciency Testing of Analytical Chemistry laboratories (IUPAC Technical report). Pure Appl. Chem. : -, ( Mäkinen, I., Suortti, A-M., Huhtala, S. and Pönni, S., 00, Interlaboratory comparison /00 PCB compounds from polluted soils, Mimeograph series of the Finnish Environment Institute no. Mäkinen, I. and Nuutinen, J., 00, SYKE Pro ciency Test /00 PCB compounds from polluted soils, Mimeograph series of the Finnish Environment Institute no. Korhonen, K., Huhtala, S., Nuutinen, J., Markkanen, A., Pyykönen, H. and Ilmakunnas, M., 00, SYKE Pro ciency Test / 00 PCBs, PBDEs and PCCDs/PCDFs in sediment, Reports of Finnish Environment Institute / 00. IBSN (pdf). /publications. ISO :00, Soil quality - Determination of organochlorine pesticides and polychlorinated biphenyls - Gas-chromatographic method with electron capture detection. ISO 0:00, Soil quality - Determination of content of hydrocarbon in the range C to C0 by gas chromatography. BS EN -:00, BS 000-.:00, Methods of test for petroleum and its products. Petroleum products and used oils. Determination of PCBs and related products. Calculation of polychlorinated biphenyl (PCB) content. Nordtest TR, Nordic Guidelines for Chemical Analysis of Contaminated Soil Samples. EPA 0, Polychlorinated Biphenyls (PCBs) by Gas Chromatography.

14 APPENDIX PARTICIPANTS Ekokem Oy Ab, Riihimäki, Finland Eurofins Scientific Finland Oy, Tampere, Finland Finnish Environment Institute (SYKE), Helsinki, Finland IVL Swedish Environment Research Institute, Sweden MILANA A/S, Humlebaek, Denmark MetropoliLab Oy, Helsinki, Finland NabLabs Ympäristöanalytiikka Oy, Oulu, Finland National Institute of Health and Welfare, Kuopio, Finland SGS Inspection Services Oy, Kotka, Finland Tubitak Butal, Bursa, Turkey

15 PREPARATION OF THE SAMPLES APPENDIX Stock solution PCB Mix 0 (Certificated Dr. Ehrenstorfer PCB Mix 0): each PCB compounds µg/ml in isooctane. Stock solution PCB Mix (Certificated Dr. Ehrenstorfer PCB Mix ); each PCB compounds µg/ml in isooctane. Preparing of sample A: 0. ml (0. g) of PCB Mix 0 and 0. ml (0. g) of PCB Mix were diluted with. g of isooctane (Mix 0 + Mix ). The sample A was prepared by diluting. g of Mix 0 + with. g of isooctane. Table. Concentrations of PCBs in the stock solutions and the sample A Compound Concentration in stock solution PCB Mix 0, µg/ml Concentration in stock solution PCB Mix, µg/ml Concentration in Mix 0 +, µg/ml Final PCB concentrations in the sample A, ng/ml PCB 0.. PCB 0.0. PCB 0.. PCB 0.0. PCB 0.. PCB 0.0. PCB 0.0. PCB 0.0. PCB 0.0. PCB 0.. PCB 0.. PCB 0.0. PCB 0.0. PCB PCB 0 0..

16 APPENDIX TESTING OF HOMOGENEITY The homogeneity of the sample was tested by analysing six sub samples as duplicate measurements. Analyte / Sample Conc. mg/kg s p % s p s a s a /s p Was s a /s p < 0.? s bb s bb c Was s bb < c? PCB / YES..0 YES PCB / YES. 0 YES PCB / YES.. YES PCB / YES.. YES PCB / YES...0 YES PCB 0 / YES.0.. YES Conc. = Concentration s p = Target deviation, total target deviation / s p % = Target deviation as percent, total target deviation / s a = Analytical deviation, mean standard deviation of results in a sub sample s bb = Between-sample deviation, standard deviation of results between sub samples c = F s all + F s a where: s all = (0. s p ) F =. when the number of sub samples is F =. when the number of sub samples is Conclusion: In each case s a /s p < 0. and s bb < c. The samples could be regarded as homogenous.

