SYKE Proficiency Test 3/2010

Transkriptio

1 REPORTS OF FINNISH ENVIRONMENT INSTITUTE 1 11 SYKE Proficiency Test 3/ Metals in waters and sediment Mirja Leivuori, Kaija Korhonen,Timo SaraAho, Teemu Näykki, Olli Järvinen, Keijo Tervonen, Sari Lanteri and Markku Ilmakunnas Finnish Environment Institute

2

3 REPORTS OF FINNISH ENVIRONMENT INSTITUTE 1 11 SYKE Proficiency Test 3/ Metals in waters and sediment Mirja Leivuori, Kaija Korhonen,Timo SaraAho, Teemu Näykki, Olli Järvinen, Keijo Tervonen, Sari Lanteri and Markku Ilmakunnas Helsinki 11 Finnish Environment Institute

4 REPORTS OF FINNISH ENVIRONMENT INSTITUTE 1 11 Finnish Environment Institute SYKE The organizer of the intercomparison test: Finnish Environment Institute SYKE, Laboratories Hakuninmaantie 6, Helsinki phone , fax Publication is available only in the internet : ISBN (PDF) ISSN (online)

5 CONTENT 3 ALKUSANAT / PREFACE 4 1 INTRODUCTION 2 ORGANIZING THE PROFICIENCY TEST 2.1 Responsibilities 2.2 Participants 2.3 Samples and delivery Homogeneity studies 6 2. Comments sent by the participants Analytical methods Processing of the data Testing of normality of data, outliers and replicate results Assigned value Standard deviation for pro ciency assessment and z score 8 3 RESULTS AND CONCLUSIONS Results Analytical methods and status to the results Uncertainties of the results 17 4 EVALUATION OF PERFORMANCE 18 SUMMARY 19 6 YHTEENVETO REFERENCES APPENDICES Appendix 1 Participants in the pro ciency test 3/ 21 Appendix 2 Preparation of the samples 22 Appendix 3 Testing of homogeneity 24 Appendix 4.1 Comments sent by the participants 2 Appendix 4.2 Comments to the participants 26 Appendix.1 Analytical methods 27 Appendix.2 Signi cant differences in the results reported using different sample digestion 29 Appendix.3 Signi cant differences in the results reported using different measurement 30 methods Appendix.4 Results groupped according to the methods 31 Appendix 6 Evaluation of the assigned values and their uncertainties 69 Appendix 7 Terms in the result tables 72 Appendix 8 Results of each participant 73 Appendix 9 Summary of the z scores 116 Appendix Examples of measurement uncertainties reported by the laboratories 121 DOCUMENTATION PAGE 146 KUVAILULEHTI 147 PRESENTATIONS BLAD 148

6 ALKUSANAT 4 Suomen ympäristökeskus (SYKE) on toiminut ympäristöalan kansallisena vertailulaboratoriona vuodesta 01 lähtien. Toiminta perustuu ympäristöministeriön määräykseen, mikä on annettu ympäristönsuojelulain (86/00) nojalla. Vertailulaboratorion tarjoamista palveluista yksi tärkeimmistä on pätevyyskokeiden ja muiden vertailumittausten järjestäminen. Vertailumittausten järjestäminen täyttää kansainvälisten ohjeiden ISO/IEC Guide 431 ja ILACG13 asettamat vaatimukset. SYKEn laboratoriot on FINASakkreditointipalvelun akkreditoima testauslaboratorio T003 ja vertailumittausten järjestäjä PT01 (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) has served as the National Reference Laboratory in the environmental sector designated by the Ministry of the Environment under the section 24 of the Environment Protection Act (86/00) since 01. 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. The pro ciency testing service is a part of the SYKE laboratory management system based on the standard EN ISO/IEC The SYKE pro ciency testing service also conforms to the requirements of ISO/IEC GUIDE 431 and ILAC G13. The SYKE laboratories have been accredited by the Finnish Accreditation service as the testing laboratory T003 and as the pro ciency testing provider PT01 (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 more general level. The success of the pro ciency test requires con dential cooperation between the provider and participants. Thank you for your cooperation! Helsingissä. Tammikuuta 11 / Helsinki January 11 Laboratorionjohtaja / Chief of laboratory

7 1 Introduction The Finnish Environment Institute (SYKE) carried out the pro ciency test (PT) for analysis of elements in waters and soil in April August. The measurements were: Al, As, Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb, Se, V, Zn (waters, sediment) and N, P, S, TC (sediment). The sample types were: arti cial and natural water, municipal and industrial waste water and sediment. A total of 4 laboratories participated in the PT. In the 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 Guide 431 [1], ISO/IEC [2], ISO 1328 [3] and IUPAC Recommendations [4]. The SYKE laboratory has been accredited by the Finnish Accreditation Service as a pro ciency testing provider (PT01, www. nas. ). SYKE is the accredited pro ciency test provider on the eld of the present test. 2 Organizing the pro ciency test 2.1 Responsibilities Organizing laboratory: Finnish Environment Institute (SYKE), Laboratories Hakuninmaantie 6, Helsinki, Finland Phone: , Fax: Subcontractors in this pro ciency test were: Centre for Economic Development, Transport and the Environment in South Ostrobothnia, Vaasa, Finland for Hg analysis in industrial waste water and in sediment (testing laboratory T184, accredited by the Finnish Accreditation Service, www. nas. ) Water Protection Association of the Kokemäenjoki River in Tampere, Finland for sieving and dividing of sediment samples (testing laboratory T064, accredited by the Finnish Accreditation Service, www. nas. ) The responsibilities in organizing the pro ciency test were as follows: Mirja Leivuori, coordinator Kaija Korhonen, substitute of coordinator Keijo Tervonen, technical assistant Sari Lanteri, technical assistant Ritva Väisänen, technical assistant Markku Ilmakunnas, technical assistant and layout of the report The analytical experts were: Olli Järvinen heavy metal analyses (AAS, ICPMS) Timo SaraAho heavy metal analyses (ICPOES, IDICPMS) Teemu Näykki Hganalyses, IDICPMS 2.2 Participants 4 laboratories from Finland, Sweden, Denmark, Germany, Uruguay and Russia participated in the PT (Appendix 1). One laboratory reported the data measured by two different analytical methods. 2 of the Finnish participating laboratories provide data for use of the Finnish environmental authorities.

8 6 About 70 % of the participating laboratories used accredited analytical methods for at least a part of the analytes. The organizing laboratory (SYKE) has the code 2 in the result tables. For lead the metrologically traceable assigned value has been measured by IDICPMS in SYKE laboratory and the laboratory code is Samples and delivery The preparation of the samples is presented in more detail in Appendix 2. In the PT three different arti cial samples were delivered. The sample was diluted from standard reference material NIST 1643e, resulting in concentration levels suitable for ICPMS/ GAAS measurement. The sample was prepared using single element Merck Certipur RM solutions and concentration levels were higher than in sample, making ICPOES or FAAS measurements possible. The sample A1Hg was diluted from the Romil CRM Hgsolution. The arti cial samples were acidi ed with nitric acid (Note! Contrary to usual practice the sample was acidi ed by ml conc. HNO 3 /0 ml). Three different types of water samples were delivered to the participating laboratories. The natural water sample was prepared using water collected from the lake Lohjanjärvi in Lohja. The nal samples for the tested metals, with the exceptions of Cu, were prepared by addition of single element standard solutions in the natural water to increase the metal content in water (Appendix 2). The sample was municipal waste water with additions of single element standard solutions except for Al, Co, Cu, Fe, Mn, Ni and Zn. The third samples were industrial waste water T3Hg for Hg measurements and the sample TN/ for measurements of other metals. These samples were prepared with additions of single element standard solutions except for Cu and Fe (Appendix 2). The water samples were acidi ed with nitric acid (Appendix 2). The purity of the laboratory vessels used in the sample preparation was checked. According to the test the used sample vessels ful lled the purity requirements. The tested sediment was a combination of estuary sediments of the Baltic Sea from several locations. The sediment was freeze dried, homogenized and divided into subsamples using a vibrating feeder distributor. The samples were delivered 27 April. Mercury was requested to be measured 30 April at the latest. All the samples were requested to be analysed and reported 2 August at the latest. 2.4 Homogeneity studies The homogeneity of the samples was studied by measuring Cd, Cu, Mn, Zn (waters and sediment), Hg (water and sediment) and P, S (sediment). According to the homogeneity test results the samples were considered to be homogenous. More detailed information of homogeneity studies is in Appendix Comments sent by the participants The comments from the participants are in Appendix 4.1. The comments mainly deal with the errors with reporting of the results. The comments from the provider to the participants are shown in Appendix 4.2. These are mainly focused to the lacking conversancy to the given information with the samples.

9 2.6 Analytical methods 7 It was allowed to use different analytical methods for the measurements in the PT. The used analytical methods of the participants are shown in more detail in Appendix.1. Mercury KBr/KBrO 3, K 2 Cr 2 O 7, SnCl 2, KMnO 4, HNO 3 /KMnO 4, HNO 3 /KMnO 4 /NaBH 4 or KMnO 4 / K 2 S 2 O 8 (with HNO 3 and without) solutions were typically used as the oxidant in mercury analyses from waters at room temperature, in water bath (9 C) in autoclave (1 121 C) or in microwave oven. Additionally for mercury analyses in sediment also oxygen, nitric acid or aqua regia was used. The sediment sample was digested using a water bath, autoclave, microwave oven or the samples were digested under oxygen ow or measured directly in an instrument using oxygen at high temperature. Mercury was measured mostly using cold vapor CV AAS instrument. Other methods were for example FIMS ( ow injection mercury system based on atomic absorption), AFS (based on uorescence), ICPOES or ICPMS. Other elements The industrial waste water was measured without pretreatment () or after nitric acid digestion (). The results of these samples were evaluated separately. The sediment sample S6M was digested either by nitric acid (+ hydrogen peroxide) () or aqua regia (SO6). No other sample pretreatment was reported by the participants. The results of these differently pretreated sediment samples were treated separately. Heavy metals were mainly measured using FAAS, GAAS, ICPOES or ICPMStechniques. Arsenic was measured mainly using GAAS, ICPOES or ICPMSinstruments. Only a few laboratories used hydride techniques for measurements of As or Se. Nitrogen in sediment samples was mainly measured using NKjeldahl or equivalent method and by CSN analyzer. Sulfur was measured mainly by CSN analyzer (eg. Leco). Phosphorus in sediment samples was measured mainly by ICPAES/OESinstrument. Total carbon was measured by CSN analyzer and in few cases TC was calculated using measured LOI (loss on ignition) value. 2.7 Processing of the data Testing of normality of data, outliers and replicate results Before the statistical treatment, the data was tested according to the KolmogorovSmirnov normality test and the possible extreme values were rejected as the outliers according to the Hampel test. 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. In case that the result has been reported to be lower than detection limit, it has not been included in the statistical calculation of the results (marked as 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/proftest) Assigned value The assigned values and their uncertainties are presented in Appendix 6. The calculated concentrations were used as the assigned values for most measurands in the arti cial samples.

10 8 For the arti cial samples the expanded combined uncertainty based on the combination of uncertainties associated with individual operations involved in the preparation of the sample. The main individual resource of the uncertainty was the uncertainty of the concentration in the stock solution. For the synthetic samples, and A1Hg the calculated concentrations were used as the assigned value with exceptions of aluminium and and iron samples. For lead the metrologically traceable assigned value has been used for samples,, (accredited method), and. The assigned values for lead in these samples are based on results analyzed by a metrologically traceable isotope dilution IDICPMS method. The method used for analyzing lead by IDICPMS has been accredited for dissolved lead in natural waters in the scope of calibration laboratory (K04; www. nas. ). For the other samples and measurements the robust mean value was used as the assigned value. In the calculation of robust mean single results were excluded as replicate results were requested (i.e. Labs, 24). The uncertainty of the assigned value was calculated using the robust standard deviation of the reported results using the formula presented in Appendix 6. For the metrologically traceable lead results, the uncertainty is the expanded measuring uncertainty of the IDICPMS method. The uncertainty of the calculated assigned value and the metrologically traceable value for metals in the arti cial sample varied between 0.4 and 3 % and for the uncertainty was lower than 3 %. When using the robust mean of the participant results as the assigned value, the uncertainties of the assigned values varied between 1.8 % and 11 % (Appendix 6). After reporting of the preliminary results no corrections has been done to the assigned values Standard deviation for pro ciency assessment and z score The performance evaluation was carried out by using z scores (Appendix 7). The total standard deviation for pro ciency assessment used for calculation of the z scores was estimated on basis of the type of the sample, the concentration of the measurand, the results of homogeneity testing, the uncertainties of the assigned values and the longterm variation in former pro ciency tests. In the performance evaluation z scores were interpreted as follows: z 2 satisfactory results 2 < z < 3 questionable results z 3 unsatisfactory results The performance evaluation of the participants using calculated z scores is presented in Appendix 8. The reliability of the assigned value was tested according to the criterion: u/s p 0.3, where u is the standard uncertainty of the assigned value (the expanded uncertainty of the assigned value (U) divided by 2) and s p the standard deviation for pro ciency assessment (total standard deviation divided by 2). In the testing of the reliability of the assigned value the criterion was not met in every case, which is indicated by the high uncertainty of the assigned values in the following cases: : Cd The reliability of the target value for total deviation and the reliability of the corresponding z score were estimated by comparing the deviation for pro ciency assessment (s p ) with the robust standard

11 9 deviation of the reported results (s rob ). The criterion s rob < 1.2*s p was met in most cases. This criterion was not met for Cu in the sample and the evaluation of performance is only informative. For the sample SO6 and measurements of TC in sediment sample the evaluation of performance has not been done due to the low number of participants (from 4 to ). However, the assigned values were reported as informative with the preliminary results of the PT. In the nal report these assigned values have, however, been ignored due to the low number of results. The deviation of selenium results in the sediment sample was high (SD rob > 60 % and the result estimation was impossible. 3 Results and conclusions 3.1 Results The results and the performance of each laboratory are presented in Appendix 8 and the summary of the results in Table 1. The summary of zscores is shown in Appendix 9. The reported results and their uncertainties are presented graphically in Appendix.4. The robust standard deviation of results was lower than % for 62 % of the results and lower than % for 9 % of the results (Table 1). Standard deviations higher than % apply mainly to the sediment sample (, SO6) with a low number of participants with the exception of problems with selenium in sample. There were two populations of selenium results in sample (mean values ca. 0. and 1.3 mgkg 1 ), which indicates analytical problems in the measurements (see 3.2). The standard deviations of the results in this PT were approximately in the same range as in the previous comparable PT SYKE 4/09 [], where the deviations varied from 4.1 % to 37.2 %. For example sensitivity differences among the used analytical instruments can increase the variability of the results. On the other hand, different sample digestion procedures and the purity of used acids can affect the variability of the results measured from solid samples. Also the use of different analytical instruments can increase the variability of the results. In this PT the participants were requested to report replicate results for all measurements. The participants reported the replicates with the exception of two laboratories (Labs, 24). The results of the replicate determinations based on the ANOVA statistical handling are presented in Table 2.

12 Table 1. Summary of the results in the pro ciency test 3/.

13 11 Table 1. Summary of the results in the pro ciency test 3/. where Ass. val. the assigned value Mean the mean value Mean rob the robust mean Md the median value SD % the standard deviation as percents SD rob the robust standard deviation SD rob % the robust standard deviation as percents Num of Labs the number of the participants 2*Targ. SD% the total standard deviation for pro ciency assessment at the 9% con dence interval (=2*s p ) Accepted zval% the satisfactory z values: the results (%), where z 2.

14 12 Table 2. Results of the replicate determinations (ANOVA statistics).

15 13 Table 2. Results of the replicate determinations (ANOVA statistics).

16 14 In this PT the repeatability (the withinlaboratory standard deviation, s w ) was an average from 2 to times lower than the reproducibility (the betweenlaboratory standard deviation, s b, Table 2). The summary of the robustness of the methods, the ratio s b /s w, is presented in Table 3. The ratio s b /s w should not exceed 3 for robust methods. However in Table 3 is seen that in many cases the robustness exceeds the value 3. For sediment samples or SO6 the ratio s b /s w was too high for several metals. Table 3. The robustness (s b /s w ) of the replicate results in the PT 3/.

17 1 3.2 Analytical methods and status to the results Effect of sample pretreatment on elemental concentrations in waste waters Elements in waste water were mainly measured from acidi ed samples without sample pretreatment with the exception of the industrial waste water sample (/). About one half of the laboratories measured the acidi ed industrial waste water without sample pretreatment (), while the second half of the participants measured the industrial waste water after nitric acid digestion (). The Figure 1 shows the results for samples and. The difference between the average concentrations of elements measured by different sample preparation methods was tested using the ttest. The results of the ttest are shown in Appendix.2. There was statistically signi cant difference between arsenic results gained using no pretreatment method () and nitric acid digested results (TYN). Figure 1. The robust means of measured elements (µg l 1 ) in the industrial waste water sample without sample pretreatment () and with nitric acid digestion (). Effect of sample pretreatment on elemental concentrations in sediment Elements in the sediment sample were measured mainly after nitric acid or nitric acid and hydrogen peroxide digestion (). Only 2 % of the participants digested the sediment sample with aqua regia (SO6). As the number of participants using aqua regia digestion was very low, only from 4 to participants, a more detailed comparison of the sample pretreatment methods is not possible. The robust mean values of both sample pretreatment methods are shown in Table 1. For Cr, Fe and V the robust mean obtained after nitric acid digestion (sample ) was 1% and for Al about 40% lower than after aqua regia digestion (sample SO6). There was a statistically signi cant difference (ttest) between aluminium results gained using nitric acid digestion () and aqua regia digestion (SO6, Appendix.2).

18 16 Effect of measurement methods on elemental results The most commonly used analytical method was ICPOES, followed by ICPMS and GAAS, while FAAS was used only in a few cases (Appendices.1 and.3). The difference between the average concentrations of metals measured by different measurement methods was tested using the ttest. The results of the ttest are shown in Appendix.3. There were some statistically signi cant differences between the results obtained using different methods from some samples. These were as follows: Measurement methods GAAS/ ICPOES GAAS/ ICPMS ICPOES/ICPMS FAAS/ICPOES CVAAS/CVAFS HydrideFIAS/CVAFS Metal/Sample Co, V ; Cr, V Se Al ; As, Co ; Cr; Pb Cu HgA1Hg HgA1Hg The signi cant differences were most abundant between GAAS and ICPOES and between ICPOES and ICPMS measurements. GAAS results were lower than ICPMS results for all measurands and sample types (Appendix.3). For Al and As ICPOES results were higher than ICPMS results, while for Co, Cr and Pb they were lower. There were two populations of Se results in sample (mean values ca. 0. and 1.3 mgkg 1 ) and the evaluation was impossible. For Se founded statistically signi cant difference between the GAAS and ICPMS results in the sample. Obtaining accurate Se results at this low concentration level is clearly a rather demanding task. Volatilization during sample pretreatment or analysis (e.g. GAAS) may cause loss of analyte, which might explain low recoveries. However, a numerous of reasons may cause results that are erroneously high. Selenium is poorly ionized in an inductively coupled plasma which limits sensitivity even if ICPMS is used. High carbon concentrations increase the sensitivity of Se in ICPMS, but this problem is usually encountered in the analysis of organic matrices like biological tissue samples, when measured against aqueous calibration standards low in carbon. This interference cannot be overcome by using collision or reaction cell instruments since it occurs in the plasma, even if the use of said instrumentation is otherwise very bene cial in the determination of Se. In ICPMS measurements internal standardization is often used to improve the reproducibility and accuracy since any uctuations in the sample introduction system during measurement are cancelled out. If matrix effects are to be corrected for, it is important the internal standard behaves similarly to the analyte being corrected. Differences in mass and/or ionization potential may result in a false correction. Internal standard correction is possible in simultaneous ICPOES as well, but the choice of internal standard can be more dif cult than in ICPMS, since spectral interferences are often complex in emission spectrometry. The internal standard must not spectrally interfere with the analyte or vice versa. It should also be kept in mind that spectral interferences cannot be corrected for by internal standardization. In addition, the emission lines of the internal standard and the analyte must behave similarly. Ionization and/or excitation potentials should match each other as closely as possible. Simultaneous array spectrometers equipped with solid state detectors are very robust and wavelength stable, thus internal standardization is not a prerequisite to reach good results in environmental samples. ICP techniques have a longer linear working range compared to AAS. In AAS multiple dilutions may be necessary, which might increase measuring uncertainties. Dilution can be used in ICP

19 17 measurements to reduce or eliminate matrix effects if the analyte concentration is high enough. As a general note, a low recovery may be an indication of loss of analyte which can occur during sample pretreatment (e.g. volatilization during acid digestion) or measurement (e.g. GAAS analysis). It may also be caused by incorrect background correction (ICPOES) or matrix effects. Recoveries that are too high may be caused by spectral interferences (overlapping wavelengths in emission spectrometry, polyatomic or isobaric interferences in mass spectrometry), matrix effects or contamination. Matrix effects can often be overcome by matrix matching the calibration standards, however this is often dif cult with environmental samples since the elemental concentrations vary a lot even within the same sample type. Effect of measurement methods on mercury results Mercury was determined using various oxidants, digestion and measuring methods (Appendix.1). Only about half of the participants reported their methods, due to this the comparison of methods is only informative. From water samples mercury was mainly measured by CVAAS, followed by CVAFS, and hydridefias methods (Appendix.4). According to the statistical treatment (ttest) the signi cant difference was evident only when comparing the results between CVAAS and CVAFS and between hydridefias and CVAFS measurements from the sample A1Hg. The difference in the results is more likely coming from different sample pretreatment procedures than different methods. And since the number of the results was very low (CVAFS n=6 and hydridefias n=3), the reliable estimation of signi cance difference cannot be made. 3.3 Uncertainties of the results At maximum about 6 % of participants reported the expanded uncertainties with their results for some measurements (Table 4, Appendix ). The range of the reported uncertainties varied greatly between the measurements and the sample types. Very low uncertainties can be considered questionable, if lower than the repeatability (the withinlaboratory standard deviation, s w, Table 2). Several approaches were used for estimating of measurement uncertainty (Appendix ). The approach based on existing IQC data (Meth 2), validation data (Meth 3) or CRM data (Meth 4) were most common. Generally, the approach for estimating measurement uncertainty has not made a de nite impact on the uncertainty estimates. It is evident that harmonization in the estimating of uncertainties should be continued.