17 FEEDBACK FROM THE PROFICIENCY TEST APPENDIX Lab Comment Action/SYKE Method description sheet was not found on the electric result sheet., The difference of the receiving weight of the sample A and the initial weight was more than 0. %. The method sheet was completed and the corrected result sheet was sent to all participants by . A new sample A was sent to the participant. FEEDBACK TO THE PARTICIPANTS Lab All Comment All participants sent their results on time. did not report duplicate results as it was requested.

18 APPENDIX ASSIGNED VALUES AND THEIR UNCERTAINTIES Analyte Abbreviation PCB- PCB- PCB-+ PCB- PCB- PCB- PCB- PCB- PCB- PCB- PCB- PCB-0 PCB-0 Sample Assigned value Unit Evaluation of the assigned value Uncertainty (U = u c ) % A. Calculated.. Robust mean 0 A. Calculated A. Calculated.. Robust mean A. Calculated. Robust mean A. Calculated. Robust mean A. Calculated.. Robust mean A A. Calculated. Robust mean. A. Calculated. Robust mean A. Calculated. Robust mean. A. Calculated.. Robust mean A. Calculated. - Robust mean - A. Calculated.. Robust mean.

19 TERMS IN THE RESULT TABLES APPENDIX 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 % 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 X * = median of x i (i =,, p) s * =. median of i x* (i =,, p) s. ( x i /( p x * i = x * - if x i < x * - x * i = x * + if x i > x * + x * i = x i otherwise x ) ) The robust estimates x * and s * can be derived by an iterative calculation, i.e. by updating the values of x * and s * several times, until the process convergences. Ref: Statistical methods for use in proficiency testing by inter laboratory comparisons, Annex C [].

20 LIITE / APPENDIX LIITE. RESULTS OF EACH PARTICIPANT APPENDIX. Analyte Unit Sample z-graphics Z- value Outl Assigned test OK value * Targ SD% Lab's result Md. Mean SD SD% Passed Outl. failed Missing Num of labs PCB- A -,0 yes, 0,,,,0, 0 0-0, yes, 0,,, 0 0 PCB- A -, yes, 0,,,0,, 0, yes,, 0,, 0 0 PCB- A -, yes, 0,,,0,, 0 0,0 yes, 0, 0,,0 0 0 PCB- A -, yes, 0,,,,, 0 0, H 0, 0,, 0 PCB-0 A -,0 yes, 0,0,,,, 0, H,,,,, 0 PCB-+ A -,0 H, 0,,,, 0, 0 -, yes,,,,, 0,0 0 PCB- A -, yes, 0,0,,,0,0 0 0, yes,,,, 0 PCB- A -0, yes, 0,,,0, 0 0-0,0 yes 0 0,,, 0 0 PCB- A 0, yes, 0,,,0,, 0 0, yes 0, 0,, 0 0 PCB- A -0, yes, 0,,,0,, 0 0-0,0 yes 0 0, 0,,0 0 0 PCB- A -0, yes, 0,,,,, 0 0-0,00 yes 0 0,, 0 PCB-0 A -0, yes, 0,,,,, 0 0, yes,,,,,, 0 PCB- A 0,0 yes, 0,,,, 0 0 0, yes,,,,, PCB- A -0, yes, 0,,,0,0 0 0, yes,,, 0 PCB- 0,0 yes, 0,,, 0 0 PCB- 0, yes,,,,,, 0 PCB- yes,,, 0,, 0 0 PCB- 0, yes,, 0,, 0 0 PCB- -0,0 yes, 0, 0,,0 0 0 PCB- 0,0 yes, 0,, 0 PCB- -0, yes,,,,,, 0 PCB-0 yes,,,,,0, 0 0 PCB-0 0, yes,,,,,, 0 PCB- -0, yes,,,,,, PCB-+ 0,0 yes,,,, 0,0 0 PCB- yes,,,,,, 0 PCB- 0, yes,,,, 0 Outlier test failed: C - Cohcran, G - Grubbs(-outlier algorithm), G - Grubbs(-outliers algorithm), H - Hampel, M - manual SYKE - Interlaboratory comparison test /0

21 LIITE APPENDIX / Analyte Unit Sample z-graphics Z- value Outl Assigned test OK value * Targ SD% Lab's result Md. Mean SD SD% Passed Outl. failed Missing Num of labs PCB- A -,0 yes, 0,,,,0, 0 0-0, yes 0, 0,,, 0 0 PCB- A -, yes, 0,0,0,,, 0 0-0, yes,,,,, 0 PCB- yes,,, 0,, 0 0 PCB- A -, yes, 0,,,0,, 0 0, yes,, 0,, 0 0 PCB- A -,0 yes, 0 0,,,0,, 0 0 -, yes, 0, 0,,0 0 0 PCB- A -, yes, 0 0,,,,, 0 0 0, yes 0, 0,, 0 PCB- A -, yes, 0,,0,,, 0 0-0, yes,,,,,, 0 PCB-0 A -, yes, 0,,0,0,, 0 0 yes, 0,,,,0, 0 0 PCB-0 A -, yes, 0 0,,,,, 0 0,0 yes,,,,,, 0 PCB- A -,0 yes, 0,0,,,, 0 0 -,0 yes,,,,,, PCB-+ A -, yes, 0,,,, 0, 0-0, yes,,,,, 0,0 0 PCB- A -,00 yes, 0,,,,, 0 yes,,,,,, 0 PCB- A -, yes, 0,,,,0,0 0-0, yes,,, 0 PCB- A -0, yes, 0,,,,0, 0 0-0, yes, 0,,, 0 0 PCB- A -, yes, 0,,0,,, 0 0 0, yes,,,,,, 0 PCB- A -, yes, 0,,0,, 0-0,0 yes,, 0,, 0 0 PCB- A -0, yes, 0,,,0,, 0 0 0, yes, 0, 0,,0 0 0 PCB- A -,0 yes, 0,,,,, 0 0-0, yes, 0,, 0 PCB- A -0, yes, 0,,0,,, 0 0, H,,,,,, 0 PCB-0 A -0,0 yes, 0,,0,0,, 0 0 yes,,,,,0, 0 0 PCB-0 A -0, yes, 0,,,,, 0-0, yes,,,,,, 0 PCB- A -, yes, 0,,,,, 0 0 -, H,,,,,, PCB-+ A -, yes, 0,,,, 0, 0 -, H,,,,, 0,0 0 PCB- A -, yes, 0,,,,, 0 M,,,,,, 0 PCB- A -, yes, 0,,,,0,0 0,000 H,,,, 0 PCB- A -, yes, 0,,,,0, 0 0 0, yes 0,,, 0 0 PCB- A -, yes, 0,0,,0,, 0-0, yes, 0,, 0 0 PCB- A -,0 yes, 0,,,0,, 0 0 0, yes 0, 0,,0 0 0 PCB- A -, yes, 0,,,,, 0 0 0, yes 0,, 0 PCB-0 A -, yes, 0,,,,, 0 0, yes,,,,,, 0 PCB- A -,0 yes, 0,,,,, 0 0, yes,,0,,,, PCB- A -, yes, 0,,,,0,0 0,00 H,,, 0 Outlier test failed: C - Cohcran, G - Grubbs(-outlier algorithm), G - Grubbs(-outliers algorithm), H - Hampel, M - manual SYKE - Interlaboratory comparison test /0