20 Table The range of the expanded measurement uncertainties reported with the results by the participants in the PT3/. 4 Evaluation of performance The evaluation of performance is based on z scores. The calculated z scores are presented with the results of each participant in Appendix 8 and the summary of z scores is presented in Appendix 9. The total number of laboratories participating in this PT was 4, of which one laboratory reported results by two different analytical methods (6 laboratories shown in Appendix 7). The robust standard deviation of the results was mostly (9 % of the results) lower than %. In the arti cial sample the concentrations were low. Accepting deviations of 1 30 % from the assigned values for 79 % of results were satisfactory. There were more dif culties in the measurement of Zn, where less than 70 % of results were satisfactory. On the other hand, in the measurement of Co over 90 % of the results were satisfactory. For Fe in the sample only 70 % of results were satisfactory. The reason to the low percentage might be that the participants have not noticed the information of the sample acidi cation given by the provider, which may have in uenced the measurements. In the measurements of the arti cial sample the concentrations were fairly high and 86 % of the results were satisfactory, when accepting deviations of % from the assigned values. The number of satisfactory results was lower than 80 % for Cr, Cu and Mn. For the natural water sample 87 % of the participants gained satisfactory results, when deviations of 1 2 % from the assigned value were accepted. For Fe and V all results were satisfactory, while for Se less than 80 % of the results were satisfactory. For the waste water samples ( and /) 93 % of the results were satisfactory, when deviations of 2 % from the assigned value were accepted. For As, Co, Cr, Ni and V all results were satisfactory at least for one sample type. For the industrial waste water without sample pretreatment 93 % of the results were satisfactory. After sample pretreatment for the sample also 93 % of the results were satisfactory.

21 19 On average the least satisfactory results were gained for Hg from all sample types (70 83 %), when accepting deviations of 2 % from the assigned value. The high variety of measuring and pretreatment techniques used by the laboratories creates differences in analysis results. The results of the sediment sample SO6 was not evaluated due to the low number of participants. The same applies to TC in the sediment. The result of Se was not evaluated due to the high deviation between the results. For the sediment sample deviations of 1 2 % from the assigned value were accepted. 87 % of the results obtained after nitric acid digestion () were satisfactory. The most dif cult elements to be measured seemed to be Cd, Pb and Hg from the sediment sample after nitric acid digestion, where less than 80 % of the results were satisfactory. In total, 87 % of the results in this pro ciency test were satisfactory. About 60 % of the participants used accredited methods and 87 % of their results were satisfactory. SYKE arranged a similar pro ciency test in 09 and then 87 % of the results were satisfactory []. SUMMARY Finnish Environment Institute (SYKE) carried out the pro ciency test for analysis of elements in waters and sediment in April August. The measured analytes were: Al, As, Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb, Se, V, Zn, N, P, S and TC. In total 4 laboratories participated in the pro ciency test. The sample types were: arti cial and natural water, municipal and industrial waste water and sediment. The calculated concentrations or the robust mean of the results reported by the participants were used as the assigned values for measurands, with the exception of Pb in water samples. For Pb metrologically traceable assigned values were used for samples,,, and. The uncertainties of the calculated assigned values and metrologically traceable values were 3 % or less. The uncertainties of the consensus assigned values (the robust mean) varied from 1.8 % to 11 %. The evaluation of the performance of the participants was carried out using z scores. In some cases the evaluation of the performance was not possible e.g. due to the low number of participants. In total, 87 % of the results in this pro ciency test were satisfactory when deviations of 30 % from the assigned values were accepted. Over half of the participants used accredited methods and 87 % of their results were satisfactory. 6 YHTEENVETO Suomen ympäristökeskuksen laboratorio järjesti pätevyyskokeen ympäristönäytteitä analysoiville laboratorioille kesällä. Pätevyyskokeessa määritettiin synteettisestä näytteestä, kolmesta erityyppisestä vesinäytteestä sekä sedimenttinäytteestä seuraavat alkuaineet: Al, As, Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb, Se, V, ja Zn, Lisäksi sedimenttinäytteestä pyydettiin määrittämään N, P, S ja TC. Pätevyyskokeeseen osallistui yhteensä 4 laboratoriota, joista kaksi laboratoriota raportoi kahdella eri menetelmällä analysoidut tulokset. Laboratorioiden pätevyyden arviointi tehtiin zarvon avulla ja sen laskemisessa käytetyn kokonaishajonnan tavoitearvot olivat välillä 30 %. Mittaussuureen vertailuarvona käytettiin pääsääntöisesti laskennallista pitoisuutta tai osallistujien ilmoittamien tulosten robustia keskiarvoa. Lyijylle käytettiin metrologisesti jäljitettävää tavoitearvoa. Tavoitearvon epävarmuus synteettisille näytteille ja metrologisesti jäljitettävälle arvolle oli pienempi kuin 3 % ja robustia keskiarvoa käytettäessä tavoitearvon epävarmuus vaihteli 1.8 %

22 11 % välillä. Sedimenttinäytteen kaikkia tuloksia ei voitu arvioida, koska testiin osallistuneiden lukumäärä oli alhainen tai tulosten välinen poikkeama oli suuri. Eri analyysimenetelmillä saatujen tulosten pitoisuuksissa esiintyi jonkin verran merkitseviä eroja varsinkin vesinäytteiden määrittämisessä. Erot eivät olleet kuitenkaan systemaattisia jonkin tietyn menetelmän suhteen. Koko tulosaineistossa hyväksyttäviä tuloksia oli 87 %, kun vertailuarvosta sallittiin 30 %:n poikkeama. Yli puolet osallistujista käytti akkreditoituja määritysmenetelmiä ja näistä tuloksista oli hyväksyttäviä 87 %. REFERENCES 1. ISO/IEC Guide 431, Pro ciency Testing by Interlaboratory Comparison Part1: Development and Operation of Pro ciency Testing Schemes. 2. ISO/IEC 17043,. Conformity assessment General requirements for pro ciency testing. 3. ISO 1328, 0. Statistical methods for use in pro ciency testing by interlaboratory comparisons. 4. Thompson, M., Ellison, S. L. R., Wood, R., 0. The International Harmonized Protocol for the Pro ciency Testing of Analytical Chemistry laboratories (IUPAC Technical report, Draft). 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.. Leivuori, M., Korhonen, K., Järvinen, O., Näykki, T., SaraAho, T., Tervonen, K., Lanteri, S. and Ilmakunnas, M. 09. SYKE Pro ciency Test 4/09. Reports of Finnish Environment Institute 28/09. Helsinki. ( /download. asp?contentid=114413&lan= )

23 21 APPENDIX 1 APPENDIX 1 PARTICIPANTS IN THE PROFICIENCY TEST 3/ ALS Scandinavia AB, Luleå, Sweden Arkhangelsk Department for Hydrometeorology and Environmental Monitoring, Russia Boliden Harjavalta Oy, Harjavalta, Finland Boliden Kokkola Oy, Kokkola, Finland Centre for Hydrometeorology and Environmental Monitoring of Komi Republic area, Russia Centre for Hydrometeorology and Environmental Monitoring of S.Petersburg and Leningrad area, Russia Centre for Laboratory Analysis and Technical Measurement in Arkhangelsk area, Russia Centre for Laboratory Analysis and Technical Measurement in Komi Republic area, Russia Centre for Laboratory Analysis and Technical Measurement in Murmansk area, Russia Centre for Laboratory Analysis and Technical Measurement in S.Petersburg and Leningrad area, Russia Danisco Sweeteners Oy, Kotka, Finland Ekoanalit laboratory of the Institute of Biology of KSC, Russia Ekokem Oy Ab, Riihimäki, Finland Eurofins Environment Sweden AB, Lidköping, Sweden Eurofins Scientic Finland Oy, Tampere, Finland FCG Finnish Consulting Group Oy, Helsinki, Finland Force Technology, Brøndby, Denmark Hortilab Oy Ab, Närpes, Finland HSY, Käyttölaboratorioyksikkö, Jätevesilaboratorio, Espoo, Finland Institute of North Industrial Ecology Problems, Kola SC RAS, Russia ITM, Stockholm University, Stockholm, Sweden IVL Swedish Environmental Research Institute, Göteborg, Sweden Jyväskylän yliopisto, Ympäristöntutkimuskeskus, Jyväskylä, Finland Jyväskylän ympäristötoimen laboratorio, Jyväskylä, Finland Kauhajoen elintarvikelaboratorio, Kauhajoki, Finland KCL Kymen laboratorio Oy, Kuusankoski, Finland Kokemäenjoen vesistön vesiensuojeluyhdistys ry, Tampere, Finland Laboratorio Ambiental DINAMA, Montevideo, Uruguay Laboratory of NevaLadoga Basin Water Administration, Russia Landesamt f. Umwelt, Naturschutz und Geologie, Güstrow, Germany Lapin Vesitutkimus Oy, Rovaniemi, Finland LounaisSuomen vesi ja ympäristötutkimus Oy, Turku, Finland MetropoliLab, Helsinki, Finland Metsäntutkimuslaitos/Keskuslaboratorio, Vantaa, Finland Murmansk Department for Hydrometeorology and Environmental Monitoring, Russia Nablabs Oy, Oulu, Finland Norilsk Nickel Harjavalta Oy, Harjavalta, Finland Outokumpu Tornio Works, Tornio, Finland Outotec Reasearch Oy, Pori, Finland Porilab, Pori, Finland Pyhäsalmi Mine Oy, Pyhäsalmi, Finland Ramboll Analytics, Lahti, Finland Rauman ympäristölaboratorio, Rauma, Finland Rautaruukki OYJ, Ruukki Metals, prosessilaboratorio, Hämeenlinna, Finland Rautaruukki OYJ, Ruukki Metals, Raahe, Finland Sachtleben Pigments Oy, Pori, Finland SavoKarjalan ympäristötutkimus Oy, vesiyksikkö, Kuopio, Finland SGS Inspection Services Oy, Kotka, Finland Suomen ympäristöpalvelu Oy, Oulu, Finland Sweden Recycling, Hovmantorp, Sweden SYKE, Laboratoriot, Helsinki, Finland SYKE, Laboratoriot, Oulu, Finland UPM Tutkimuskeskus, Lappeenranta, Finland Viljavuuspalvelu Oy, Mikkeli, Finland Water Research & Control Center joint stock Company Limited, Russia Ålands miljö och hälsoskyddsmyndighet Laboratoriet, Jomala Åland, Finland

24 APPENDIX 2/1 APPENDIX 2 22 PREPARATION OF THE SAMPLES The artificial sample was prepared by diluting the SRM NIST 1643e with acidified water (1:). The artificial sample was prepared by mixing some separate Merck Certipur RM metal solutions and diluting with acidified water. The artificial sample A1Hg was prepared by diluting the CRM Romil Hg solution with acidified water. The water samples,, TM (/) and N3Hg were prepared by adding some separate metal solutions into the original water sample. The sediment sample S6M (/SO6/ST6) was prepared by combining various dried estuary sediments of the Baltic Sea and homogenization the mixture sediment sample. Al As Cd Co Cr Cu Fe Hg Mn Ni Pb Se Analyte Original Dilution Additon Ass. value 1.6 Original Dilution Additon Ass. value 6.0 Original Dilution Additon Ass. value 0.66 Original Dilution Additon Ass. value 2.71 Original Dilution Additon Ass. value 2.04 Original Dilution Additon Ass. value 2.28 Original Dilution Additon Ass. value.2 Original Dilution Additon Ass. value Original Dilution Additon Ass. value 3.9 Original Dilution Additon Ass. value 6.24 Original Dilution Additon Ass. value 1.99 Original Dilution Additon Ass. value < / / / / / / / / / / /6.6 < /2.3 A1Hg N3Hg < THg < /SO / / / / / / / / / / V Zn Original Dilution Additon Ass. value 3.79 Original Dilution Additon Ass. value / / / /179

25 APPENDIX 2 23 APPENDIX PREPARATION OF THE SAMPLES (continued) 2/2 N P S TC Analyte Original Dilution Additon Ass. value Original Dilution Additon Ass. value Original Dilution Additon Ass. value Original Dilution Additon Ass. value S6M/ Original = the original concentration Dilution = the ratio of dilution Addition = the addition concentration Ass. value = the assigned value

26 APPENDIX 3 24 APPENDIX 3 TESTING OF HOMOGENEITY Analyte/sample Concentration (µg l 1 or mg kg 1 ) s p % s p s a s a /s p Is s a /s p <0.? s bb s bb 2 c Is s bb 2 <c? Cd/ Yes Yes Cu/ Yes Yes Hg/N3Hg Yes Yes Mn/ Yes Yes Zn/ Yes Yes Cd/ Yes Yes Cu/ Yes Yes Mn/ Yes Yes Zn/ Yes Yes Cd/ Yes Yes Cu/ Yes Yes Hg/THg Yes Yes Mn/ Yes Yes Zn/ Yes Yes Cd/S6M Yes Yes Cu/S6M Yes Yes Hg/S6M Yes Yes Mn/S6M Yes Yes P/S6M Yes Yes S/S6M Yes Yes Zn/S6M Yes Yes s p % = standard deviation for proficiency assessment s a = analytical deviation, standard deviation of the results in a sub sample s bb = betweensample deviation, standard deviation of results between sub samples c = F1 s all 2 + F2 s a 2 where: s all 2 = (0.3s p ) 2 F1 = 1.88 and F2 = 1.01, when the number of sub samples is The analytical deviation filled up the criteria s a /s p <0. for each sample and analyte. Also in the each case the s bb 2 was smaller than the criteria c. Conclusion: The samples could be regarded as homogenous.

27 APPENDIX APPENDIX COMMENTS SENT BY THE PARTICIPANTS 4.1 Laboratory Comments on samples Action/SYKE 22 The concentrations of metals were too From the participant has asked by , which sample low for the AASmeasurements. and metals the comment stand for. The participant has International participants In the letter sent with the samples to the foreign participants, was erroneously mentioned Sb to be measured from the sediment sample (S6M). not given any reply. To the participants sent information from this issue by . Laboratory Comments on results Action/SYKE 1 The results of Cr were reported also for Cu. The Cu results were: 2.1 µg l 1 in, 7. µg l 1 in, 11.9 µg l 1 in,.4 µg l 1 in, 82. µg l 1 in. The data is not corrected in the original database. If the results should have been reported rightly they should have been satisfactory. 31 The results of N and P in the sediment sample were reported in g kg 1 unit, when the right one was mg kg 1. 7 Error in reporting the results of Pb in the samples and. The participant can recalculate z scores according to the guide for participating laboratories in Proftest proficiency testing schemes ( The results were not corrected in the original database. If the results should have been reported rightly they should have been satisfactory. The participant can recalculate z scores according to the guide for participating laboratories in Proftest proficiency testing schemes ( The right results were: Pb in 6.88 µg l 1 and in 3.41 µg l 1. If the results should have been reported rightly they should have been satisfactory. The participant can recalculate z scores according to the guide for participating laboratories in Proftest proficiency testing schemes (

28 APPENDIX 4.2 APPENDIX COMMENTS TO THE PARTICIPANTS Laboratory Comments on results, 24 Laboratories reported only one result, though replicate results were requested. These results were not included in the calculation of assigned values. The laboratory has reported the measurement uncertainties as ± instead of UC %. The values were corrected by the provider. 7 The laboratory has reported the measurement uncertainties UC % by formulas, which were excluded from the handling. From the Fe results in the sample was seen that all participants have not read the information about the sample preparation (acidification) in the letter sent with the samples. Fewer errors than previously were found in the wrongly reported units, which is a good feedback. In the future the wrong unit will be not corrected by the provider, unless the total amount of results is too low for the statistical calculations.

29 APPENDIX.1 ANALYTICAL METHODS Hg/Pretreatment/Measurement: 27 APPENDIX.1/1 Lab 1) Sample Oxidant/ Equipment and temperature in Measurement reducing digestion 1 A1HgTHg KMnO 4 /K 2 S 2 O 8 CETAC M6000A HNO 3 /H 2 SO 4 A1Hg, THg SnCl 2 Microwave digestor: Alton Para Perkin Elmer FIMS 0 Multiwave 30000Solv S6M SnCl 2 Microwave digestor: Alton Para Perkin Elmer FIMS 0 Multiwave 30000Solv 11 A1HgTHg KMnO 4 /K 2 S 2 O 8 Water bath 9 C +/ 3 C CVAAS S6M HNO 3 Microwave oven MARS CVAAS 12 THg HNO 3 Microwave oven CEM. Mars 17 C CVAAS S6M HNO 3 /HCl Microwave oven CEM. Mars 17 C CVAAS 14 N3Hg K 2 Cr 2 O 7 Microwave digestion, Tmax = 17 C CV/AFS S6M Aqua regia Microwave digestion, Tmax = 10 C CV/AFS 18 A1Hg, THg SnCl 2 Autoclave 121 C Hydride generation / FIAS S6M SnCl 2 Autoclave 121 C Hydride generation / FIAS 21 A1Hg ICPOES S6M HCl+HNO 3 Microwave oven 17 C ICPOES 22 A1Hg, N3Hg HNO 3 CVAAS THg KMnO 4 Water bath 9 C Oxidation with O 2 + AAS S6M KMnO 4 Water bath 9 C Oxidation with O 2 + AAS 26 A1Hg, N3Hg HNO 3 CV/AFS KBr/KBrO 3 THg HNO 3 Microwave oven closed vessels, 0 C CV/AFS KBr/KBrO 3 S6M HNO 3 Microwave oven closed vessels, 0 C Oxidation with O 2 + AAS 31 A1HgTHg KMnO 4 Direct measuring CVAAS S6M O 2 Milestone DMA80: drying 300 C and Oxidation with O 2 + AAS combustion 80 C 32 A1HgTHg HNO 3 ICPMS S6M Mikrowave oven ICPMS 33 A1HgTHg KBr/KBrO 3 Room temperature 30 min. CV/AFS 3 A1Hg, THg KMnO 4 /HNO 3 / Water bath 9 C 2 h CVAAS K 2 S 2 O 8 36 A1Hg, THg K 2 Cr 2 O 7 CVAAS S6M K 2 Cr 2 O 7 CEM MDS microwave oven CVAAS 40 A1Hg, THg KMnO 4 + HNO 3 Autoclave, 1 C CVAFS 43 A1HgTHg KMnO 4 CVAAS S6M KMnO 4 Microwave oven, 17 C CVAAS 49 N3Hg,THg Hydride / FIAS S6M HNO 3 Microwave oven Hydride / FIAS 3 THg HNO 3 Autoclave 1 C ICPMS S6M HNO 3 Autoclave 1 C ICPMS 1) Laboratories 3,, 8, 16, 17, 19, 23, 2, 28, 29, 39, 44,0, 1, 4, didn't report the pretreatment method.