22 LIITE / 0 APPENDIX Analyte Unit Sample z-graphics Z- value Outl Assigned test OK value * Targ SD% Lab's result Md. Mean SD SD% Passed Outl. failed Missing Num of labs PCB- A -,0 yes, 0,,,,0, 0 0-0, yes, 0,,, 0 0 PCB- A -, yes, 0,,,0,, 0-0,0 yes,, 0,, 0 0 PCB- A -, yes, 0,,,0,, 0 0 -, yes 00 0, 0,,0 0 0 PCB- A -, yes, 0 0,,,,, 0 0 0,00 yes 0,, 0 PCB-0 A -, yes, 0,,,,, 0 -,0 yes, 0,,,, 0 PCB- A -, yes, 0,,,,, 0 0 -, yes,,,,, PCB- A -, yes, 0,,,,0,0 0-0, yes 0,,,, 0 PCB- A -0,00 yes, 0,,,,0, 0 0-0, yes 0,,, 0 0 PCB- A -0, yes, 0,,0,,, 0 0 0, yes,,,,,, 0 PCB- A <,,E 0 0 yes,, 0,, 0 0 PCB- A -0,0 yes, 0,,,0,, 0 0, yes, 0,, 0 0 PCB- A -0, yes, 0,,,0,, 0 0 -, yes 0 0, 0,,0 0 0 PCB- A -0, yes, 0,,,,, 0 0-0, yes, 0,, 0 PCB- A -0,0 yes, 0,0,0,,, 0 0 0, yes,,,,,, 0 PCB-0 A 0,0 yes, 0,,0,0,, 0 0 yes,,,,,0, 0 0 PCB-0 A 0,0 yes, 0,,,,, 0 0, yes,,,,,, 0 PCB- A -0, yes, 0,,,,, 0 0-0, yes,,,,,, PCB-+ A -, yes, 0,,,, 0, 0-0,0 yes,,,,, 0,0 0 PCB- A -, yes, 0,,,,, 0 yes,,,,,, 0 PCB- A -0,0 yes, 0,,,,0,0 0 0,0 yes,,, 0 Outlier test failed: C - Cohcran, G - Grubbs(-outlier algorithm), G - Grubbs(-outliers algorithm), H - Hampel, M - manual SYKE - Interlaboratory comparison test /0

23 LIITE APPENDIX / Analyte Unit Sample z-graphics Z- value Outl Assigned test OK value * Targ SD% Lab's result Md. Mean SD SD% Passed Outl. failed Missing Num of labs PCB- A, yes, 0,0,,,0, 0 0, yes 0, 0,,, 0 0 PCB- A, yes, 0,,0,,, 0 0-0, yes,,,,,, 0 PCB- A,0 C, 0,,,0,, 0-0, yes,, 0,, 0 0 PCB- A, yes, 0,,,0,, 0 0, yes 0, 0, 0,,0 0 0 PCB- A,00 yes, 0,,,,, 0 0-0, yes 0, 0,, 0 PCB- A,0 yes, 0,0,0,,, 0 0 -, yes,,,,,, 0 PCB-0 A, yes, 0,,0,0,, 0 0 yes,,,,,0, 0 0 PCB-0 A 0,0 C, 0,,,,, 0 0,0 yes,,,,,, 0 PCB- A,0 yes, 0,,,,, 0 0 -, yes,,,,,, PCB-+ A, yes, 0,,,, 0, 0 0,00 yes,,,,, 0,0 0 PCB- A,0 H, 0,,,,, 0 yes,,,,,, 0 PCB- A, C, 0,,,,0,0 0, yes 0,,,, 0 PCB- A 0,0 yes, 0,,,,0, 0 0 -, yes 0,,, 0 0 PCB- A -, yes, 0,0,0,,, 0 0, H,,,,, 0 PCB- A -, yes, 0,,,0,, 0-0, yes,, 0,, 0 0 PCB- A 0, yes, 0,,,0,, 0 0 0, yes, 0, 0,,0 0 0 PCB- A, yes, 0,,,,, 0 0,0 yes 0,, 0 PCB- A 0, yes, 0,,0,,, 0 0, yes,,,,,, 0 PCB-0 A 0,0 yes, 0,,,,, 0 0, yes,,,,,, 0 PCB- A,0 yes, 0,,,,, 0 0, yes,,,,,, PCB-+ A -, yes, 0,,,, 0, 0 0, yes,,,,, 0,0 0 PCB- A 0, C, 0,,,0,0 0, H,,,, 0 PCB- A -, yes, 0 0,,,,0, 0 0, yes, 0,,, 0 0 PCB- A -, yes, 0,,,0,, 0-0, yes,, 0,, 0 0 PCB- A -,0 yes, 0 0,,,0,, 0 0-0, yes, 0, 0,,0 0 0 PCB- A -, yes, 0,,,,, 0 0-0, yes 0,, 0 PCB-0 A -, yes, 0,,,,, 0-0, yes,,,,,, 0 PCB- A -, yes, 0,0,,,, 0 0 H, <,,,,, PCB- A -, yes, 0,,,,0,0 0 -, yes,,, 0 Outlier test failed: C - Cohcran, G - Grubbs(-outlier algorithm), G - Grubbs(-outliers algorithm), H - Hampel, M - manual SYKE - Interlaboratory comparison test /0