30 APPENDIX.1/2 APPENDIX.1 ANALYTICAL METHODS (continue) 28 Metals/Pretreatment the waste water sample TM no digestion digestion with acid Metals/Pretreatment the sediment S6M digestion with HNO 3 SO6 digestion with HNO 3 + HCl ST6 digestion with HNO 3 + HF Metals/ Measurement from the water and the sediment samples Analyte Code Method Al, Cd, Co, Cr, 1 FAAS Cu, Fe, Mn, Ni, 2 GAAS Pb, Se, V, Zn 3 ICPOES 4 ICPMS Hydride generation 6 Other method, please specify As 2 GAAS 3 ICPOES 4 ICPMS Hydride generation 6 Other method, please specify Hg/ Measurement from the water samples and the sediment Analyte Code Method Hg 1 CVAAS 2 ICPOES 3 Hydride/FIAS 4 Oxidation with O 2 + AAS (e.g. Lecoanalyser) CVAFS 6 Other method, please specify N, P, S and TC Measurement from the sediment Analyte Code Method N 1 NKjeldahl or equivalent method 2 Equipment, please specify: 3 Other method, please specify: P 1 Kjeldahl or equivalent method 2 Equipment, please specify: 3 Other method, please specify: S 1 Equipment, please specify: 2 Other method, please specify: TC 1 Equipment, please specify: Combustion temperature ( o C) : 2 Other method, please specify:

31 29 APPENDIX Appendix.2 SIGNIFICANT DIFFERENCES IN THE RESULTS REPORTED USING DIFFERENT SAMPLE DIGESTION.2 In the statistical comparison of the digestion methods has included the data, in which the number of the results was 3. Digestion Samples and Analyte Sample/Method 1) X (µg l 1 ) sd n Significant difference As X Digestion Samples and SO6 Analyte Sample/Method 2) X (mg kg 1 ) sd n Significant difference Al X SO where X: the mean value sd: the standard deviation n: the number of the results 1) 2) no digestion digestion with HNO 3 digestion with HNO 3 or HNO 3 + H 2 O 2 SO6 digestion with HNO 3 + HCl (aqua regia)

32 APPENDIX.3 Appendix.3 SIGNIFICANT DIFFERENCES IN THE RESULTS REPORTED USING DIFFERENT MEASUREMENT METHODS 30 In the statistical comparison of the methods has been treated the data, in which the number of the results was 3. Analyte Sample Method X sd n Significant difference Al 3. ICPOES X: meth ICPMS As 3. ICPOES X: meth ICPMS 8 8 Co 2. GAAS X: meth 23, ICPOES ICPMS Cr 2. GAAS X: meth ICPOES ICPOES X: meth ICPMS Cu 2. GAAS X: meth ICPOES FAAS X: meth ICPOES Hg A1Hg 1. CVAAS X: meth 1, 3 3. Hydride/FIAS CVAFS Pb 3. ICPOES X: meth ICPMS Se 2. GAAS X, sd: meth ICPMS V 2. GAAS X, sd: meth ICPOES GAAS X, sd: meth ICPOES where. X: the mean value sd: the standard deviation n: the number of the result

33 LIITE.4. RESULTS GROUPPED ACCORDING TO THE METHODS APPENDIX.4.Method code see appendix.1 31 LIITE APPENDIX.4 / 1 Al Meth 2 Meth 3 Meth 4 Al Meth 1 Meth 2 Meth 3 Meth 4 Al Meth 1 Meth 2 Meth 3 Meth 4 Meth 6 SYKE Interlaboratory comparison test 3/

34 LIITE APPENDIX.4 / 2 32 Al Meth 1 Meth 2 Meth 3 Meth 4 Al SO Meth 3 Al Meth 1 Meth 2 Meth 3 Meth 4 SYKE Interlaboratory comparison test 3/

35 33 LIITE APPENDIX.4 / 3 Al Meth 2 Meth 3 Meth 4 Al Meth 1 Meth 2 Meth 3 Meth 4 Meth 6 As 9 8, 8 7, 7 6, 6, 4, 4 3, Meth 1 Meth 2 Meth 3 Meth 4 Meth SYKE Interlaboratory comparison test 3/

36 LIITE APPENDIX.4 / 4 34 As Meth 1 Meth 2 Meth 3 Meth 4 Meth Meth 6 As 6, 4, 4 3, 3 2, 2 1, Meth 1 Meth 2 Meth 3 Meth 4 Meth 6 As Meth 2 Meth 3 Meth 4 SYKE Interlaboratory comparison test 3/

37 3 LIITE APPENDIX.4 / As SO Meth 2 Meth 3 Meth 4 As Meth 1 Meth 2 Meth 3 Meth 4 Meth As Meth 2 Meth 3 Meth 4 Meth SYKE Interlaboratory comparison test 3/

38 LIITE APPENDIX.4 / 6 36 As 7, 7 6, 6, 4, 4 3, 3 2, 2 Meth 1 Meth 2 Meth 3 Meth 4 Meth Meth 6 Cd 0,9 0,9 0,8 0,8 0,7 0,7 0,6 0,6 0, 0, 0,4 0,4 0,3 Meth 1 Meth 2 Meth 3 Meth 4 Meth 6 Cd 8, 8 7, 7 6, 6, 4, Meth 1 Meth 2 Meth 3 Meth 4 Meth 6 SYKE Interlaboratory comparison test 3/

39 37 LIITE APPENDIX.4 / 7 Cd 1,2 1,1 1 0,9 0,8 0,7 0,6 0, Meth 2 Meth 3 Meth 4 Meth 6 Cd 1,1 1 0,9 0,8 0,7 0,6 0, 0,4 0,3 Meth 2 Meth 3 Meth 4 Cd SO6 1,4 1,3 1,2 1,1 1 0,9 0,8 0,7 0,6 0, 0,4 Meth 2 Meth 3 Meth 4 SYKE Interlaboratory comparison test 3/

40 LIITE APPENDIX.4 / 8 38 Cd Meth 1 Meth 2 Meth 3 Meth 4 Meth 6 Cd Meth 1 Meth 2 Meth 3 Meth 4 Cd 3,8 3,6 3,4 3,2 3 2,8 2,6 2,4 2,2 2 1,8 Meth 2 Meth 3 Meth 4 Meth 6 SYKE Interlaboratory comparison test 3/

41 39 LIITE APPENDIX.4 / 9 Co 4 3,8 3,6 3,4 3,2 3 2,8 2,6 2,4 2,2 2 1,8 1,6 1,4 Meth 1 Meth 2 Meth 3 Meth 4 Meth 6 Co Meth 1 Meth 2 Meth 3 Meth 4 Meth 6 Co 4, 4 3, 3 2, 2 Meth 1 Meth 2 Meth 3 Meth 4 Meth 6 SYKE Interlaboratory comparison test 3/

42 LIITE APPENDIX.4 / 40 Co Meth 1 Meth 2 Meth 3 Meth 4 Co SO Meth 3 Meth 4 Co Meth 1 Meth 2 Meth 3 Meth 4 Meth 6 SYKE Interlaboratory comparison test 3/

43 41 LIITE APPENDIX.4 / 11 Co Meth 1 Meth 2 Meth 3 Meth 4 Co Meth 1 Meth 2 Meth 3 Meth 4 Meth 6 Cr 3 2,8 2,6 2,4 2,2 2 1,8 1,6 1,4 1,2 Meth 2 Meth 3 Meth 4 Meth 6 SYKE Interlaboratory comparison test 3/

44 LIITE APPENDIX.4 / Cr Meth 1 Meth 2 Meth 3 Meth 4 Meth 6 Cr Meth 2 Meth 3 Meth 4 Meth 6 Cr Meth 1 Meth 2 Meth 3 Meth 4 SYKE Interlaboratory comparison test 3/

45 43 LIITE APPENDIX.4 / 13 Cr SO Meth 3 Meth 4 Cr Meth 1 Meth 2 Meth 3 Meth 4 Meth 6 Cr Meth 1 Meth 2 Meth 3 Meth 4 SYKE Interlaboratory comparison test 3/

46 LIITE APPENDIX.4 / Cr Meth 2 Meth 3 Meth 4 Meth 6 Cu 3,4 3,2 3 2,8 2,6 2,4 2,2 2 1,8 1,6 1,4 1,2 Meth 1 Meth 2 Meth 3 Meth 4 Meth 6 Cu Meth 1 Meth 2 Meth 3 Meth 4 Meth 6 SYKE Interlaboratory comparison test 3/

47 4 LIITE APPENDIX.4 / 1 Cu Meth 1 Meth 2 Meth 3 Meth 4 Meth 6 Cu Meth 1 Meth 2 Meth 3 Meth 4 Cu SO Meth 3 Meth 4 SYKE Interlaboratory comparison test 3/

48 LIITE APPENDIX.4 / Cu Meth 1 Meth 2 Meth 3 Meth 4 Meth 6 Cu Meth 1 Meth 2 Meth 3 Meth 4 Cu Meth 1 Meth 2 Meth 3 Meth 4 Meth 6 SYKE Interlaboratory comparison test 3/

49 47 LIITE APPENDIX.4 / 17 Fe Meth 1 Meth 2 Meth 3 Meth 4 Meth 6 Fe Meth 1 Meth 3 Meth 4 Meth 6 Fe Meth 1 Meth 3 Meth 4 Meth 6 SYKE Interlaboratory comparison test 3/

50 LIITE APPENDIX.4 / Fe Meth 1 Meth 3 Meth 4 Fe SO Meth 3 Fe Meth 1 Meth 3 Meth 4 Meth 6 SYKE Interlaboratory comparison test 3/

51 49 LIITE APPENDIX.4 / 19 Fe Meth 1 Meth 3 Meth 4 Fe Meth 1 Meth 3 Meth 4 Meth 6 Hg A1Hg 1,2 1,1 1 0,9 0,8 0,7 0,6 0, Meth 1 Meth 3 Meth 4 Meth Meth 6 SYKE Interlaboratory comparison test 3/

52 LIITE APPENDIX.4 / 0 Hg N3Hg 0,26 0,24 0,22 0,2 0,18 0,16 0,14 0,12 0,1 0,08 Meth 1 Meth 3 Meth 4 Meth Meth 6 Hg S6M 0,2 0,18 0,16 0,14 0,12 0,1 0,08 0,06 Meth 1 Meth 2 Meth 3 Meth 4 Meth Meth 6 Hg THg 3,6 3,4 3,2 3 2,8 2,6 2,4 2,2 2 1,8 1,6 1,4 1,2 1 Meth 1 Meth 3 Meth 4 Meth Meth 6 SYKE Interlaboratory comparison test 3/

53 1 LIITE APPENDIX.4 / 21 Mn 6, 4, 4 3, 3 2, 2 1, Meth 1 Meth 2 Meth 3 Meth 4 Meth 6 Mn Meth 1 Meth 2 Meth 3 Meth 4 Meth 6 Mn Meth 1 Meth 2 Meth 3 Meth 4 Meth 6 SYKE Interlaboratory comparison test 3/

54 LIITE APPENDIX.4 / 22 2 Mn Meth 1 Meth 3 Meth 4 Mn SO Meth 3 Mn Meth 1 Meth 2 Meth 3 Meth 4 Meth 6 SYKE Interlaboratory comparison test 3/

55 3 LIITE APPENDIX.4 / 23 Mn Meth 1 Meth 3 Meth 4 Mn Meth 1 Meth 2 Meth 3 Meth 4 Meth 6 N S6M Meth 1 Meth 2 Meth 3 SYKE Interlaboratory comparison test 3/

56 LIITE APPENDIX.4 / 24 4 Ni 9 8, 8 7, 7 6, 6, 4, 4 3, Meth 2 Meth 3 Meth 4 Meth 6 Ni Meth 1 Meth 2 Meth 3 Meth 4 Meth 6 Ni 9 8, 8 7, 7 6, 6, 4, 4 3, Meth 2 Meth 3 Meth 4 Meth 6 SYKE Interlaboratory comparison test 3/

57 LIITE APPENDIX.4 / 2 Ni Meth 1 Meth 2 Meth 3 Meth 4 Ni SO Meth 3 Meth 4 Ni Meth 1 Meth 2 Meth 3 Meth 4 Meth 6 SYKE Interlaboratory comparison test 3/

58 LIITE APPENDIX.4 / 26 6 Ni Meth 1 Meth 2 Meth 3 Meth 4 Ni Meth 2 Meth 3 Meth 4 Meth 6 P S6M Meth 1 Meth 2 Meth 3 SYKE Interlaboratory comparison test 3/

59 7 LIITE APPENDIX.4 / 27 Pb 2,8 2,6 2,4 2,2 2 1,8 1,6 1,4 1,2 1 Meth 2 Meth 3 Meth 4 Meth 6 Meth 7 Pb Meth 1 Meth 2 Meth 3 Meth 4 Meth 6 Meth 7 Pb 8 7, 7 6, 6, 4, 4 Meth 2 Meth 3 Meth 4 Meth 6 Meth 7 SYKE Interlaboratory comparison test 3/

60 LIITE APPENDIX.4 / 28 8 Pb Meth 1 Meth 2 Meth 3 Meth 4 Pb SO Meth 3 Meth 4 Pb Meth 1 Meth 2 Meth 3 Meth 4 Meth 6 Meth 7 SYKE Interlaboratory comparison test 3/

61 9 LIITE APPENDIX.4 / 29 Pb Meth 2 Meth 3 Meth 4 Pb 4, 4 3, 3 2, 2 Meth 2 Meth 3 Meth 4 Meth 6 Meth 7 S S6M Meth 1 Meth 2 Meth 3 SYKE Interlaboratory comparison test 3/

62 LIITE APPENDIX.4 / Se 1,7 1,6 1, 1,4 1,3 1,2 1,1 1 0,9 0,8 0,7 Meth 2 Meth 4 Meth Meth 6 Se Meth 2 Meth 3 Meth 4 Meth Meth 6 Se 3,8 3,6 3,4 3,2 3 2,8 2,6 2,4 2,2 2 1,8 1,6 1,4 Meth 2 Meth 4 Meth Meth 6 SYKE Interlaboratory comparison test 3/

63 61 LIITE APPENDIX.4 / 31 Se Meth 2 Meth 3 Meth 4 Meth 6 Se SO6 3 2, 2 1, 1 0, 0 Meth 3 Meth 4 Se Meth 2 Meth 3 Meth 4 Meth SYKE Interlaboratory comparison test 3/

64 LIITE APPENDIX.4 / Se Meth 2 Meth 3 Meth 4 Meth Meth 6 Se 9, 9 8, 8 7, 7 6, 6, 4, 4 3, Meth 2 Meth 4 Meth Meth 6 TC S6M Meth 1 Meth 2 SYKE Interlaboratory comparison test 3/

65 63 LIITE APPENDIX.4 / 33 V,2 4,8 4,6 4,4 4,2 4 3,8 3,6 3,4 3,2 3 2,8 2,6 2,4 Meth 2 Meth 3 Meth 4 V Meth 2 Meth 3 Meth 4 V 7 6, 6, 4, 4 3, 3 2, Meth 2 Meth 3 Meth 4 SYKE Interlaboratory comparison test 3/

66 LIITE APPENDIX.4 / V Meth 2 Meth 3 Meth 4 V SO Meth 3 Meth 4 V Meth 2 Meth 3 Meth 4 SYKE Interlaboratory comparison test 3/

67 6 LIITE APPENDIX.4 / 3 V Meth 2 Meth 3 Meth 4 V Meth 2 Meth 3 Meth 4 Zn Meth 1 Meth 2 Meth 3 Meth 4 Meth 6 SYKE Interlaboratory comparison test 3/

68 LIITE APPENDIX.4 / Zn Meth 1 Meth 2 Meth 3 Meth 4 Meth 6 Zn Meth 1 Meth 2 Meth 3 Meth 4 Meth 6 Zn Meth 1 Meth 2 Meth 3 Meth 4 SYKE Interlaboratory comparison test 3/

69 67 LIITE APPENDIX.4 / 37 Zn SO Meth 3 Zn Meth 1 Meth 3 Meth 4 Meth 6 Zn Meth 1 Meth 2 Meth 3 Meth 4 SYKE Interlaboratory comparison test 3/

70 LIITE APPENDIX.4 / Zn Meth 1 Meth 2 Meth 3 Meth 4 Meth 6 SYKE Interlaboratory comparison test 3/

71 69 APPENDIX 6/1 APPENDIX 6 EVALUATION OF THE ASSIGNED VALUES AND THEIR UNCERTAINTIES Analyte Sample Assigned value Evaluation of the assigned value Expanded uncertainty of the assigned value, U Al 1.6 Robust mean 4.9 % 840 Robust mean 2.8 % 477 Robust mean 3.2 % 177 Robust mean 6.3 % 784 Robust mean 1.8 % 786 Robust mean.8 % Robust mean 7. % SO6 As 6.0 Calculated value 1.2 % 7 Calculated value 0.7 % 3.77 Robust mean 7.7 % 4.86 Robust mean 6. % 97.7 Robust mean 2.3 % 91.1 Robust mean 6.3 % 16.3 Robust mean 8.2 % SO6 Cd 0.66 Calculated value 1.1 % 6.40 Calculated value 0.8 % 0.81 Robust mean 4.9 % 2.82 Robust mean 3.8 % 30.1 Robust mean 2.9 % 30.3 Robust mean 4.4 % 0.71 Robust mean 11 % SO6 Co 2.71 Calculated value 1.2 % 47 Calculated value 0. % 3.12 Robust mean 3.6 % 1. Robust mean 3.9 % 40.3 Robust mean 2.3 % 40. Robust mean 3.4 % 16.9 Robust mean 8.0 % SO6 Cr 2.04 Calculated value 1.2 % 79 Calculated value 0.8%.3 Robust mean 4.2 % 8.37 Robust mean 6.2 % 121 Robust mean 1.9 % 1 Robust mean.2 % 6 Robust mean 7.9 % SO6

72 APPENDIX 6/2 APPENDIX 6 EVALUATION OF THE ASSIGNED VALUES AND THEIR UNCERTAINTIES (continue) Analyte Sample Assigned value Evaluation of the assigned value Expanded uncertainty of the assigned value, U Cu 2.28 Calculated value 1.3 % 67 Calculated value 0. % 12.2 Robust mean 3.3 % 9.92 Robust mean.2 % 83.4 Robust mean 2.4 % 8.6 Robust mean 3,0 % 40 Robust mean 8.1 % SO6 Fe.2 Robust mean 8.8 % 614 Calculated value 0.3 % 36 Robust mean 2.2 % 2490 Robust mean 2.7 % 803 Robust mean 2.1 % 79 Robust mean 4.1 % 4190 Robust mean 6.3 % SO6 Hg A1Hg 0.83 Calculated value 0.4 % N3Hg 0.17 Robust mean 8.7 % THg 2.28 Robust mean 8.6 % S6M 0.13 Robust mean 8.2 % Mn 3.9 Calculated value 1.2 % 90 Calculated value 0. % 44.2 Robust mean 3.4 % 81 Robust mean 2.4 % 41 Robust mean 2.6 % 43 Robust mean 3.3 % 14 Robust mean 6.4 % SO6 N S6M 462 Robust mean.9 % Ni 6.24 Calculated value 1.1 % 69 Calculated value 0. % 6.17 Robust mean 4.9 % 11.2 Robust mean.4 % 162 Robust mean 2.0 % 164 Robust mean 4.0 % 38.3 Robust mean 6.6 % SO6 P S6M 120 Robust mean.3 % Pb 1.99 IDICPMS 3.0 % 92.9 IDICPMS 3.0 % 6.12 IDICPMS 3.0 % 3.32 IDICPMS 3.0 % 67.6 IDICPMS 3.0 % 6.6 Robust mean.9 % 46. Robust mean 4.4 % SO6 S S6M 6800 Robust mean 3.6 % 70

73 71 APPENDIX 6/3 APPENDIX 6 EVALUATION OF THE ASSIGNED VALUES AND THEIR UNCERTAINTIES (continue) Analyte Sample Assigned value Evaluation of the assigned value Expanded uncertainty of the assigned value, U Se 1.2 Calculated value 1.2 % 43 Calculated value 0.7 % 2.67 Mean of ICPMS results 8.8 % 6.72 mg/l Robust mean 7.0% 30.1 Robust mean 6.0 % 29.3 Robust mean 7.3 % SO6 TC S6M V 3.79 Calculated value 1. % 86 Calculated value 0.7 % 4.83 Robust mean.4 % 12.6 Robust mean.3 % 82.8 Robust mean 1.9 % 82.4 Robust mean 4.2 % 70.3 Robust mean.2 % SO6 Zn 7.8 Calculated value 2.2 % 186 Calculated value 0.7 % 1.8 Robust mean 6. % 2.3 Robust mean 4.8 % 163 Robust mean 3.4 % 166 Robust mean 1. % 186 Robust mean 4.6 % SO6 Robust mean 1. Samples and the uncertainty was estimated on the basis of the sample preparation. 2. Other samples the uncertainty was estimated using the data of the results as follows: 0 U% where: n AV s rob U% = the expanded uncertainty of the assigned value n = the number of the results s rob = the robust standard deviation AV = the assigned value

74 APPENDIX 7 72 APPENDIX 7 TERMS IN THE RESULT TABLES Results of each participants (Appendix 8) Sample the code of the sample zgraphics z score the graphical presentation z score 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 (a test for the mean value) In addition, in robust statistics some results deviating from the original robust mean have been rejected Assigned value the reference value 2* Targ SD % the target value of total standard deviation for proficiency assessment (s p ) at the 9 % confidence level, equal 2 * s p Lab s result the result reported by the participant (the mean value of the replicates) Md. Median Mean Mean Robust mean Robust mean SD Standard deviation SD% Standard deviation, % SD %rob Robust standard deviation, % Passed The results passed the outlier test Missing i.e. < DL Num of labs the total number of the participants Summary on the z scores (Appendix 9) S satisfactory ( 2 z 2) Q questionable ( 2< z < 3), positive error, the result deviates more than 2 * s p from the assigned value q questionable ( 3 > z< 2), negative error, the result deviates more than 2 * s p from the assigned value U unsatisfactory (z 3), positive error, the result deviates more than 3 * s p from the assigned value u unsatisfactory (z 3), negative error, the result deviates more than 3 * s p from the assigned value Robust analysis: The items of data is sorted into increasing order, x 1, x 2, x i,,x p. Initial values for x * and s * are calculated as: X * = median of x i (i = 1, 2, p) s * = median of x i x* (i = 1, 2, p) x * i = x * if x i < x * x * i = x * + if x i > x * + x * i = x i otherwise The new values of x * and s * are calculated from: * x xi / p * s ( x i x ) 2 /( p 1) 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 [3].

75 73 LIITE APPENDIX 8 / 1 LIITE 8. RESULTS OF EACH PARTICIPANTS APPENDIX 8. Analyte Unit Sample zgraphics Z value Outl Assigned test OK value 2* Targ SD% Lab's result Md. Mean SD SD% Passed Outl. failed Missing Num of labs Laboratory Al As Cd Co Cr Cu Fe Hg Mn Ni Pb Se V 1 A1Hg N3Hg THg 1,490 yes 1,6 2 18, 1,4 1, 1,91 12, ,09 yes , ,741 yes ,9 7, ,281 yes ,1 4, ,2 yes ,8 14, ,16 yes 6,0 6,1 6,01,9 0,82 14, ,468 yes ,8 3,68 6, ,4 yes 3,77 2 3,1 3,71 3,7 0,877 24, ,23 yes 97,7 0 97,7 97,6 6,31 6, ,288 yes 4,86 2,04 4,97 4,8 0,731 1, ,12 yes 0,66 0,6 0,628 0,634 0, , ,031 yes 6,4 1 6,38 6,41 6,44 0,426 6, ,123 yes 0,81 0,82 0,797 0,80 0,073 9, ,399 yes 30, ,8 30,3 2,24 7, ,449 yes 2,82 1 2,72 2,8 2,83 0,241 8, ,99 yes 2,71 2,4 2,7 2,68 0,299 11, ,213 C 47 47, 46,8 46, 2,37, ,112 yes 3,12 3,08 3,1 3,09 0,176, ,397 yes 40,3 1 41, 40,6 40,3 2, ,860 yes 1, 1 16, 1, 1,4 1,32 8, ,221 yes 2,04 2 2,06 2,03 0,24 11, ,127 yes 79 79, 78,2 78, 4,8 6, ,097 yes,3,2,4,3 0,938 9, ,496 yes ,43 4, ,042 yes 8,37 8,41 8,6 8,48 0,99 11, ,20 yes 2,28 2 2,3 2,21 0,31 1, ,890 H 7 79, 6,3 6,1 3, ,190 yes 12,2 1,2 12,3 12,2 1,06 8, ,290 H 83, ,1 4,09 4, ,30 yes 9,92 8,41 9,8 9,91 1,02, ,23 yes, ,91 9,64 2,93 30, ,130 yes ,9, ,473 yes , ,73 yes ,000 yes , ,771 yes 0,83 0,766 0,766 0,78 0,118 1, ,729 yes 0,17 2 0,14 0,163 0,164 0, , ,018 yes 2,28 2 2,27 2,3 2,3 0,6 23, ,072 yes 3,9 2 3,87 3,86 3,8 0,37 9, ,440 yes 90 96, 92,3 91,9 7,04 7, ,241 C 44, ,8 44,4 3,42 7, ,488 yes ,2 4, ,034 yes ,4, ,721 yes 6,24,79,84, , ,000 yes ,4 67 4, ,389 yes 6,17 6,41 6,22 6,14 0,61 9, ,802 yes ,92 4, ,714 yes 11, ,1 1,26 11, ,1 yes 1,99 1,9 1,98 2,01 0,363 18, ,990 yes 92,9 97, 92,8 93,2,66 6, ,468 yes 6,12 1,9,96 6,02 0,4 9, ,429 yes 67,6 70, 67,4 67,2 4,89 7, ,467 yes 3,32 3,17 3,16 3,2 0,37 11, ,460 yes 1,2 1,38 1,1 1,14 0,237, ,240 yes ,7 4 3,18 7, ,112 yes 2,67 2,7 2,71 2,3 0,22, ,797 yes 30,1 32, 29,9 30,3 2,9 9, ,97 yes 6,72 7,38 6,7 6,66 0,709, ,668 yes 3,79 1 3,6 3,6 3,6 0,332 9, ,698 yes ,7 84,6 4,04 4, ,321 yes 4,83 4,68 4,78 4,7 0,449 9, ,048 yes 82,8 1 82, 82,8 82,3 4,0 4, Outlier test failed: C Cohcran, G1 Grubbs(1outlier algorithm), G2 Grubbs(2outliers algorithm), H Hampel, M manual SYKE Interlaboratory comparison test 3/

76 LIITE 8 / 2 74 APPENDIX Analyte Unit Sample zgraphics Z value Outl Assigned test OK value 2* Targ SD% Lab's result Md. Mean SD SD% Passed Outl. failed Missing Num of labs Laboratory Zn Laboratory Al As Cd Co Cr Cu Fe Mn Ni Pb Se V Zn 1 2 0,079 yes 12,6 12, 12,6 12,7 1,17 9, ,9 yes 7,8 2 8,0 8,1 8,1 1,94 22, ,8 yes ,84, ,1 yes 1, ,9 1,9 2,41 1, ,736 yes ,6 8, ,038 yes 2,3 2, 3,1 2,3,42, ,268 yes , ,68 yes ,9 7, ,918 yes ,1 4, ,008 yes ,8 14, ,080 yes 6,0 3,8 6,01,9 0,82 14, ,40 yes 7 1 0,8 7 6,8 3,68 6, ,849 yes 3,77 2 3,37 3,71 3,7 0,877 24, ,060 yes 97,7 87,3 97,7 97,6 6,31 6, ,860 yes 4,86 2 3,73 4,97 4,8 0,731 1, ,270 yes 0,66 0,1 0,628 0,634 0, , ,330 yes 6,4 1,28 6,41 6,44 0,426 6, ,617 yes 0,81 0,76 0,797 0,80 0,073 9, ,700 yes 30,1 1 26,3 29,8 30,3 2,24 7, ,780 yes 2,82 1 2,66 2,8 2,83 0,241 8, ,290 yes 2,71 3,33 2,7 2,68 0,299 11, ,2 C 47 44,1 46,8 46, 2,37, ,70 C 3,12 3,67 3,1 3,09 0,176, ,74 yes 40,3 1 38,6 40,6 40,3 2, ,2 yes 1, 1 14,1 1, 1,4 1,32 8, ,343 yes 2,04 1,97 2,06 2,03 0,24 11, ,30 yes 79 77,8 78,2 78, 4,8 6, ,131 yes,3,2,4,3 0,938 9, ,144 yes ,43 4, ,9 yes 8,37 9,96 8,6 8,48 0,99 11, ,066 yes 2,28 2,27 2,3 2,21 0,31 1, ,0 yes 7 2,6 6,3 6,1 3, ,623 yes 12,2 1 11,6 12,3 12,2 1,06 8, ,391 yes 83, ,1 4,09 4, ,70 yes 9,92 9,36 9,8 9,91 1,02, ,260 yes,2 30 8,28 9,91 9,64 2,93 30, ,840 yes ,9, ,4 yes , ,780 yes ,1 yes , ,923 yes 3,9 2 3,4 3,86 3,8 0,37 9, ,8 yes 90 77,3 92,3 91,9 7,04 7, ,240 yes 44,2 1 40,1 44,8 44,4 3,42 7, ,030 yes ,2 4, ,3 yes ,4, ,7 H 6,24 9,8,84, , ,128 yes 69 68,1 67,4 67 4, ,430 yes 6,17 7,0 6,22 6,14 0,61 9, ,719 yes ,92 4, ,299 yes 11,2 11, 11 11,1 1,26 11, ,0 H 1,99 11,2 1,98 2,01 0,363 18, ,227 yes 92,9 91,8 92,8 93,2,66 6, ,370 yes 6,12 1,9,96 6,02 0,4 9, ,24 yes 67,6 6,9 67,4 67,2 4,89 7, ,904 yes 3,32 3,02 3,16 3,2 0,37 11, ,300 H 1,2 2,6 1,1 1,14 0,237, ,91 yes ,9 44,7 4 3,18 7, ,712 yes 2,67 2,86 2,71 2,3 0,22, ,42 yes 30,1 28, 29,9 30,3 2,9 9, ,870 H 6,72 3,4 6,7 6,66 0,709, ,440 yes 3,79 1 3,67 3,6 3,6 0,332 9, ,040 H 86 68,6 84,7 84,6 4,04 4, ,0 yes 4,83,41 4,78 4,7 0,449 9, ,662 yes 82,8 1 78,7 82,8 82,3 4,0 4, ,20 yes 12,6 12,9 12,6 12,7 1,17 9, ,484 yes 7,8 2 7,38 8,1 8,1 1,94 22, Outlier test failed: C Cohcran, G1 Grubbs(1outlier algorithm), G2 Grubbs(2outliers algorithm), H Hampel, M manual SYKE Interlaboratory comparison test 3/

77 7 LIITE APPENDIX 8 / 3 Analyte Unit Sample zgraphics Z value Outl Assigned test OK value 2* Targ SD% Lab's result Md. Mean SD SD% Passed Outl. failed Missing Num of labs Laboratory 2 Zn Laboratory 3 Hg Laboratory 4 Fe Mn Laboratory Cd Co Cr Cu Fe Hg Mn Ni Pb Zn A1Hg N3Hg THg A1Hg N3Hg THg 1,160 yes ,84, ,47 yes 1,8 2 14,7 1,9 1,9 2,41 1, ,260 yes ,6 8, ,337 yes 2,3 4,1 3,1 2,3,42, ,42 yes 0,83 0,87 0,766 0,78 0,118 1, ,118 yes 0,17 2 0,172 0,163 0,164 0, , ,670 yes 2,28 2 3,61 2,3 2,3 0,6 23, ,080 H, , 9,91 9,64 2,93 30, ,228 yes ,9, ,348 yes , ,380 H 3,9 2 7, 3,86 3,8 0,37 9, ,1 yes 90 99, 92,3 91,9 7,04 7, ,10 C 44, ,8 44,4 3,42 7, ,78 yes 0,66 0,71 0,628 0,634 0, , ,4 H 6,4 1 8,2 6,41 6,44 0,426 6, ,370 yes 0,81 0,84 0,797 0,80 0,073 9, ,886 yes 30,1 1 32,1 29,8 30,3 2,24 7, ,946 yes 2,82 1 2,62 2,8 2,83 0,241 8, ,070 yes 2,71 3,00 2,7 2,68 0,299 11, ,230 yes 47 2,23 46,8 46, 2,37, ,000 H 3,12 42,0 3,1 3,09 0,176, ,700 yes 40,3 1 4,44 40,6 40,3 2, ,89 yes 1, 1 16,4 1, 1,4 1,32 8, ,196 yes 2,04 2,00 2,06 2,03 0,24 11, ,060 yes 79 87,12 78,2 78, 4,8 6, ,270 yes,3 12,64,4,3 0,938 9, ,060 yes , ,43 4, ,789 yes 8,37 9,03 8,6 8,48 0,99 11, ,40 yes 2,28 2,61 2,3 2,21 0,31 1, ,60 yes 7 64,4 6,3 6,1 3, ,370 yes 12,2 1 13,4 12,3 12,2 1,06 8, ,4 yes 83,4 1 92, ,1 4,09 4, ,484 yes 9,92,40 9,8 9,91 1,02, ,600 H, ,4 9,91 9,64 2,93 30, ,170 yes , ,9, ,906 yes , , ,700 yes , ,162 yes , , ,1 H 0,83 0,24 0,766 0,78 0,118 1, ,000 H 0,17 2 0,08 0,163 0,164 0, , ,860 yes 2,28 2 1,7 2,3 2,3 0,6 23, ,230 yes 3,9 2 3,30 3,86 3,8 0,37 9, ,490 yes 90 1,21 92,3 91,9 7,04 7, ,80 yes 44,2 1 3,66 44,8 44,4 3,42 7, ,160 H 41 44, ,2 4, ,90 yes , ,4, ,230 yes 6,24 2,3,84, , ,31 yes 69 71,42 67,4 67 4, ,7 H 6,17 2,6 6,22 6,14 0,61 9, ,170 yes , ,92 4, ,630 yes 11,2 7, ,1 1,26 11, ,060 yes 1,99 2,40 1,98 2,01 0,363 18, ,70 H 92,9 1,33 92,8 93,2,66 6, ,090 yes 6,12 1 6,62,96 6,02 0,4 9, ,00 yes 67,6 60,47 67,4 67,2 4,89 7, ,241 yes 3,32 3,24 3,16 3,2 0,37 11, ,81 yes 7,8 2 8,42 8,1 8,1 1,94 22, ,1 yes , ,84, ,866 yes 1,8 2 17,1 1,9 1,9 2,41 1, ,4 yes , ,6 8, ,94 yes 2,3 7,24 3,1 2,3,42, Outlier test failed: C Cohcran, G1 Grubbs(1outlier algorithm), G2 Grubbs(2outliers algorithm), H Hampel, M manual SYKE Interlaboratory comparison test 3/

78 LIITE 8 / 4 76 APPENDIX Analyte Unit Sample zgraphics Z value Outl Assigned test OK value 2* Targ SD% Lab's result Md. Mean SD SD% Passed Outl. failed Missing Num of labs Laboratory Al As Cd Co Cr Cu Fe Mn Ni Pb Se V Zn 6 0,449 yes 1,6 2 16, 1,4 1, 1,91 12, ,63 yes , ,41 yes ,9 7, ,63 yes ,1 4, ,127 yes ,8 14, ,114 yes 6,0 6,12 6,01,9 0,82 14, ,172 yes 7 1 6,3 7 6,8 3,68 6, H 3,77 2 <4 3,71 3,7 0,877 24, ,122 yes 97,7 98,9 97,7 97,6 6,31 6, ,604 yes 4,86 2,23 4,97 4,8 0,731 1, , yes 0,66 0,6 0,628 0,634 0, , ,840 H 6,4 1 9,2 6,41 6,44 0,426 6, ,988 yes 0,81 0,73 0,797 0,80 0,073 9, ,830 yes 30,1 1 34,2 29,8 30,3 2,24 7, ,8 yes 2,82 1 2,7 2,8 2,83 0,241 8, ,040 yes 2,71 2,99 2,7 2,68 0,299 11, ,090 yes 47 49,6 46,8 46, 2,37, ,434 yes 3,12 3,26 3,1 3,09 0,176, ,8 yes 40,3 1 40,6 40,6 40,3 2, ,422 yes 1, 1 1 1, 1,4 1,32 8, ,440 C 2,04 2,33 2,06 2,03 0,24 11, ,019 yes 79 79,1 78,2 78, 4,8 6, ,277 yes,3,6,4,3 0,938 9, ,039 yes ,43 4, ,004 yes 8,37 8,37 8,6 8,48 0,99 11, ,1 yes 2,28 1,8 2,3 2,21 0,31 1, ,826 yes 7 9,4 6,3 6,1 3, ,680 yes 12,2 1 8,83 12,3 12,2 1,06 8, ,679 yes 83,4 1 87, ,1 4,09 4, ,449 yes 9,92 9,47 9,8 9,91 1,02, ,860 yes, ,1 9,91 9,64 2,93 30, ,819 yes ,9, ,739 yes , ,808 yes ,900 yes , ,26 yes 3,9 2 3,78 3,86 3,8 0,37 9, ,10 yes 90 9,2 92,3 91,9 7,04 7, ,973 yes 44,2 1 47,4 44,8 44,4 3,42 7, ,927 yes ,2 4, ,814 yes ,4, ,7 yes 6,24 8,6,84, , ,139 yes ,4 67 4, ,30 yes 6,17,22 6,22 6,14 0,61 9, ,278 yes ,92 4, ,2 yes 11,2 9, ,1 1,26 11, ,830 yes 1,99 2, 1,98 2,01 0,363 18, ,600 yes 92,9 0 92,8 93,2,66 6, ,7 yes 6,12 1 7,37,96 6,02 0,4 9, ,634 yes 67,6 71,9 67,4 67,2 4,89 7, ,137 yes 3,32 3,27 3,16 3,2 0,37 11, H 1,2 <4 1,1 1,14 0,237, ,499 yes ,6 44,7 4 3,18 7, H 2,67 <4 2,71 2,3 0,22, ,326 yes 30,1 31,1 29,9 30,3 2,9 9, ,041 yes 6,72 6,7 6,7 6,66 0,709, ,472 yes ,7 84,6 4,04 4, ,390 C 4,83, 4,78 4,7 0,449 9, ,68 yes 82,8 1 86,9 82,8 82,3 4,0 4, ,42 yes 12,6 13,2 12,6 12,7 1,17 9, ,2 C 7, ,1 8,1 1,94 22, ,07 yes ,84, ,00 yes 1,8 2 17,9 1,9 1,9 2,41 1, ,4 yes ,6 8, ,090 yes 2,3 2,8 3,1 2,3,42, Outlier test failed: C Cohcran, G1 Grubbs(1outlier algorithm), G2 Grubbs(2outliers algorithm), H Hampel, M manual SYKE Interlaboratory comparison test 3/