24 LIITE APPENDIX / LIITE. RESULTS AND THEIR UNCERTAINTIES APPENDIX. PCB- A 0 0 PCB PCB- A SYKE - Interlaboratory comparison test /0

25 LIITE APPENDIX / PCB PCB- A 0 PCB SYKE - Interlaboratory comparison test /0

26 LIITE APPENDIX / PCB- A PCB PCB- A 0 0 SYKE - Interlaboratory comparison test /0

27 LIITE APPENDIX / PCB PCB- A 0 0 PCB SYKE - Interlaboratory comparison test /0

28 LIITE APPENDIX / PCB- A PCB- 0 0 PCB-0 A SYKE - Interlaboratory comparison test /0

29 LIITE APPENDIX / PCB PCB-0 A 0 0 PCB SYKE - Interlaboratory comparison test /0

30 LIITE APPENDIX / PCB- A 0 0 PCB- 0 PCB-+ A SYKE - Interlaboratory comparison test /0

31 LIITE APPENDIX / PCB-+ 0 PCB- A PCB- SYKE - Interlaboratory comparison test /0

32 LIITE APPENDIX / PCB- A 0 0 PCB SYKE - Interlaboratory comparison test /0

33 LIITE APPENDIX / LIITE. SUMMARY OF THE z SCORES APPENDIX. Analyte Sample\Lab PCB- A S S. S S q q S S S q 0 S S S S S S S S Q S S PCB- A... q S.. S Q S. 0.. S S S.. S S U. PCB- A PCB- A S S. q S S S S Q S u 0 S S S S S S S S S S S 0 PCB- A S S. q S S S S S S q 0 S S S S S S S S U S S PCB- A q S. q S S q S S S q 0 U S S S S S S S S S S PCB- A... q S.. S Q S. 0.. S S U.. S S S. PCB-0 A... q S.. S Q PCB-0 A q S. q S S S S S S q 0 U S S S S S S S S S S PCB- A. S. S S S S S Q Q u. S S S u S S S S Q. PCB-+ A u.. S q.. S Q S. 0 q. S S u.. S S S. PCB- A... S u.. u U PCB- A S S. S S S u S S S q 0 S S S S U U S S S U S % Accredited yes yes yes yes yes yes yes yes yes % %* - percentage of satisfactory results Totally satisfactory, % In all: In accredited: In non-accredited: SYKE - Interlaboratory comparison test /0

34 APPENDIX. ANALYTICAL METHODS Soil Lab Extraction Internal standard Sampling / Injection Equipment Reference Shaking PCB- Splitless GC-MS ISO Soxhlet PCB-, NCB PTV GC-ECD? ASE PCB-, TeCB Splitless GC-ECD In house method Ultrasonic PCB-, TeCB Splitless GC-ECD In house method Shaking Deuterated biphenyl Splitless GC-MS EPA 0 modified Shaking PCB- Splitless GC-MS Nordtest TR Ultrasonic PCB-, PCB-0 Splitless GC-ECD ISO Soxhlet PCB-, PCB-[ C], PCB-[ C], [PCB- [ C], [PCB-[ C], [PCB- [ C] Spitless GC-HRMS In house method Shaking PCB-0 Splitless GC-MS ISO 0, ISO - Shaking PCB- Pulsed splitless GC-MS ISO modified Shaking PCB-0 Splitless GC-ECD ISO ASE, Accelerated solvent extractor PTV, Programmable Temperature Vaporization Injector

35 APPENDIX. RESULTS GROUPED ACCORDING TO THE METHODS No statistical comparison between the different techniques could be done because of the low number of the results. In this appendix the results of the participants are grouped according to the instrument techniques (A) and extraction techniques () as follows: Sample A Meth. Meth. Meth. GC-MS GC-ECD GC-HRMS Sample Meth. Meth. Meth. Meth. Shaking Soxhlet ASE Ultrasonic

36 LIITE APPENDIX. / LIITE.. APPENDIX.. PCB- A 0 0 Meth Meth Meth PCB Meth Meth Meth Meth PCB- A Meth Meth Meth SYKE - Interlaboratory comparison test /0