79 77 LIITE APPENDIX 8 / Analyte Unit Sample zgraphics Z value Outl Assigned test OK value 2* Targ SD% Lab's result Md. Mean SD SD% Passed Outl. failed Missing Num of labs Laboratory Al As Cd Cr Cu Mn Ni Pb Laboratory Al As Cd Co Cr Cu 7 8 2,360 yes 1, ,4 1, 1,91 12, ,330 H ,9 7, ,8 yes , ,8 14, ,80 yes 6,0 7 6,01,9 0,82 14, ,3 yes 7 1 1,3 7 6,8 3,68 6, ,764 yes 3,77 2 3,41 3,71 3,7 0,877 24, ,140 yes 4,86 2 4,78 4,97 4,8 0,731 1, ,060 yes 0,66 0,73 0,628 0,634 0, , ,040 yes 6,4 1 6,9 6,41 6,44 0,426 6, ,802 yes 0,81 0,87 0,797 0,80 0,073 9, ,61 yes 2,82 1 2,9 2,8 2,83 0,241 8, ,6 yes 2,04 1, 2,06 2,03 0,24 11, ,40 H 79 7,1 78,2 78, 4,8 6, ,340 H,3 6,86,4,3 0,938 9, ,040 H 8,37 4,99 8,6 8,48 0,99 11, ,636 yes 2,28 2,42 2,3 2,21 0,31 1, ,8 yes 7 1,8 6,3 6,1 3, ,219 yes 12, ,3 12,2 1,06 8, ,61 yes 9,92 9,31 9,8 9,91 1,02, ,80 yes 3,9 2 3,13 3,86 3,8 0,37 9, ,860 H 44,2 1 28,1 44,8 44,4 3,42 7, ,630 H ,4, ,380 yes 6,24 7,1,84, , ,0 yes ,4 67 4, ,0 H 6,17 8,36 6,22 6,14 0,61 9, ,20 yes 11,2 12, ,1 1,26 11, ,870 yes 1,99 2,96 1,98 2,01 0,363 18, ,872 yes 92,9 88,8 92,8 93,2,66 6, ,900 H 6,12 1 3,41,96 6,02 0,4 9, ,700 H 3,32 6,88 3,16 3,2 0,37 11, ,360 yes 1,6 2 12,9 1,4 1, 1,91 12, ,446 yes , ,000 yes ,9 7, ,390 yes , ,02 yes ,1 4, ,440 yes ,8 14, ,248 yes 6,0 6,2 6,01,9 0,82 14, ,12 yes 7 1 7,6 7 6,8 3,68 6, ,912 yes 3,77 2 4,2 3,71 3,7 0,877 24, ,800 H 16,3 2 8,7 16,2 16,4 1,92 11, ,260 yes 97,7 1 97,7 97,6 6,31 6, ,642 yes 4,86 2,2 4,97 4,8 0,731 1, ,909 yes 0,66 0,6 0,628 0,634 0, , ,30 yes 6,4 1 7,0 6,41 6,44 0,426 6, ,1 yes 0,81 0,9 0,797 0,80 0,073 9, ,700 yes 0,71 2 0,9 0,701 0,712 0,119 16, ,4 yes 30,1 1 31,4 29,8 30,3 2,24 7, ,331 yes 2,82 1 2,7 2,8 2,83 0,241 8, ,99 yes 2,71 2,4 2,7 2,68 0,299 11, ,74 yes 47 48,8 46,8 46, 2,37, ,224 yes 3,12 3,0 3,1 3,09 0,176, ,700 yes 16,9 2 22,6 16,9 17,2 2,46 14, ,480 yes 40,3 1 41,8 40,6 40,3 2, ,000 yes 1, 1 1, 1, 1,4 1,32 8, ,8 H 2,04 0,6 2,06 2,03 0,24 11, ,177 yes 79 78,3 78,2 78, 4,8 6, ,070 yes,3 9,2,4,3 0,938 9, ,3 yes 6 2 7,7 6,7 63,8 9,07 14, ,2 yes ,43 4, ,700 yes 8,37 6,9 8,6 8,48 0,99 11, ,40 yes 2,28 1,9 2,3 2,21 0,31 1, ,000 yes 7 9,8 6,3 6,1 3, ,4 yes 12,2 1 13, 12,3 12,2 1,06 8, ,640 yes 40 46,6 40,2 39,8,16 12, ,663 yes 83,4 1 87, 83 83,1 4,09 4, ,121 yes 9,92 9,8 9,8 9,91 1,02, Outlier test failed: C Cohcran, G1 Grubbs(1outlier algorithm), G2 Grubbs(2outliers algorithm), H Hampel, M manual SYKE Interlaboratory comparison test 3/

80 LIITE 8 / 6 78 APPENDIX Analyte Unit Sample zgraphics Z value Outl Assigned test OK value 2* Targ SD% Lab's result Md. Mean SD SD% Passed Outl. failed Missing Num of labs Fe Laboratory 8 Fe Hg Mn N Ni P Pb S Se V Zn A1Hg N3Hg S6M S6M S6M S6M 0,163 yes,2 30 9,9 9,91 9,64 2,93 30, ,40 yes ,9, ,41 yes , ,0 yes , ,3 yes ,44 yes , ,084 yes 0,83 0,837 0,766 0,78 0,118 1, ,73 yes 0,17 2 0,186 0,163 0,164 0, , ,738 yes 0,13 2 0,142 0,134 0,126 0,023, ,080 H 3,9 2 2,4 3,86 3,8 0,37 9, ,44 yes 90 92,4 92,3 91,9 7,04 7, ,8 yes 44, ,8 44,4 3,42 7, ,8 yes , ,08 yes ,2 4, ,270 yes ,4, ,718 yes , ,830 yes 6,24,1,84, , ,181 yes 69 70,3 67,4 67 4, ,843 yes 6,17,6 6,22 6,14 0,61 9, ,270 yes 38,3 43, ,8 4,37 11, ,611 yes ,92 4, ,982 yes 11,2, ,1 1,26 11, ,840 yes , ,2 C 1,99 1, 1,98 2,01 0,363 18, ,17 yes 92,9 9,3 92,8 93,2,66 6, ,000 yes 6,12 1,2,96 6,02 0,4 9, ,2 yes 46, 40,9 46,3 4,4 6 13, ,01 yes 67,6 67, 67,4 67,2 4,89 7, ,392 C 3,32 3,4 3,16 3,2 0,37 11, ,390 H , ,670 yes 1,2 0,64 1,1 1,14 0,237, ,0 H 43 1,4 44,7 4 3,18 7, ,900 H 2,67 13,1 2,71 2,3 0,22, ,660 H 30,1 13,1 29,9 30,3 2,9 9, ,3 H 6,72 3,1 6,7 6,66 0,709, ,20 yes 3,79 1 3,1 3,6 3,6 0,332 9, ,384 yes 86 84,3 84,7 84,6 4,04 4, ,14 yes 4,83 4,9 4,78 4,7 0,449 9, ,3 yes 70,3 86,6 69,7 70,3 8,34 11, ,298 yes 82, ,8 82,3 4,0 4, ,476 yes 12, ,6 12,7 1,17 9, ,780 yes 7,8 2 6,1 8,1 8,1 1,94 22, ,190 yes ,84, ,040 yes 1,8 2 13,8 1,9 1,9 2,41 1, ,3 yes ,2, ,094 yes ,6 8, ,784 yes 2,3 48,2 3,1 2,3,42, Outlier test failed: C Cohcran, G1 Grubbs(1outlier algorithm), G2 Grubbs(2outliers algorithm), H Hampel, M manual SYKE Interlaboratory comparison test 3/

81 79 LIITE APPENDIX 8 / 7 Analyte Unit Sample zgraphics Z value Outl Assigned test OK value 2* Targ SD% Lab's result Md. Mean SD SD% Passed Outl. failed Missing Num of labs Laboratory 9 Al H 1,6 2 <30 1,4 1, 1,91 12, ,474 yes , ,14 yes ,9 7, Cd H 0,66 <1 0,628 0,634 0, , ,833 yes 6,4 1 6,8 6,41 6,44 0,426 6, H 0,81 <1 0,797 0,80 0,073 9, Cr 0,049 yes 2,04 2,0 2,06 2,03 0,24 11, ,090 yes 79 74,7 78,2 78, 4,8 6, ,194 yes,3,1,4,3 0,938 9, Cu H 2,28 <4 2,3 2,21 0,31 1, ,702 yes 7 6,3 6,1 3, ,0 yes 12,2 1 12,2 12,3 12,2 1,06 8, Fe 2,2 yes,2 30 6,8 9,91 9,64 2,93 30, ,477 yes ,9, ,02 yes , Mn 1,030 yes 3,9 2 4,4 3,86 3,8 0,37 9, ,090 yes 90 94,9 92,3 91,9 7,04 7, ,42 yes 44,2 1 4,7 44,8 44,4 3,42 7, Ni H 6,24 <,84, , ,486 yes 69 6,7 67,4 67 4, H 6,17 < 6,22 6,14 0,61 9, Pb H 1,99 <1 1,98 2,01 0,363 18, ,323 yes 92,9 91,4 92,8 93,2,66 6, H 6,12 1 <,96 6,02 0,4 9, Zn 1,170 yes 7,8 2 6,7 8,1 8,1 1,94 22, ,387 yes ,84, ,70 yes 1,8 2 12,7 1,9 1,9 2,41 1, Laboratory Cd H 0,71 2 <1 0,701 0,712 0,119 16, ,080 C 30,3 1 27,9 30,1 30,1 1,93 6, Cr 1,130 yes 6 2,8 6,7 63,8 9,07 14, Cu 0,762 yes ,2 39,8,16 12, ,69 C 8, ,3 8,6 3,6 4, Fe 2,1 yes ,9, Hg A1Hg H 0,83 <0,08 0,766 0,78 0,118 1, S6M 3,7 yes 0,13 2 0,0697 0,134 0,126 0,023, THg 6,0 H 2,28 2 0,42 2,3 2,3 0,6 23, Mn 2,440 yes ,3 91,9 7,04 7, ,264 yes , ,331 yes ,7 4, Ni 0,770 yes 38,3 3, ,8 4,37 11, Pb 0,04 yes 46, 46,3 46,3 4,4 6 13, Zn 0,64 yes ,84, ,036 yes ,2, ,060 yes ,27 3, Outlier test failed: C Cohcran, G1 Grubbs(1outlier algorithm), G2 Grubbs(2outliers algorithm), H Hampel, M manual SYKE Interlaboratory comparison test 3/

82 LIITE 8 / 8 80 APPENDIX Analyte Unit Sample zgraphics Z value Outl Assigned test OK value 2* Targ SD% Lab's result Md. Mean SD SD% Passed Outl. failed Missing Num of labs Laboratory 11 Al 2,6 C 1,6 2,7 1,4 1, 1,91 12, ,37 yes , ,881 yes ,9 7, ,780 yes , ,612 yes ,1 4, ,90 yes , 9, ,876 yes ,8 14, As 7,80 H 6,0,8 6,01,9 0,82 14, ,6 yes 7 1 9,6 7 6,8 3,68 6, H 3,77 2 < 3,71 3,7 0,877 24, ,840 yes 16,3 2,1 16,2 16,4 1,92 11, ,328 yes 97,7 94, 97,7 97,6 6,31 6, ,088 yes 91,1 90,3 91,9 90,8 7,66 8, H 4,86 2 < 4,97 4,8 0,731 1, Cd 0,78 C 0,66 0,71 0,628 0,634 0, , ,2 yes 6,4 1,81 6,41 6,44 0,426 6, H 0,81 <1 0,797 0,80 0,073 9, , yes 0,71 2 0,84 0,701 0,712 0,119 16, ,487 yes 30, ,8 30,3 2,24 7, ,0 yes 30,3 1 2,7 30,1 30,1 1,93 6, ,91 yes 2,82 1 2,9 2,8 2,83 0,241 8, Co 0,332 yes 2,71 2,8 2,7 2,68 0,299 11, ,319 yes 47 46,3 46,8 46, 2,37, H 3,12 < 3,1 3,09 0,176, ,426 yes 16, ,9 17,2 2,46 14, ,099 yes 40, ,6 40,3 2, ,988 yes 40, 1 37, 40,8 40, 1,77 4, ,043 yes 1, 1 1,4 1, 1,4 1,32 8, Cr 1,180 yes 2,04 1,8 2,06 2,03 0,24 11, ,443 yes 79 77,3 78,2 78, 4,8 6, ,194 yes,3,,4,3 0,938 9, ,37 yes ,1 6,7 63,8 9,07 14, ,2 yes ,43 4, ,6 yes ,6, ,263 yes 8,37 8,1 8,6 8,48 0,99 11, Cu 2,280 yes 2,28 2,8 2,3 2,21 0,31 1, ,281 yes 7 7,8 6,3 6,1 3, ,0 yes 12,2 1 13,3 12,3 12,2 1,06 8, ,90 yes 40 32,2 40,2 39,8,16 12, ,112 yes 83,4 1 84, ,1 4,09 4, ,140 yes 8,6 1 84,7 8,3 8,6 3,6 4, ,181 yes 9,92,1 9,8 9,91 1,02, Fe 0,392 yes,2 30,8 9,91 9,64 2,93 30, ,081 yes ,9, ,174 yes , ,091 yes , ,349 yes ,260 yes , 6, ,602 yes , Hg A1Hg 0,1 yes 0,83 0,82 0,766 0,78 0,118 1, N3Hg 2,30 C 0,17 2 0,22 0,163 0,164 0, , S6M 3,480 yes 0,13 2 0,073 0,134 0,126 0,023, THg 3,740 yes 2,28 2 3,34 2,3 2,3 0,6 23, Mn 0,000 yes 3,9 2 3,9 3,86 3,8 0,37 9, ,233 yes ,3 91,9 7,04 7, ,090 yes 44,2 1 44, 44,8 44,4 3,42 7, ,32 yes , ,443 yes ,2 4, ,0 yes ,7 4, ,0 yes ,4, Ni 0,70 yes 6,24,8,84, , ,232 yes 69 67,4 67,4 67 4, ,130 yes 6,17 6,2 6,22 6,14 0,61 9, ,992 yes 38,3 34, 38 37,8 4,37 11, ,062 yes ,92 4, ,84 yes ,92 4, ,223 yes 11,2 11, ,1 1,26 11, Outlier test failed: C Cohcran, G1 Grubbs(1outlier algorithm), G2 Grubbs(2outliers algorithm), H Hampel, M manual SYKE Interlaboratory comparison test 3/

83 81 LIITE APPENDIX 8 / 9 Analyte Unit Sample zgraphics Z value Outl Assigned test OK value 2* Targ SD% Lab's result Md. Mean SD SD% Passed Outl. failed Missing Num of labs Pb H 1,99 < 1,98 2,01 0,363 18, Laboratory 11 Pb 0,377 yes 92,9 91,2 92,8 93,2,66 6, H 6,12 1 <,96 6,02 0,4 9, ,92 yes 46, 42,2 46,3 4,4 6 13, ,148 yes 67,6 66,6 67,4 67,2 4,89 7, ,427 yes 6,6 62,8 6, 64,7,03 7, H 3,32 < 3,16 3,2 0,37 11, Se H 1,2 <30 1,1 1,14 0,237, ,29 yes ,7 4 3,18 7, ,00 yes 30,1 29,9 29,9 30,3 2,9 9, ,770 yes 29,3 34, 29, 29,1 3,79 13,0 0 0 V 1,0 yes 3,79 1 3, 3,6 3,6 0,332 9, ,709 yes ,7 84,6 4,04 4, H 4,83 < 4,78 4,7 0,449 9, ,26 yes 70,3 68, 69,7 70,3 8,34 11, ,06 yes 82,8 1 82, 82,8 82,3 4,0 4, ,113 yes 82,4 1 83,1 82,3 82,3 3,96 4, ,873 yes 12,6 11, 12,6 12,7 1,17 9, Zn 2,140 yes 7,8 2,7 8,1 8,1 1,94 22, ,00 H ,84, ,230 yes 1,8 2 11,4 1,9 1,9 2,41 1, ,7 yes ,2, ,8 yes ,6 8, ,360 H ,27 3, ,480 yes 2,3 39,4 3,1 2,3,42, Laboratory 12 Al 0,143 yes , SO6 yes , ,01 yes ,1 4, As 0,199 yes 7 1 7,8 7 6,8 3,68 6, SO6 yes 18,4 17,4 16,9 1, ,0 yes 97,7 97,8 97,7 97,6 6,31 6, Cd 0,313 yes 6,4 1 6,2 6,41 6,44 0,426 6, SO6 yes 0,8 0,748 0,793 0,162, ,266 yes 30,1 1 29, 29,8 30,3 2,24 7, Co 0,319 yes 47 47,8 46,8 46, 2,37, SO6 yes 17,7 18,8 19,1 1,82 9, 0 0 0,26 yes 40,3 1 41,1 40,6 40,3 2, Cr 0,468 yes 79 80,8 78,2 78, 4,8 6, SO6 yes 77, 77, 73,2 8,61 11, ,16 yes ,43 4, Cu 0,263 yes 7 7,8 6,3 6,1 3, SO6 yes 43,9 39, 39,9 2,91 7, ,160 yes 83,4 1 84, ,1 4,09 4, Fe 0,309 yes ,9, SO6 yes , ,399 yes Hg S6M 0,431 yes 0,13 2 0,137 0,134 0,126 0,023, THg 0,333 yes 2,28 2 2,19 2,3 2,3 0,6 23, Mn 0,189 yes 90 89,2 92,3 91,9 7,04 7, SO6 yes ,1 2, ,244 yes ,2 4, Ni 0,217 yes 69 70, 67,4 67 4, SO6 yes 39 38,6 38,2 6,44 16, ,679 yes ,92 4, Pb 0,172 yes 92,9 93,7 92,8 93,2,66 6, SO6 yes 47,4 47,3 47,3 0,40 0, ,044 yes 67,6 67,3 67,4 67,2 4,89 7, Se 0,496 yes ,6 44,7 4 3,18 7, SO6 <4 0,938 0,98 1, 17, ,033 yes 30, ,9 30,3 2,9 9, V 0,128 yes 86 86,6 84,7 84,6 4,04 4, SO6 yes 83,8 80,6 80,3 14,7 18, ,000 yes 82,8 1 82,8 82,8 82,3 4,0 4, Zn 0,036 yes ,84, SO6 yes ,4 11, ,286 yes ,6 8, Outlier test failed: C Cohcran, G1 Grubbs(1outlier algorithm), G2 Grubbs(2outliers algorithm), H Hampel, M manual SYKE Interlaboratory comparison test 3/

84 LIITE 8 / 82 APPENDIX Analyte Unit Sample zgraphics Z value Outl Assigned test OK value 2* Targ SD% Lab's result Md. Mean SD SD% Passed Outl. failed Missing Num of labs Laboratory Al As Cd Co Cr Cu Fe Mn Ni Pb Zn 13 0,462 yes 1,6 2 16, 1,4 1, 1,91 12, ,31 yes , ,06 yes ,9 7, ,61 yes ,1 4, ,42 yes ,8 14, ,331 yes 6,0,8 6,01,9 0,82 14, ,667 yes 7 1 9,9 7 6,8 3,68 6, ,41 yes 3,77 2 3,1 3,71 3,7 0,877 24, ,133 yes 97, ,7 97,6 6,31 6, ,9 yes 4,86 2 4,28 4,97 4,8 0,731 1, ,740 yes 0,66 0,4 0,628 0,634 0, , ,2 yes 6,4 1 6,67 6,41 6,44 0,426 6, ,309 yes 0,81 0,78 0,797 0,80 0,073 9, ,166 yes 30,1 1 30, 29,8 30,3 2,24 7, ,67 yes 2,82 1 2,94 2,8 2,83 0,241 8, ,221 yes 2,71 2,6 2,7 2,68 0,299 11, ,74 yes 47 48,8 46,8 46, 2,37, ,38 yes 3,12 3 3,1 3,09 0,176, ,397 yes 40,3 1 41, 40,6 40,3 2, ,473 yes 1, 1 14,9 1, 1,4 1,32 8, ,030 yes 2,04 2,2 2,06 2,03 0,24 11, ,46 yes 79 80,8 78,2 78, 4,8 6, ,3 yes,3 11,6,4,3 0,938 9, ,81 yes ,43 4, ,812 yes 8,37 9,0 8,6 8,48 0,99 11, ,70 yes 2,28 2,1 2,3 2,21 0,31 1, ,632 yes 7,2 6,3 6,1 3, ,164 yes 12,2 1 12,4 12,3 12,2 1,06 8, ,76 yes 83,4 1 79, ,1 4,09 4, ,030 yes 9,92 9,9 9,8 9,91 1,02, ,2 yes, ,1 9,91 9,64 2,93 30, ,37 yes ,9, ,634 yes , ,73 yes ,060 yes , ,923 yes 3,9 2 4,3 3,86 3,8 0,37 9, ,667 yes ,3 91,9 7,04 7, ,13 yes 44,2 1 4,9 44,8 44,4 3,42 7, ,044 yes ,2 4, ,7 yes ,4, ,38 yes 6,24 6,84, , ,319 yes 69 66,8 67,4 67 4, ,049 yes 6,17 6,2 6,22 6,14 0,61 9, ,296 yes ,92 4, ,80 yes 11,2, ,1 1,26 11, ,330 yes 1,99 1,73 1,98 2,01 0,363 18, ,4 yes 92,9 4 92,8 93,2,66 6, ,893 yes 6,12 1 6,3,96 6,02 0,4 9, ,969 yes 67,6 74,2 67,4 67,2 4,89 7, ,873 yes 3,32 3,03 3,16 3,2 0,37 11, ,030 yes 7,8 2 11,8 8,1 8,1 1,94 22, ,287 yes ,84, ,490 yes 1,8 2 22,7 1,9 1,9 2,41 1, ,123 yes ,6 8, ,2 C 2,3 1,1 3,1 2,3,42, Outlier test failed: C Cohcran, G1 Grubbs(1outlier algorithm), G2 Grubbs(2outliers algorithm), H Hampel, M manual SYKE Interlaboratory comparison test 3/

85 83 LIITE APPENDIX 8 / 11 Analyte Unit Sample zgraphics Z value Outl Assigned test OK value 2* Targ SD% Lab's result Md. Mean SD SD% Passed Outl. failed Missing Num of labs Laboratory 14 Al 7,990 H 1,6 2 0,02 1,4 1, 1,91 12, ,990 H 840 0, , ,300 H , ,9 7, SO6 yes , ,990 H 177 0, ,8 14, As 0,248 yes 6,0,9 6,01,9 0,82 14, ,269 yes 7 1,9 7 6,8 3,68 6, ,297 C 3,77 2 3,91 3,71 3,7 0,877 24, SO6 yes 14,6 17,4 16,9 1, ,16 yes 4,86 2 4,96 4,97 4,8 0,731 1, Cd 0,144 yes 0,66 0,669 0,628 0,634 0, , ,12 yes 6,4 1 6,46 6,41 6,44 0,426 6, ,06 yes 0,81 0,80 0,797 0,80 0,073 9, SO6 yes 0,748 0,748 0,793 0,162, ,142 yes 2,82 1 2,79 2,8 2,83 0,241 8, Co 0,092 yes 2,71 2,69 2,7 2,68 0,299 11, ,191 yes 47 46, 46,8 46, 2,37, ,176 yes 3,12 3,17 3,1 3,09 0,176, SO6 yes 17, 18,8 19,1 1,82 9, 0 0 0,086 yes 1, 1 1,4 1, 1,4 1,32 8, Cr 1,30 yes 2,04 2,31 2,06 2,03 0,24 11, ,12 yes 79 79,6 78,2 78, 4,8 6, ,070 C,3 11,4,4,3 0,938 9, SO6 yes 62,4 77, 73,2 8,61 11, ,197 yes 8,37 8,4 8,6 8,48 0,99 11, Cu 0,417 yes 2,28 2,38 2,3 2,21 0,31 1, ,246 yes 7 6,3 6,3 6,1 3, ,164 yes 12,2 1 12,1 12,3 12,2 1,06 8, SO6 yes 37 39, 39,9 2,91 7, ,2 yes 9,92 8,72 9,8 9,91 1,02, Fe 6,660 yes,2 30 0,012 9,91 9,64 2,93 30, ,000 H 614 0, ,9, ,300 H , , SO6 H , ,000 H , , Hg N3Hg 0,729 yes 0,17 2 0,18 0,163 0,164 0, , S6M 1,260 yes 0,13 2 0,11 0,134 0,126 0,023, Mn 7,990 H 3,9 2 0,0042 3,86 3,8 0,37 9, ,000 H 90 0,098 92,3 91,9 7,04 7, ,300 H 44,2 1 0,049 44,8 44,4 3,42 7, SO6 H ,1 2, ,300 H , ,4, N S6M 0,238 yes , Ni 0,064 yes 6,24 6,28,84, , ,232 yes 69 67,4 67,4 67 4, ,23 yes 6,17 6,31 6,22 6,14 0,61 9, SO6 yes 38,8 38,6 38,2 6,44 16, ,402 yes 11,2, ,1 1,26 11, P S6M 0,080 yes , Pb 0,07 yes 1,99 2 1,98 2,01 0,363 18, ,92 yes 92,9 90,2 92,8 93,2,66 6, ,229 yes 6,12 1 6,02,96 6,02 0,4 9, SO6 yes 47,7 47,3 47,3 0,40 0, ,377 yes 3,32 3,2 3,16 3,2 0,37 11, S S6M 0,4 yes , Se 2,4 yes 1,2 0,91 1,1 1,14 0,237, ,37 yes ,2 44,7 4 3,18 7, ,80 yes 2,67 2,17 2,71 2,3 0,22, SO6 yes 0,3 0,938 0,98 1, 17, ,141 yes 6,72 6,63 6,7 6,66 0,709, TC S6M yes V 0,141 yes 3,79 1 3,7 3,6 3,6 0,332 9, ,174 yes 86 8,3 84,7 84,6 4,04 4, ,973 yes 4,83,3 4,78 4,7 0,449 9, SO6 yes 76,9 80,6 80,3 14,7 18, ,119 yes 12,6 12,4 12,6 12,7 1,17 9, Zn 1,040 yes 7,8 2 8,88 8,1 8,1 1,94 22, Outlier test failed: C Cohcran, G1 Grubbs(1outlier algorithm), G2 Grubbs(2outliers algorithm), H Hampel, M manual SYKE Interlaboratory comparison test 3/

86 LIITE 8 / APPENDIX Analyte Unit Sample zgraphics Z value Outl Assigned test OK value 2* Targ SD% Lab's result Md. Mean SD SD% Passed Outl. failed Missing Num of labs 0,323 C ,84, Laboratory 14 Zn 0,380 yes 1,8 2 16,6 1,9 1,9 2,41 1, SO6 yes ,4 11, ,076 yes 2,3 2,7 3,1 2,3,42, Laboratory 1 Al 0,39 yes 1,6 2 16,3 1,4 1, 1,91 12, ,083 yes , ,028 yes ,9 7, ,11 yes ,1 4, ,169 yes ,8 14, As 0,936 C ,8 3,68 6, ,271 yes 97,7 9,1 97,7 97,6 6,31 6, Cd 1,8 yes 0,66 0,4 0,628 0,634 0, , ,48 yes 6,4 1 6,62 6,41 6,44 0,426 6, ,360 yes 0,81 0,7 0,797 0,80 0,073 9, ,044 yes 30, ,8 30,3 2,24 7, ,81 yes 2, ,8 2,83 0,241 8, Co 0,426 yes ,8 46, 2,37, ,064 yes 3,12 3,1 3,1 3,09 0,176, ,26 yes 40,3 1 41,1 40,6 40,3 2, ,774 yes 1, 1 14,6 1, 1,4 1,32 8, Cr 0,343 yes 2,04 2,11 2,06 2,03 0,24 11, ,06 yes ,2 78, 4,8 6, ,388 yes,3,7,4,3 0,938 9, ,1 yes ,43 4, ,681 yes 8,37 8,94 8,6 8,48 0,99 11, Cu 1,230 yes 2,28 2 2,3 2,21 0,31 1, ,31 yes 7 8 6,3 6,1 3, ,090 yes 12,2 1 13,2 12,3 12,2 1,06 8, ,264 yes 83, ,1 4,09 4, ,090 yes 9, ,8 9,91 1,02, Fe 1,180 yes, ,91 9,64 2,93 30, ,814 yes ,9, ,199 yes , ,73 yes ,723 yes , Mn 0,61 yes 3,9 2 4,2 3,86 3,8 0,37 9, ,444 yes ,3 91,9 7,04 7, ,030 yes 44,2 1 44,3 44,8 44,4 3,42 7, ,089 yes ,2 4, ,069 yes ,4, Ni 0,329 yes 6,24 6,04,84, , ,000 yes ,4 67 4, ,211 yes 6,17 6,3 6,22 6,14 0,61 9, ,123 yes ,92 4, ,714 yes 11,2, ,1 1,26 11, Pb 2,600 yes 92,9 92,8 93,2,66 6, ,479 yes 6,12 1,9,96 6,02 0,4 9, ,917 yes 67,6 73,8 67,4 67,2 4,89 7, V 0,233 yes ,7 84,6 4,04 4, ,032 yes 82, ,8 82,3 4,0 4, Zn 4,740 yes 7,8 2 12, 8,1 8,1 1,94 22, ,430 C ,84, ,840 C 1,8 2 21,4 1,9 1,9 2,41 1, ,082 yes ,6 8, ,380 yes 2,3 9, 3,1 2,3,42, Outlier test failed: C Cohcran, G1 Grubbs(1outlier algorithm), G2 Grubbs(2outliers algorithm), H Hampel, M manual SYKE Interlaboratory comparison test 3/

87 8 LIITE APPENDIX 8 / 13 Analyte Unit Sample zgraphics Z value Outl Assigned test OK value 2* Targ SD% Lab's result Md. Mean SD SD% Passed Outl. failed Missing Num of labs Laboratory 16 Al As Cd Co Cr Cu Fe Hg Mn Ni Pb Se A1Hg N3Hg S6M THg 0,14 yes 1,6 2 1,3 1,4 1, 1,91 12, ,060 yes , ,060 yes ,9 7, ,92 yes , ,1 yes , 9, ,904 yes ,8 14, ,30 H 6,0 3,42 6,01,9 0,82 14, ,1 yes 7 1 2,3 7 6,8 3,68 6, ,0 yes 3,77 2 1,63 3,71 3,7 0,877 24, ,196 yes 16,3 2 1,9 16,2 16,4 1,92 11, ,017 yes 91, ,9 90,8 7,66 8, ,280 yes 4,86 2 2,87 4,97 4,8 0,731 1, ,227 yes 0,66 0,64 0,628 0,634 0, , ,260 yes 6,4 1 6,28 6,41 6,44 0,426 6, ,173 yes 0,81 0,796 0,797 0,80 0,073 9, ,690 yes 0,71 2 0,6 0,701 0,712 0,119 16, ,308 yes 30,3 1 29,6 30,1 30,1 1,93 6, ,236 yes 2,82 1 2,77 2,8 2,83 0,241 8, ,70 yes 2,71 2,29 2,7 2,68 0,299 11, ,490 yes 47 43, 46,8 46, 2,37, ,962 yes 3,12 2,82 3,1 3,09 0,176, ,024 yes 16,9 2 16,9 16,9 17,2 2,46 14, ,724 yes 40, 1 38,3 40,8 40, 1,77 4, ,64 yes 1, 1 14,8 1, 1,4 1,32 8, ,24 yes 2,04 1,99 2,06 2,03 0,24 11, ,44 yes 79 76,8 78,2 78, 4,8 6, ,340 yes,3,6,4,3 0,938 9, ,29 yes ,4 6,7 63,8 9,07 14, ,6 yes ,6, ,729 yes 8,37 8,98 8,6 8,48 0,99 11, ,230 yes 2,28 2 2,3 2,21 0,31 1, ,79 yes 7,3 6,3 6,1 3, ,164 yes 12,2 1 12,1 12,3 12,2 1,06 8, ,113 yes 40 39, 40,2 39,8,16 12, ,33 yes 8,6 1 87,8 8,3 8,6 3,6 4, ,449 yes 9,92 9,47 9,8 9,91 1,02, ,216 yes,2 30 9,87 9,91 9,64 2,93 30, ,330 yes ,9, ,130 yes , ,446 yes , ,688 yes , 6, ,884 yes , , yes 0,83 0,70 0,766 0,78 0,118 1, ,612 yes 0,17 2 0,17 0,163 0,164 0, , ,060 yes 0,13 2 0,096 0,134 0,126 0,023, ,880 yes 2,28 2 3,38 2,3 2,3 0,6 23, ,79 yes 3,9 2 3,3 3,86 3,8 0,37 9, ,390 yes 90 79,3 92,3 91,9 7,04 7, ,1 yes 44,2 1 40, 44,8 44,4 3,42 7, ,070 yes , ,397 yes ,7 4, ,07 yes ,4, ,140 yes 6,24,3,84, , ,8 yes 69 6,2 67,4 67 4, ,446 yes 6,17,89 6,22 6,14 0,61 9, ,431 yes 38, ,8 4,37 11, ,28 yes ,92 4, ,36 yes 11,2, ,1 1,26 11, , yes 1,99 1,69 1,98 2,01 0,363 18, ,334 yes 92,9 94, 92,8 93,2,66 6, ,360 yes 6,12 1,,96 6,02 0,4 9, ,183 yes 46, 47,3 46,3 4,4 6 13, ,046 yes 6,6 6,9 6, 64,7,03 7, ,0 yes 3,32 2,8 3,16 3,2 0,37 11, ,20 yes 1,2 1,17 1,1 1,14 0,237, ,8 yes ,8 44,7 4 3,18 7, ,787 yes 2,67 2,88 2,71 2,3 0,22, Outlier test failed: C Cohcran, G1 Grubbs(1outlier algorithm), G2 Grubbs(2outliers algorithm), H Hampel, M manual SYKE Interlaboratory comparison test 3/

88 LIITE 8 / APPENDIX Analyte Unit Sample zgraphics Z value Outl Assigned test OK value 2* Targ SD% Lab's result Md. Mean SD SD% Passed Outl. failed Missing Num of labs yes,94 0,924 1,6 1,9 1, Laboratory 16 Se 0,700 yes 29,3 31,4 29, 29,1 3,79 13, ,20 yes 6,72 7,6 6,7 6,66 0,709, V 1,790 yes 3,79 1 3,28 3,6 3,6 0,332 9, ,70 yes 86 79,3 84,7 84,6 4,04 4, ,921 yes 4,83 4,38 4,78 4,7 0,449 9, ,7 yes 70,3 69, 69,7 70,3 8,34 11, ,809 yes 82,4 1 77,4 82,3 82,3 3,96 4, ,67 yes 12,6 11,8 12,6 12,7 1,17 9, Zn 1,030 yes 7,8 2 6,84 8,1 8,1 1,94 22, ,860 yes ,84, ,02 yes 1,8 2 1,8 1,9 1,9 2,41 1, ,21 yes ,2, ,843 yes ,27 3, ,49 yes 2,3 49,9 3,1 2,3,42, Laboratory 17 Al As Cd Co Cr Cu Fe Hg Mn Ni Pb A1Hg N3Hg THg 2,8 yes 1,6 2 21,1 1,4 1, 1,91 12, ,018 yes , ,790 yes ,9 7, ,661 yes ,1 4, ,0 yes ,8 14, ,802 yes 6,0,6 6,01,9 0,82 14, ,117 yes 7 1 7, 7 6,8 3,68 6, ,460 yes 3,77 2 3,08 3,71 3,7 0,877 24, ,14 yes 97,7 99,2 97,7 97,6 6,31 6, ,84 yes 4,86 2 4, 4,97 4,8 0,731 1, ,470 yes 0,66 0,629 0,628 0,634 0, , ,271 yes 6,4 1 6,27 6,41 6,44 0,426 6, ,199 yes 30,1 1 29,6 29,8 30,3 2,24 7, ,280 yes 2,82 1 2, 2,8 2,83 0,241 8, ,369 yes 2,71 2,61 2,7 2,68 0,299 11, ,6 yes 47 47,3 46,8 46, 2,37, ,032 yes 3,12 3,11 3,1 3,09 0,176, ,298 yes 40,3 1 41,2 40,6 40,3 2, ,16 yes 1, 1 16,1 1, 1,4 1,32 8, ,123 yes 2,04 2,02 2,06 2,03 0,24 11, ,380 yes 79 80, 78,2 78, 4,8 6, ,097 yes,3,2,4,3 0,938 9, ,623 yes ,43 4, ,73 yes 8,37 8,8 8,6 8,48 0,99 11, ,088 yes 2,28 2,3 2,3 2,21 0,31 1, ,930 yes 7 9,7 6,3 6,1 3, ,76 yes 12,2 1 12,9 12,3 12,2 1,06 8, ,68 yes 83, ,1 4,09 4, ,8 yes 9,92, 9,8 9,91 1,02, ,131 yes,2 30 9,91 9,64 2,93 30, ,3 yes ,9, ,162 yes , ,199 yes ,48 yes , ,030 yes 0,83 0,744 0,766 0,78 0,118 1, ,824 yes 0,17 2 0,12 0,163 0,164 0, , ,323 yes 2,28 2 2,19 2,3 2,3 0,6 23, ,308 yes 3,9 2 3,7 3,86 3,8 0,37 9, ,630 yes ,3 91,9 7,04 7, ,01 yes 44,2 1 44,3 44,8 44,4 3,42 7, ,364 yes ,2 4, ,161 yes ,4, ,873 yes 6,24,7,84, , ,27 yes 69 70,9 67,4 67 4, ,616 yes 6,17 6, 6,22 6,14 0,61 9, ,4 yes ,92 4, ,380 yes 11,2 12, ,1 1,26 11, ,980 yes 1,99 2,38 1,98 2,01 0,363 18, ,334 yes 92,9 94,4 92,8 93,2,66 6, ,23 yes 6,12 1 6,36,96 6,02 0,4 9, ,090 yes 67,6 60,3 67,4 67,2 4,89 7, Outlier test failed: C Cohcran, G1 Grubbs(1outlier algorithm), G2 Grubbs(2outliers algorithm), H Hampel, M manual SYKE Interlaboratory comparison test 3/

89 87 LIITE APPENDIX 8 / 1 Analyte Unit Sample zgraphics Z value Outl Assigned test OK value 2* Targ SD% Lab's result Md. Mean SD SD% Passed Outl. failed Missing Num of labs 0,377 yes 3,32 3,4 3,16 3,2 0,37 11, Laboratory 17 Se 1,160 yes ,8 44,7 4 3,18 7, ,360 yes 30,1 37,2 29,9 30,3 2,9 9, V 1,790 yes 3,79 1 4,3 3,6 3,6 0,332 9, ,372 yes 86 84,4 84,7 84,6 4,04 4, ,14 yes 4,83 4,9 4,78 4,7 0,449 9, ,008 yes 82,8 1 82,8 82,8 82,3 4,0 4, ,260 yes 12,6 1,4 12,6 12,7 1,17 9, Zn 0,306 yes 7,8 2 8,1 8,1 8,1 1,94 22, ,07 yes ,84, ,228 yes 1,8 2 16,3 1,9 1,9 2,41 1, ,4 yes ,6 8, ,048 yes 2,3 2 3,1 2,3,42, Laboratory 18 Hg A1Hg 2,80 C 0,83 0,61 0,766 0,78 0,118 1, S6M 3,030 H 0,13 2 0,179 0,134 0,126 0,023, THg 1,40 yes 2,28 2 2,72 2,3 2,3 0,6 23, TC S6M H Laboratory 19 Al 0, yes 1,6 2 1,2 1,4 1, 1,91 12, ,030 yes , ,797 yes ,9 7, ,791 yes ,1 4, ,2 yes ,8 14, As 0,760 yes 6,0 6,1 6,01,9 0,82 14, ,00 yes , 7 6,8 3,68 6, ,78 yes 3,77 2 4,14 3,71 3,7 0,877 24, ,486 yes 97,7 2 97,7 97,6 6,31 6, ,7 yes 4,86 2 4,92 4,97 4,8 0,731 1, Cd 0,742 yes 0,66 0,611 0,628 0,634 0, , ,0 yes 6,4 1 6,41 6,41 6,44 0,426 6, ,611 yes 0,81 0,76 0,797 0,80 0,073 9, ,642 yes 30,1 1 31,6 29,8 30,3 2,24 7, ,284 yes 2,82 1 2,88 2,8 2,83 0,241 8, Co 0,31 yes 2,71 2,8 2,7 2,68 0,299 11, ,74 yes 47 48,8 46,8 46, 2,37, ,673 yes 3,12 3,33 3,1 3,09 0,176, ,96 yes 40,3 1 42,1 40,6 40,3 2, ,1 yes 1, 1 16,8 1, 1,4 1,32 8, Cr 0,147 yes 2,04 2,07 2,06 2,03 0,24 11, ,06 yes ,2 78, 4,8 6, ,184 yes,3,,4,3 0,938 9, ,226 yes ,43 4, ,042 yes 8,37 8,4 8,6 8,48 0,99 11, Cu 2, yes 2,28 2,86 2,3 2,21 0,31 1, ,702 yes 7 9 6,3 6,1 3, ,7 yes 12,2 1 11,7 12,3 12,2 1,06 8, ,280 yes 83,4 1 8, ,1 4,09 4, ,076 yes 9,92 9,8 9,91 1,02, Fe 3,600 yes,2 30 4,69 9,91 9,64 2,93 30, ,163 yes ,9, ,112 yes , ,149 yes ,361 yes , Hg A1Hg 1,690 yes 0,83 0,69 0,766 0,78 0,118 1, N3Hg 0,729 yes 0,17 2 0,14 0,163 0,164 0, , THg 0,89 yes 2,28 2 2,4 2,3 2,3 0,6 23, Mn 0,113 yes 3,9 2 3,96 3,86 3,8 0,37 9, ,689 yes 90 93,1 92,3 91,9 7,04 7, ,468 yes 44,2 1 4,8 44,8 44,4 3,42 7, ,76 yes ,2 4, ,7 yes ,4, Ni 0,441 yes 6,24,96,84, , ,181 yes 69 70,3 67,4 67 4, ,284 yes 6,17 6,3 6,22 6,14 0,61 9, ,060 yes ,92 4, Outlier test failed: C Cohcran, G1 Grubbs(1outlier algorithm), G2 Grubbs(2outliers algorithm), H Hampel, M manual SYKE Interlaboratory comparison test 3/