37 LIITE APPENDIX. / PCB Meth Meth Meth Meth PCB- A PCB Meth Meth Meth SYKE - Interlaboratory comparison test /0

38 LIITE APPENDIX. / PCB- A Meth Meth Meth PCB Meth Meth Meth Meth PCB- A 0 0 Meth Meth Meth SYKE - Interlaboratory comparison test /0

39 LIITE APPENDIX. / PCB Meth Meth Meth Meth PCB- A 0 0 Meth Meth Meth PCB Meth Meth Meth Meth SYKE - Interlaboratory comparison test /0

40 LIITE APPENDIX. / PCB- A Meth Meth Meth PCB- 0 0 Meth Meth Meth Meth PCB-0 A Meth Meth Meth SYKE - Interlaboratory comparison test /0

41 LIITE APPENDIX. / PCB Meth Meth Meth Meth PCB-0 A 0 0 Meth Meth Meth PCB Meth Meth Meth Meth SYKE - Interlaboratory comparison test /0

42 LIITE APPENDIX. / 0 PCB- A 0 0 Meth Meth Meth PCB- 0 Meth Meth Meth Meth PCB-+ A Meth Meth Meth SYKE - Interlaboratory comparison test /0

43 LIITE APPENDIX. / PCB-+ 0 Meth Meth Meth Meth PCB- A Meth Meth Meth PCB- Meth Meth Meth Meth SYKE - Interlaboratory comparison test /0

44 LIITE APPENDIX. / PCB- A 0 0 Meth Meth Meth PCB Meth Meth Meth Meth SYKE - Interlaboratory comparison test /0

45 APPENDIX EXAMPLES OF MEASUREMENT UNCERTAINTIES REPORTED BY THE LABORATORIES For evaluation of the measurement uncertainty the participants have used the procedures as follows:. Using the variation of the results in X chart (for the artificial samples). Using the variation of the results in X chart and the variation of the replicates (r%- or R- chart for real samples). Using the data obtained in method validation and IQC, see e.g. NORDTEST TR ). Using the data obtained in the analysis of CRM (besides IQC data). see e.g. NORDTEST TR ). Using the IQC data and the results obtained in proficiency tests. see e.g. NORDTEST TR ). Using the "modelling approach" (GUM Guide or EURACHEM Guide Quantifying Uncertainty in Analytical Measurements ). Other procedure. No uncertainty estimation IQC = internal quality control In the figures the procedures have been presented using the same code number. ) )

46 LIITE APPENDIX / LIITE. APPENDIX. PCB- 0 0 Uncertainty, % 0 Meth Meth Meth Meth Meth PCB- Uncertainty, % Meth Meth Meth Meth Meth PCB- Uncertainty, % Meth Meth Meth Meth Meth SYKE - Interlaboratory comparison test /0

47 LIITE APPENDIX / PCB-0 Uncertainty, % Meth Meth Meth Meth Meth PCB- 0 0 Uncertainty, % 0 Meth Meth Meth Meth Meth 0 0 SYKE - Interlaboratory comparison test /0

48 Documentation page Publisher Finnish Environment Institute (SYKE) Date April 0 Author(s) Jari Nuutinen, Kaija Korhonen-Ylönen, Mirja Leivuori and Markku Ilmakunnas Title of publication Proficiency Test SYKE /0 PCB compounds in soil Parts of publication/ other project publications Abstract The publication is available only on the internet Proftest SYKE carried out the proficiency test for analysis of PCB compounds in soil in end of 0. In total laboratories participated in the proficiency test. The sample types were: a reference PCB solution in isooctane and a contaminated soil sample. Basically, the calculated concentrations or the robust mean of the results reported by the participant were used as the assigned values for measurands. The evaluation of the performance of the participants was carried out using z score. In some cases the evaluation of the performance was not possible e.g. due to the low number of the participants. In total, % of the total data in this proficiency test were satisfactory when the deviations of 0 % from the assigned values were accepted. Keywords Publication series and number Theme of publication PCB compounds, soil, environmental laboratories, proficiency test, interlaboratory comparisons Reports of Finnish Environment Institute /0 Project name and number, if any Financier/ commissioner Project organization ISSN ISBN - (online) (PDF) No. of pages Language English Restrictions Public Price For sale at/ distributor Financier of publication Printing place and year Helsinki 0 Other information Finnish Environment Institute, Customer service neuvonta.syke@ymparisto.fi Phone + 0 Fax Finnish Environment Institute, P.O. Box 0, FI-00 Helsinki, Finland