90 LIITE 8 / APPENDIX Analyte Unit Sample zgraphics Z value Outl Assigned test OK value 2* Targ SD% Lab's result Md. Mean SD SD% Passed Outl. failed Missing Num of labs Laboratory Pb Se V Zn Laboratory Al Cd Co Cr Cu Fe Mn Ni Pb 0,36 yes 11,2 11, ,1 1,26 11, ,11 yes 1,99 2,02 1,98 2,01 0,363 18, ,4 yes 92,9 94,8 92,8 93,2,66 6, ,66 yes 6,12 1,86,96 6,02 0,4 9, ,496 yes 67,6 70,9 67,4 67,2 4,89 7, ,904 yes 3,32 3,62 3,16 3,2 0,37 11, H 1,2 < 1,1 1,14 0,237, ,4 yes , 44,7 4 3,18 7, H 2,67 < 2,71 2,3 0,22, ,030 yes 30,1 33,2 29,9 30,3 2,9 9, ,1 yes 6,72 7,46 6,7 6,66 0,709, ,090 yes 3,79 1 3,48 3,6 3,6 0,332 9, ,884 yes 86 89,8 84,7 84,6 4,04 4, ,124 yes 4,83 4,89 4,78 4,7 0,449 9, ,032 yes 82,8 1 82,6 82,8 82,3 4,0 4, ,068 yes 12,6 12,7 12,6 12,7 1,17 9, ,611 yes 7,8 2 8,4 8,1 8,1 1,94 22, ,323 yes ,84, ,149 yes 1,8 2 16,1 1,9 1,9 2,41 1, ,64 yes ,6 8, ,249 yes 2,3 3,6 3,1 2,3,42, ,490 H 1,6 2 22,4 1,4 1, 1,91 12, ,370 yes , ,8 yes ,9 7, ,090 H ,1 4, ,00 H ,8 14, ,2 yes 0,66 0,8 0,628 0,634 0, , ,417 yes 6,4 1 6,2 6,41 6,44 0,426 6, ,988 yes 0,81 0,73 0,797 0,80 0,073 9, ,32 yes 30,1 1 28,9 29,8 30,3 2,24 7, ,800 yes 2,82 1 2,44 2,8 2,83 0,241 8, ,80 yes 2,71 2,21 2,7 2,68 0,299 11, ,2 yes 47 41,8 46,8 46, 2,37, ,70 yes 3,12 2,9 3,1 3,09 0,176, ,2 yes 40,3 1 36,6 40,6 40,3 2, ,6 yes 1, 1 11,3 1, 1,4 1,32 8, ,907 yes 2,04 2,22 2,06 2,03 0,24 11, ,0 yes 79 87,7 78,2 78, 4,8 6, ,388 yes,3,7,4,3 0,938 9, ,4 yes ,43 4, ,484 yes 8,37 7,96 8,6 8,48 0,99 11, ,197 yes 2,28 2,33 2,3 2,21 0,31 1, ,400 yes 7 3 6,3 6,1 3, ,4 yes 12,2 1 13, 12,3 12,2 1,06 8, ,44 yes 83,4 1 86, ,1 4,09 4, ,40 C 9,92 12,4 9,8 9,91 1,02, ,440 yes, ,91 9,64 2,93 30, ,326 yes ,9, ,02 yes , ,199 yes ,273 yes , ,697 yes 3,9 2 3,6 3,86 3,8 0,37 9, ,670 yes ,3 91,9 7,04 7, ,090 yes 44,2 1 44, 44,8 44,4 3,42 7, ,290 yes ,2 4, ,436 yes ,4, ,940 yes 6,24,03,84, , ,440 yes 69 2,2 67,4 67 4, ,713 yes 6,17,73 6,22 6,14 0,61 9, ,82 yes ,92 4, ,40 yes 11,2 9, ,1 1,26 11, ,3 yes 1,99 1,13 1,98 2,01 0,363 18, ,790 H 92, ,8 93,2,66 6, ,697 yes 6,12 1,8,96 6,02 0,4 9, ,760 yes 67,6,7 67,4 67,2 4,89 7, ,211 yes 3,32 3,2 3,16 3,2 0,37 11, Outlier test failed: C Cohcran, G1 Grubbs(1outlier algorithm), G2 Grubbs(2outliers algorithm), H Hampel, M manual SYKE Interlaboratory comparison test 3/

91 89 LIITE APPENDIX 8 / 17 Analyte Unit Sample zgraphics Z value Outl Assigned test OK value 2* Targ SD% Lab's result Md. Mean SD SD% Passed Outl. failed Missing Num of labs V 2,430 yes 3,79 1 3,1 3,6 3,6 0,332 9, Laboratory V 8,9 H 86 47,7 84,7 84,6 4,04 4, ,340 yes 4,83 3,7 4,78 4,7 0,449 9, ,990 H 82,8 1 1,8 82,8 82,3 4,0 4, ,330 H 12,6 8,4 12,6 12,7 1,17 9, Zn 2,900 C ,84, ,80 yes ,6 8, ,60 H 2,3 28 3,1 2,3,42, Laboratory 21 Al 0,214 yes , As 0,912 yes 7 1 3,1 7 6,8 3,68 6, ,074 yes 16,3 2 16,1 16,2 16,4 1,92 11, SO6 yes 17,4 17,4 16,9 1, Cd 0,8 yes 6,4 1 6, 6,41 6,44 0,426 6, ,63 yes 0,71 2 0,66 0,701 0,712 0,119 16, SO6 yes 0,73 0,748 0,793 0,162,3 0 0 Co 0,298 yes 47 46,3 46,8 46, 2,37, ,330 yes 16,9 2 14,1 16,9 17,2 2,46 14, SO6 yes 18,9 18,8 19,1 1,82 9, 0 0 Cr 2,30 yes ,2 78, 4,8 6, ,3 yes 6 2 4,3 6,7 63,8 9,07 14, SO6 yes 64,3 77, 73,2 8,61 11,7 0 0 Cu 0,684 yes 7 6,3 6,1 3, ,800 yes 40 36,8 40,2 39,8,16 12, SO6 yes 37 39, 39,9 2,91 7,3 0 0 Fe 0,879 yes ,9, Hg A1Hg H 0,83 <8,0 0,766 0,78 0,118 1, S6M 7,080 H 0,13 2 0,24 0,134 0,126 0,023, Ni 0,413 yes 69 66,2 67,4 67 4, ,7 yes 38,3 31, ,8 4,37 11, SO6 yes 29,4 38,6 38,2 6,44 16,8 0 0 Pb 1,7 yes 92,9 84,9 92,8 93,2,66 6, ,840 yes 46, 33,3 46,3 4,4 6 13, SO6 yes 46,9 47,3 47,3 0,40 0, V 0,76 yes 86 82,8 84,7 84,6 4,04 4, ,128 yes 70,3 69,4 69,7 70,3 8,34 11, SO6 yes 61 80,6 80,3 14,7 18, Zn 0,8 yes ,84, ,080 yes ,2, SO6 yes ,4 11,3 0 0 Laboratory 22 Al As Cd Co Cr 0,128 yes 1,6 2 1,4 1,4 1, 1,91 12, ,60 yes , ,363 yes ,9 7, ,428 yes , , yes ,1 4, ,330 yes ,8 14, ,490 yes 6,0,1 6,01,9 0,82 14, ,96 yes 7 1 9, 7 6,8 3,68 6, ,90 yes 3,77 2 4,69 3,71 3,7 0,877 24, ,640 yes 16,3 2 12,9 16,2 16,4 1,92 11, ,290 yes 91,1 79,3 91,9 90,8 7,66 8, ,041 yes 4,86 2 4,88 4,97 4,8 0,731 1, ,939 yes 0,66 0,98 0,628 0,634 0, , ,36 yes 6,4 1 6,22 6,41 6,44 0,426 6, ,80 yes 0,81 0,763 0,797 0,80 0,073 9, ,7 yes 0,71 2 0,761 0,701 0,712 0,119 16, ,0 yes 30,1 1 27,8 29,8 30,3 2,24 7, ,9 yes 2,82 1 2,42 2,8 2,83 0,241 8, ,800 H 2,71 6,99 2,7 2,68 0,299 11, ,430 C 47 2,7 46,8 46, 2,37, ,000 H 3,12 7,0 3,1 3,09 0,176, ,071 yes 16,9 2 17,1 16,9 17,2 2,46 14, ,29 H 40,3 1 38,7 40,6 40,3 2, ,460 H 1, 1 26, 1, 1,4 1,32 8, ,098 yes 2,04 2,02 2,06 2,03 0,24 11, Outlier test failed: C Cohcran, G1 Grubbs(1outlier algorithm), G2 Grubbs(2outliers algorithm), H Hampel, M manual SYKE Interlaboratory comparison test 3/

92 LIITE 8 / APPENDIX Analyte Unit Sample zgraphics Z value Outl Assigned test OK value 2* Targ SD% Lab's result Md. Mean SD SD% Passed Outl. failed Missing Num of labs 2,130 yes 79 70,6 78,2 78, 4,8 6, Laboratory 22 Cr 1,00 yes,3 9,21,4,3 0,938 9, ,271 yes ,8 6,7 63,8 9,07 14, ,2 yes ,6, ,0 yes 8,37 6,3 8,6 8,48 0,99 11, Cu 4,690 H 2,28 3,3 2,3 2,21 0,31 1, ,330 yes 7 3,2 6,3 6,1 3, ,929 yes 12,2 1 13,1 12,3 12,2 1,06 8, ,860 yes 40 47, 40,2 39,8,16 12, ,249 yes 8,6 1 87,2 8,3 8,6 3,6 4, ,6 yes 9,92 9,36 9,8 9,91 1,02, Fe 0,402 yes,2 30,8 9,91 9,64 2,93 30, ,00 yes ,9, ,800 yes , ,00 yes , ,60 yes ,460 yes , Hg A1Hg 1,140 yes 0,83 0,73 0,766 0,78 0,118 1, N3Hg 1,880 yes 0,17 2 0,13 0,163 0,164 0, , S6M 1,260 yes 0,13 2 0,11 0,134 0,126 0,023, THg 0,96 yes 2,28 2 2,4 2,3 2,3 0,6 23, Mn 23,0 H 3,9 2 1,2 3,86 3,8 0,37 9, ,670 C 90 97, 92,3 91,9 7,04 7, ,392 C 44,2 1 4, 44,8 44,4 3,42 7, , yes , ,909 C ,2 4, ,861 C ,7 4, ,92 yes ,4, N S6M 0,37 yes , Ni 2,40 yes 6,24 4,66,84, , ,070 yes 69 61,6 67,4 67 4, ,1 yes 6,17 6,86 6,22 6,14 0,61 9, ,313 yes 38,3 37, ,8 4,37 11, ,741 yes ,92 4, ,223 yes 11,2, ,1 1,26 11, P S6M 0,0 yes , Pb 0,00 yes 1,99 2,00 1,98 2,01 0,363 18, ,721 yes 92,9 89,6 92,8 93,2,66 6, ,8 yes 6,12 1,29,96 6,02 0,4 9, ,194 yes 46, 47,4 46,3 4,4 6 13, ,69 yes 67,6 62,9 67,4 67,2 4,89 7, ,70 H 3,32 0,474 3,16 3,2 0,37 11, Zn 0,21 yes ,2, Laboratory 23 Al 0,463 yes , As 0,638 yes 16, ,2 16,4 1,92 11, Cd 0,98 yes 0,71 2 0,79 0,701 0,712 0,119 16, Co 0,899 yes 16, ,9 17,2 2,46 14, Cr 0,492 yes ,7 63,8 9,07 14, Cu 0,70 C ,2 39,8,16 12, Fe 2,060 yes , Hg S6M 0,000 yes 0,13 2 0,13 0,134 0,126 0,023, Mn 1,0 yes , N S6M 0,162 yes , Ni 0,9 yes 38,3 37, 38 37,8 4,37 11, P S6M 0,400 yes , Pb 0,38 yes 46, 49 46,3 4,4 6 13, S S6M 1,760 yes , Se yes 1,3 0,924 1,6 1,9 1, TC S6M H V 0,41 yes 70,3 66, 69,7 70,3 8,34 11, Zn 0,789 yes ,2, Outlier test failed: C Cohcran, G1 Grubbs(1outlier algorithm), G2 Grubbs(2outliers algorithm), H Hampel, M manual SYKE Interlaboratory comparison test 3/

93 91 LIITE APPENDIX 8 / 19 Analyte Unit Sample zgraphics Z value Outl Assigned test OK value 2* Targ SD% Lab's result Md. Mean SD SD% Passed Outl. failed Missing Num of labs Laboratory Cd Co Cu Fe Pb Zn Laboratory Al As Cd Co Cr Cu Fe Hg Mn 24 2 A1Hg N3Hg 3,800 H 0,66 0,911 0,628 0,634 0, , ,80 H 6,4 1 3,243 6,41 6,44 0,426 6, ,700 H 30,1 1 1,39 29,8 30,3 2,24 7, ,800 H 47 19,21 46,8 46, 2,37, ,6 H 2,28 3,79 2,3 2,21 0,31 1, ,600 H 7 23,84 6,3 6,1 3, ,60 H 12,2 1,28 12,3 12,2 1,06 8, ,000 H 83,4 1 8, ,1 4,09 4, ,140 H 9,92 0,88 9,8 9,91 1,02, ,676 yes , ,9, ,240 yes , , ,400 yes , ,8 H , , ,380 H 92,9 63,2 92,8 93,2,66 6, ,0 H 67,6 6,60 67,4 67,2 4,89 7, ,340 yes , ,84, ,460 yes , ,6 8, ,0 yes 2,3 41,80 3,1 2,3,42, ,077 yes 1,6 2 1,4 1,4 1, 1,91 12, ,417 yes , ,307 yes ,9 7, ,40 yes , ,013 yes ,1 4, ,07 yes ,8 14, ,87 yes 6,0,7 6,01,9 0,82 14, , yes 7 1 7, 7 6,8 3,68 6, ,127 yes 3,77 2 3,71 3,71 3,7 0,877 24, ,8 yes 16,3 2 17,9 16,2 16,4 1,92 11, ,067 yes 97, ,7 97,6 6,31 6, ,017 yes 4,86 2 4,8 4,97 4,8 0,731 1, ,04 yes 0,66 0,663 0,628 0,634 0, , ,292 yes 6,4 1 6,4 6,41 6,44 0,426 6, ,086 yes 0,81 0,817 0,797 0,80 0,073 9, ,0 yes 0,71 2 0,817 0,701 0,712 0,119 16, ,3 yes 30,1 1 30,8 29,8 30,3 2,24 7, ,213 yes 2,82 1 2,87 2,8 2,83 0,241 8, ,074 yes 2,71 2,73 2,7 2,68 0,299 11, ,043 yes 47 47,1 46,8 46, 2,37, ,817 yes 3,12 3,38 3,1 3,09 0,176, ,180 yes 16,9 2 19,4 16,9 17,2 2,46 14, ,79 yes 40, ,6 40,3 2, ,20 yes 1, 1 16,9 1, 1,4 1,32 8, ,368 yes 2,04 2,12 2,06 2,03 0,24 11, ,127 yes 79 78, 78,2 78, 4,8 6, ,728 yes,3 11,1,4,3 0,938 9, ,670 yes ,6 6,7 63,8 9,07 14, ,386 yes ,43 4, ,27 yes 8,37 8,6 8,6 8,48 0,99 11, ,28 yes 2,28 2,34 2,3 2,21 0,31 1, ,211 yes 7 7,6 6,3 6,1 3, ,090 yes 12,2 1 13,2 12,3 12,2 1,06 8, ,440 yes 40 4,8 40,2 39,8,16 12, ,36 yes 83,4 1 86, ,1 4,09 4, ,790 yes 9,92 11,7 9,8 9,91 1,02, ,288 yes,2 30 9,76 9,91 9,64 2,93 30, ,114 yes ,9, ,386 yes , ,808 yes , ,411 yes ,20 yes , ,140 yes 0,83 0,92 0,766 0,78 0,118 1, ,612 yes 0,17 2 0,183 0,163 0,164 0, , ,01 yes 3,9 2 3,88 3,86 3,8 0,37 9, ,378 yes 90 88,3 92,3 91,9 7,04 7, ,618 yes 44,2 1 46,3 44,8 44,4 3,42 7, ,813 yes , Outlier test failed: C Cohcran, G1 Grubbs(1outlier algorithm), G2 Grubbs(2outliers algorithm), H Hampel, M manual SYKE Interlaboratory comparison test 3/

94 LIITE 8 / 92 APPENDIX Analyte Unit Sample zgraphics Z value Outl Assigned test OK value 2* Targ SD% Lab's result Md. Mean SD SD% Passed Outl. failed Missing Num of labs 0,333 yes ,2 4, Laboratory 2 Mn 0,746 yes ,4, Ni 0,080 yes 6,24 6,29,84, , ,000 yes ,4 67 4, ,843 yes 6,17 6,69 6,22 6,14 0,61 9, ,480 yes 38, ,8 4,37 11, ,864 yes ,92 4, ,848 yes 11,2 12, ,1 1,26 11, P S6M 0,332 yes , Pb 0,63 yes 1,99 2,12 1,98 2,01 0,363 18, ,732 yes 92,9 96,3 92,8 93,2,66 6, ,490 yes 6,12 1 6,34,96 6,02 0,4 9, ,871 yes 46, 0, 46,3 4,4 6 13, ,214 yes 67, ,4 67,2 4,89 7, ,42 yes 3,32 3, 3,16 3,2 0,37 11, S S6M 0,246 yes , Se 1,170 yes 1,2 1,06 1,1 1,14 0,237, ,8 yes ,8 44,7 4 3,18 7, ,6 yes 2,67 2,84 2,71 2,3 0,22, yes 2,02 0,924 1,6 1,9 1, ,133 yes 30,1 29,7 29,9 30,3 2,9 9, ,424 yes 6,72 7 6,7 6,66 0,709, V 0,03 yes 3,79 1 3,78 3,6 3,6 0,332 9, ,337 yes 86 84,6 84,7 84,6 4,04 4, ,642 yes 4,83,14 4,78 4,7 0,449 9, ,690 yes 70,3 82,2 69,7 70,3 8,34 11, ,217 yes 82,8 1 84,2 82,8 82,3 4,0 4, ,63 yes 12,6 13,4 12,6 12,7 1,17 9, Zn 0,418 yes 7,8 2 7,44 8,1 8,1 1,94 22, ,143 yes ,84, ,02 yes 1,8 2 1,9 1,9 1,9 2,41 1, ,932 yes ,2, ,409 yes ,6 8, ,229 yes 2,3 3, 3,1 2,3,42, Laboratory 26 Al As Cd Co Cr Cu 0,61 yes 1,6 2 16,8 1,4 1, 1,91 12, ,37 yes , ,0 yes ,9 7, ,669 yes , ,636 yes , 9, ,07 yes ,8 14, ,083 yes 6,0 6,1 6,01,9 0,82 14, ,012 yes ,8 3,68 6, ,297 yes 3,77 2 3,63 3,71 3,7 0,877 24, ,319 yes 16, ,2 16,4 1,92 11, ,040 yes 91,1 1 91,9 90,8 7,66 8, ,02 yes 4,86 2 4,88 4,97 4,8 0,731 1, ,379 yes 0,66 0,63 0,628 0,634 0, , ,479 yes 6,4 1 6,63 6,41 6,44 0,426 6, ,790 yes 0,81 0,874 0,797 0,80 0,073 9, ,22 yes 0,71 2 0,73 0,701 0,712 0,119 16, ,924 yes 30,3 1 32,4 30,1 30,1 1,93 6, ,090 yes 2,82 1 3,0 2,8 2,83 0,241 8, ,0 yes 2,71 2,73 2,7 2,68 0,299 11, ,681 yes 47 48,6 46,8 46, 2,37, ,481 yes 3,12 3,27 3,1 3,09 0,176, ,40 yes 16,9 2 17,9 16,9 17,2 2,46 14, ,790 yes 40, 1 42,9 40,8 40, 1,77 4, ,030 yes 1, 1 16,7 1, 1,4 1,32 8, ,96 yes 2,04 2,24 2,06 2,03 0,24 11, ,848 yes 79 82,3 78,2 78, 4,8 6, ,922 yes,3 11,3,4,3 0,938 9, ,8 yes ,8 6,7 63,8 9,07 14, ,170 yes ,6, ,914 yes 8,37 9,13 8,6 8,48 0,99 11, ,724 yes 2,28 2,4 2,3 2,21 0,31 1, ,89 yes 7 9, 6,3 6,1 3, Outlier test failed: C Cohcran, G1 Grubbs(1outlier algorithm), G2 Grubbs(2outliers algorithm), H Hampel, M manual SYKE Interlaboratory comparison test 3/