49 Kuvailulehti Julkaisija Suomen ympäristökeskus (SYKE) Julkaisuaika Huhtikuu 0 Tekijä(t) Jari Nuutinen, Kaija Korhonen-Ylönen, Mirja Leivuori ja Markku Ilmakunnas Julkaisun nimi Proficiency Test SYKE /0 PCB compounds in soil Julkaisun osat/ muut saman projektin tuottamat julkaisut Tiivistelmä Julkaisu on saatavana vain internetistä. Suomen ympäristökeskuksen laboratorio järjesti pätevyyskokeen ympäristönäytteitä analysoiville laboratorioille loppuvuonna 0. Pätevyyskokeen näytteinä oli synteettinen PCB-liuos isooktaanissa ja kontaminoitunut maanäyte. Pätevyyskokeeseen osallistui yhteensä laboratoriota, joista yksi raportoi kahdella eri menetelmällä analysoidut tulokset. Laboratorioiden pätevyyden arviointi tehtiin z-arvon avulla. Mittaussuureen vertailuarvona käytettiin synteettisessä näytteessä laskennallista pitoisuutta ja maanäytteessä osallistujien ilmoittamien tulosten robustia keskiarvoa. Koko tulosaineistossa hyväksyttäviä tuloksia oli %, kun vertailuarvosta sallittiin 0 %:n poikkeama. Asiasanat Julkaisusarjan nimi ja numero Julkaisun teema maa-analyysi, PCB-yhdisteet, vesi- ja ympäristölaboratoriot, pätevyyskoe, laboratorioiden välinen vertailumittaus Reports of Finnish Environment Institute /0 Projektihankkeen nimi ja projektinumero Rahoittaja/ toimeksiantaja Projektiryhmään kuuluvat organisaatiot ISSN ISBN - (verkkoj.) (PDF) Sivuja Kieli Englanti Luottamuksellisuus Julkinen Hinta Julkaisun myynti/ jakaja Julkaisun kustantaja Painopaikka ja -aika Helsinki 0 Muut tiedot Suomen ympäristökeskus, asiakaspalvelu Sähköpostiosoite: neuvonta.syke@ymparisto.fi puh. 00 faksi Suomen ympäristökeskus, PL 0, 00 Helsinki

50 Presentationsblad Utgivare Finlands Miljöcentral (SYKE) Datum April 0 Författare Jari Nuutinen, Kaija Korhonen-Ylönen, Mirja Leivuori och Markku Ilmakunnas Publikationens titel Proficiency Test SYKE /0 PCB compounds in soil Publikationens delar/ andra publikationer inom samma projekt Sammandrag Publikationen finns tillgänglig på internet Under slutåret 0 genomförde Finlands Miljöcentral en provningsjämförelse, som omfattade bestämningen av PCB-föreningar in jord. Provet bestod av syntetiska och därtill ett jordprov. Tillsammans laboratorier deltog i jämförelsen. Som referensvärde av analytens koncentration användes mest det teoretiska värdet eller robust medelvärdet av deltagarnas resultat. Resultaten värderades med hjälp av z-värden. I jämförelsen var % av alla resultaten tillfredsställande, när total deviation på 0 % från referensvärdet accepterades. Nyckelord Publikationsserie och nummer jordanalyser, PCB-föreningar, provningsjämförelse, vatten- och miljölaboratorier Reports of Finnish Environment Institute /0 Publikationens tema Projektets namn och nummer Finansiär/ uppdragsgivare Organisationer i projektgruppen ISSN ISBN - (online) (PDF) Sidantal Språk Engelska Offentlighet Offentlig Pris Beställningar/ distribution Förläggare Tryckeri/ tryckningsort och år Finlands miljöcentral, informationstjänsten neuvonta.syke@ymparisto.fi Tfn 00 Fax Finlands Miljöcentral, PB 0, 00 Helsingfors Helsingfors 0 Övriga uppgifter

51 SYKE PROFICIENCY TEST /0 ISBN (PDF) ISSN - (online) SYKE FINNISH ENVIRONMENT INSTITUTE