95 93 LIITE APPENDIX 8 / 21 Analyte Unit Sample zgraphics Z value Outl Assigned test OK value 2* Targ SD% Lab's result Md. Mean SD SD% Passed Outl. failed Missing Num of labs 1,0 yes 12,2 1 13,3 12,3 12,2 1,06 8, Laboratory 26 Cu 0,0 yes 40 42,2 40,2 39,8,16 12, ,740 yes 8,6 1 90,3 8,3 8,6 3,6 4, ,190 yes 9,92 11,1 9,8 9,91 1,02, Fe 2,780 C, ,4 9,91 9,64 2,93 30, ,423 yes ,9, ,323 yes , ,660 yes , ,864 yes , 6, ,770 yes , Hg A1Hg 1,170 yes 0,83 0,732 0,766 0,78 0,118 1, N3Hg 0,424 yes 0,17 2 0,161 0,163 0,164 0, , S6M 0,4 yes 0,13 2 0,139 0,134 0,126 0,023, THg 0,912 yes 2,28 2 2,02 2,3 2,3 0,6 23, Mn 0,677 yes 3,9 2 4,23 3,86 3,8 0,37 9, ,490 yes 90 96,7 92,3 91,9 7,04 7, ,20 yes 44,2 1 48,4 44,8 44,4 3,42 7, ,99 yes , ,080 yes ,7 4, ,60 yes ,4, Ni 0,78 yes 6,24 6,73,84, , ,8 yes 69 72,8 67,4 67 4, ,070 yes 6,17 6,83 6,22 6,14 0,61 9, ,93 yes 38, ,8 4,37 11, ,894 yes ,92 4, ,670 yes 11,2 11, ,1 1,26 11, P S6M 0,440 yes , Pb 0,02 yes 1,99 1,98 1,98 2,01 0,363 18, ,60 yes 92,9 90,3 92,8 93,2,66 6, ,381 yes 6,12 1,9,96 6,02 0,4 9, ,247 yes 46, 47,6 46,3 4,4 6 13, ,412 yes 6,6 68,3 6, 64,7,03 7, ,482 yes 3,32 3,48 3,16 3,2 0,37 11, S S6M 0,392 yes , Se 0,98 yes 1,2 1,31 1,1 1,14 0,237, ,8 yes ,7 4 3,18 7, ,468 yes 2,67 2,79 2,71 2,3 0,22, yes 0,8 0,924 1,6 1,9 1, ,29 yes 29,3 27,8 29, 29,1 3,79 13, ,1 yes 6,72,97 6,7 6,66 0,709, V 0,668 yes 3,79 1 3,98 3,6 3,6 0,332 9, ,130 yes 86 90,8 84,7 84,6 4,04 4, ,600 yes 4,83,12 4,78 4,7 0,449 9, ,6 yes 70,3 71,8 69,7 70,3 8,34 11, ,639 yes 82,4 1 86,3 82,3 82,3 3,96 4, ,16 yes 12,6 13,3 12,6 12,7 1,17 9, Zn 2,70 yes 7,8 2,4 8,1 8,1 1,94 22, ,609 yes ,84, ,329 yes 1,8 2 16,4 1,9 1,9 2,41 1, ,21 yes ,2, ,70 yes ,27 3, ,290 yes 2,3 9 3,1 2,3,42, Laboratory 27 Cd 1,430 yes 30,3 1 33, 30,1 30,1 1,93 6, Cr 1,670 C ,6, Cu 2,240 C 8, ,3 8,6 3,6 4, Fe 1,680 yes ,9, ,000 yes , 6, , H , Mn 0,419 yes ,7 4, ,74 yes ,4, Ni 0,6 yes ,92 4, Zn 0,179 yes ,84, ,422 yes ,27 3, Outlier test failed: C Cohcran, G1 Grubbs(1outlier algorithm), G2 Grubbs(2outliers algorithm), H Hampel, M manual SYKE Interlaboratory comparison test 3/

96 LIITE 8 / APPENDIX Analyte Unit Sample zgraphics Z value Outl Assigned test OK value 2* Targ SD% Lab's result Md. Mean SD SD% Passed Outl. failed Missing Num of labs Laboratory 28 Al As Cd Co Cr Cu Fe Hg Mn N Ni Pb Se A1Hg N3Hg S6M THg S6M 0,61 yes 1,6 2 14,4 1,4 1, 1,91 12, ,690 yes , ,940 yes ,9 7, ,673 yes , ,070 yes , 9, ,380 yes ,8 14, ,496 C 6,0,7 6,01,9 0,82 14, ,374 yes 7 1,4 7 6,8 3,68 6, ,382 yes 3,77 2 3,9 3,71 3,7 0,877 24, ,294 yes 16,3 2 16,9 16,2 16,4 1,92 11, ,800 yes 91,1 74,7 91,9 90,8 7,66 8, ,724 yes 4,86 2,3 4,97 4,8 0,731 1, ,78 yes 0,66 0,61 0,628 0,634 0, , ,8 yes 6,4 1 6,3 6,41 6,44 0,426 6, ,432 yes 0,81 0,77 0,797 0,80 0,073 9, ,3 yes 0,71 2 0,679 0,701 0,712 0,119 16, ,836 yes 30,3 1 28,4 30,1 30,1 1,93 6, ,3 yes 2,82 1 3,1 2,8 2,83 0,241 8, ,140 yes 2,71 2,4 2,7 2,68 0,299 11, ,979 yes 47 44,7 46,8 46, 2,37, ,86 yes 3,12 2,8 3,1 3,09 0,176, ,180 C 16,9 2 12,3 16,9 17,2 2,46 14, ,16 yes 40, ,8 40, 1,77 4, ,080 yes 1, 1 16,8 1, 1,4 1,32 8, ,39 yes 2,04 2,1 2,06 2,03 0,24 11, ,190 yes 79 79,8 78,2 78, 4,8 6, ,680 yes,3 9,6,4,3 0,938 9, ,700 yes 6 2 1,2 6,7 63,8 9,07 14, ,683 yes ,6, ,140 yes 8, ,6 8,48 0,99 11, ,789 yes 2,28 2,1 2,3 2,21 0,31 1, ,680 yes 7 2,2 6,3 6,1 3, ,929 yes 12,2 1 11,3 12,3 12,2 1,06 8, ,840 yes 40 28,6 40,2 39,8,16 12, ,732 yes 8,6 1 80,9 8,3 8,6 3,6 4, ,333 yes 9,92,3 9,8 9,91 1,02, ,26 yes, ,91 9,64 2,93 30, ,38 yes ,9, ,31 yes , ,379 yes , ,084 yes , 6, ,321 yes , ,361 yes 0,83 0,8 0,766 0,78 0,118 1, ,60 C 0,17 2 0, 0,163 0,164 0, , ,1 yes 0,13 2 0,148 0,134 0,126 0,023, ,470 yes 2,28 2 2,7 2,3 2,3 0,6 23, , yes 3,9 2 3,8 3,86 3,8 0,37 9, ,011 yes ,3 91,9 7,04 7, ,400 yes 44,2 1 39, 44,8 44,4 3,42 7, ,9 yes , ,066 yes ,7 4, ,241 yes ,4, ,900 yes , ,86 yes 6,24,7,84, , ,797 yes 69 63, 67,4 67 4, ,681 yes 6,17,7 6,22 6,14 0,61 9, ,60 yes 38,3 28, ,8 4,37 11, ,016 yes ,92 4, ,740 yes 11,2 13, ,1 1,26 11, ,3 yes 1,99 2,4 1,98 2,01 0,363 18, ,9 yes 92,9 79,3 92,8 93,2,66 6, ,06 C 6,12 1 6,1,96 6,02 0,4 9, ,430 yes 46, 44, 46,3 4,4 6 13, ,0 yes 6,6 7,8 6, 64,7,03 7, ,0 yes 3,32 4,0 3,16 3,2 0,37 11, ,833 yes 1,2 1,3 1,1 1,14 0,237, ,40 yes , 44,7 4 3,18 7, Outlier test failed: C Cohcran, G1 Grubbs(1outlier algorithm), G2 Grubbs(2outliers algorithm), H Hampel, M manual SYKE Interlaboratory comparison test 3/

97 9 LIITE APPENDIX 8 / 23 Analyte Unit Sample zgraphics Z value Outl Assigned test OK value 2* Targ SD% Lab's result Md. Mean SD SD% Passed Outl. failed Missing Num of labs 1,4 yes 2,67 3,0 2,71 2,3 0,22, Laboratory 28 Se yes 1,67 0,924 1,6 1,9 1, ,7 yes 29,3 21,4 29, 29,1 3,79 13, ,193 yes 6,72 6,8 6,7 6,66 0,709, V 0,668 yes 3,79 1 3,6 3,6 3,6 0,332 9, ,080 yes 86 90,7 84,7 84,6 4,04 4, ,787 yes 4,83 4,4 4,78 4,7 0,449 9, ,2 yes 70,3 4,8 69,7 70,3 8,34 11, ,744 yes 82, ,3 82,3 3,96 4, ,430 yes 12,6 14,4 12,6 12,7 1,17 9, Zn 0, yes 7,8 2 8,3 8,1 8,1 1,94 22, ,670 yes ,84, ,734 yes 1,8 2 17,3 1,9 1,9 2,41 1, ,30 yes ,2, ,23 yes ,27 3, ,30 yes 2,3 60,3 3,1 2,3,42, Laboratory 29 Al As Cd Co Cr Cu Fe Hg Mn A1Hg N3Hg S6M THg 0,897 yes 1,6 2 13,8 1,4 1, 1,91 12, ,90 yes , ,40 yes ,9 7, ,1 yes , ,700 yes ,1 4, ,840 yes ,8 14, ,30 yes 6,0,23 6,01,9 0,82 14, ,890 yes ,9 7 6,8 3,68 6, ,849 yes 3,77 2 3,37 3,71 3,7 0,877 24, , yes 16,3 2 19,4 16,2 16,4 1,92 11, ,600 yes 97,7 82,1 97,7 97,6 6,31 6, ,782 yes 4,86 2 4,38 4,97 4,8 0,731 1, ,818 yes 0,66 0,606 0,628 0,634 0, , ,0 yes 6,4 1,87 6,41 6,44 0,426 6, ,040 yes 0,81 0,726 0,797 0,80 0,073 9, ,783 yes 0,71 2 0,78 0,701 0,712 0,119 16, ,400 yes 30,1 1 26,9 29,8 30,3 2,24 7, ,61 yes 2,82 1 2,69 2,8 2,83 0,241 8, ,240 yes 2,71 2,38 2,7 2,68 0,299 11, ,280 yes 47 41,6 46,8 46, 2,37, ,833 yes 3,12 2,86 3,1 3,09 0,176, ,994 yes 16, ,9 17,2 2,46 14, ,370 yes 40,3 1 36,2 40,6 40,3 2, ,1 yes 1, 1 14,2 1, 1,4 1,32 8, , yes 2,04 1,73 2,06 2,03 0,24 11, ,60 yes 79 68, 78,2 78, 4,8 6, ,230 yes,3 9,04,4,3 0,938 9, ,270 yes 6 2 7,3 6,7 63,8 9,07 14, ,870 yes ,43 4, ,370 yes 8,37 7,22 8,6 8,48 0,99 11, ,066 yes 2,28 2,29 2,3 2,21 0,31 1, ,0 yes 7 1,3 6,3 6,1 3, ,8 yes 12,2 1 11,4 12,3 12,2 1,06 8, ,2 yes 40 44,8 40,2 39,8,16 12, ,4 yes 83,4 1 74, ,1 4,09 4, ,912 yes 9,92 9,02 9,8 9,91 1,02, ,461 yes,2 30 9, 9,91 9,64 2,93 30, ,740 yes ,9, ,2 yes , ,19 yes , ,830 yes ,970 yes , ,140 yes 0,83 1,01 0,766 0,78 0,118 1, ,3 H 0,17 2 0,24 0,163 0,164 0, , ,23 yes 0,13 2 0,121 0,134 0,126 0,023, ,090 yes 2,28 2 2,9 2,3 2,3 0,6 23, ,81 yes 3,9 2 3,48 3,86 3,8 0,37 9, ,960 yes 90 81,2 92,3 91,9 7,04 7, ,2 yes 44,2 1 40,2 44,8 44,4 3,42 7, ,6 yes , Outlier test failed: C Cohcran, G1 Grubbs(1outlier algorithm), G2 Grubbs(2outliers algorithm), H Hampel, M manual SYKE Interlaboratory comparison test 3/

98 LIITE 8 / APPENDIX Analyte Unit Sample zgraphics Z value Outl Assigned test OK value 2* Targ SD% Lab's result Md. Mean SD SD% Passed Outl. failed Missing Num of labs 2,3 yes ,2 4, Laboratory 29 Mn 1,330 yes ,4, N S6M 0,19 yes , Ni 1,190 yes 6,24,,84, , ,1 yes 69 61,3 67,4 67 4, ,67 yes 6,17,82 6,22 6,14 0,61 9, ,370 yes 38,3 43, 38 37,8 4,37 11, ,80 yes ,92 4, ,888 yes 11,2, ,1 1,26 11, P S6M 2,160 yes , Pb 0,980 yes 1,99 1,79 1,98 2,01 0,363 18, ,3 yes 92,9 86,8 92,8 93,2,66 6, ,784 yes 6,12 1,76,96 6,02 0,4 9, ,4 yes 46, 3,1 46,3 4,4 6 13, ,9 yes 67,6 61, 67,4 67,2 4,89 7, ,798 yes 3,32 3,0 3,16 3,2 0,37 11, S S6M 0,0 yes , Se 0,708 yes 1,2 1,11 1,1 1,14 0,237, ,83 yes ,3 44,7 4 3,18 7, ,768 yes 2,67 2,46 2,71 2,3 0,22, yes 0,788 0,924 1,6 1,9 1, ,080 yes 30,1 26,9 29,9 30,3 2,9 9, ,424 yes 6,72 6,44 6,7 6,66 0,709, TC S6M yes V 2,130 yes 3,79 1 3,19 3,6 3,6 0,332 9, ,900 yes 86 73,6 84,7 84,6 4,04 4, ,70 yes 4,83 3,98 4,78 4,7 0,449 9, ,932 yes 70,3 76,8 69,7 70,3 8,34 11, ,130 yes 82,8 1 69, 82,8 82,3 4,0 4, , yes 12,6,7 12,6 12,7 1,17 9, Zn 0,44 yes 7,8 2 7,41 8,1 8,1 1,94 22, ,360 yes ,84, ,481 yes 1,8 2 14,8 1,9 1,9 2,41 1, ,824 yes ,2, ,0 yes ,6 8, ,841 yes 2,3 47,9 3,1 2,3,42, Laboratory 30 Al 0,026 yes 1,6 2 1,7 1,4 1, 1,91 12, ,2 yes , ,307 yes ,9 7, ,012 yes , ,61 yes ,1 4, ,407 yes , 9, ,000 yes ,8 14, As 1,040 yes 6,0 6,68 6,01,9 0,82 14, ,17 yes 7 1 7,8 7 6,8 3,68 6, ,488 yes 3, ,71 3,7 0,877 24, ,319 yes 16,3 2 16,9 16,2 16,4 1,92 11, ,026 yes 97, ,7 97,6 6,31 6, ,291 yes 91,1 93,8 91,9 90,8 7,66 8, ,642 yes 4,86 2,2 4,97 4,8 0,731 1, Cd 0,879 yes 0,66 0,602 0,628 0,634 0, , ,34 yes 6,4 1 6,23 6,41 6,44 0,426 6, ,796 yes 0,81 0,746 0,797 0,80 0,073 9, ,011 yes 0,71 2 0,709 0,701 0,712 0,119 16, ,09 yes 30, ,8 30,3 2,24 7, ,638 yes 30,3 1 28,9 30,1 30,1 1,93 6, ,709 yes 2,82 1 2,67 2,8 2,83 0,241 8, Co 0,3 yes 2,71 2,6 2,7 2,68 0,299 11, ,6 yes 47 43,2 46,8 46, 2,37, ,272 yes 3,12 3,04 3,1 3,09 0,176, ,140 yes 16,9 2 19,3 16,9 17,2 2,46 14, ,447 yes 40, ,6 40,3 2, ,790 yes 40, 1 38,1 40,8 40, 1,77 4, ,64 yes 1, 1 14,8 1, 1,4 1,32 8, Cr 0,784 yes 2,04 1,88 2,06 2,03 0,24 11, ,114 yes 79 79, 78,2 78, 4,8 6, Outlier test failed: C Cohcran, G1 Grubbs(1outlier algorithm), G2 Grubbs(2outliers algorithm), H Hampel, M manual SYKE Interlaboratory comparison test 3/

99 97 LIITE APPENDIX 8 / 2 Analyte Unit Sample zgraphics Z value Outl Assigned test OK value 2* Targ SD% Lab's result Md. Mean SD SD% Passed Outl. failed Missing Num of labs 0,194 yes,3,1,4,3 0,938 9, Laboratory 30 Cr 0,11 yes ,2 6,7 63,8 9,07 14, ,16 yes ,43 4, ,00 yes ,6, ,04 yes 8,37 8,41 8,6 8,48 0,99 11, Cu 0,373 yes 2,28 2,37 2,3 2,21 0,31 1, ,26 yes 7, 6,3 6,1 3, ,46 yes 12,2 1 12,7 12,3 12,2 1,06 8, ,63 yes 40 42,3 40,2 39,8,16 12, ,743 yes 83,4 1 88, ,1 4,09 4, ,483 yes 8,6 1 88,7 8,3 8,6 3,6 4, ,267 yes 9,92,2 9,8 9,91 1,02, Fe,2 30 < 9,91 9,64 2,93 30, ,160 yes ,9, ,112 yes , ,46 yes , ,00 yes ,612 yes , 6, , yes , Mn H 3,9 2 < 3,86 3,8 0,37 9, ,111 yes 90 89, 92,3 91,9 7,04 7, ,99 yes 44,2 1 47, 44,8 44,4 3,42 7, ,27 yes , ,1 yes ,2 4, ,221 yes ,7 4, ,184 yes ,4, N S6M 1,1 yes , Ni 1,9 yes 6,24,04,84, , ,942 yes 69 62, 67,4 67 4, ,090 yes 6,17, 6,22 6,14 0,61 9, ,326 yes 38,3 39, 38 37,8 4,37 11, ,864 yes ,92 4, ,772 yes ,92 4, ,130 yes 11,2 9, ,1 1,26 11, P S6M 0,76 yes , Pb 0,829 yes 1,99 1,82 1,98 2,01 0,363 18, ,743 yes 92,9 89,4 92,8 93,2,66 6, ,440 yes 6,12 1,46,96 6,02 0,4 9, ,183 yes 46, 4,7 46,3 4,4 6 13, ,7 yes 67,6 66,2 67,4 67,2 4,89 7, ,33 yes 6,6 63,4 6, 64,7,03 7, ,8 yes 3,32 2,71 3,16 3,2 0,37 11, Zn H 7,8 2 < 8,1 8,1 1,94 22, ,681 yes ,84, ,9 yes 1, ,9 1,9 2,41 1, ,323 yes ,2, ,000 yes ,6 8, ,1 yes ,27 3, ,470 yes 2,3 60 3,1 2,3,42, Outlier test failed: C Cohcran, G1 Grubbs(1outlier algorithm), G2 Grubbs(2outliers algorithm), H Hampel, M manual SYKE Interlaboratory comparison test 3/

100 LIITE 8 / APPENDIX Analyte Unit Sample zgraphics Z value Outl Assigned test OK value 2* Targ SD% Lab's result Md. Mean SD SD% Passed Outl. failed Missing Num of labs Laboratory 31 Al As Cd Co Cr Cu Fe Hg Mn N Ni A1Hg N3Hg S6M THg S6M 0,692 yes 1,6 2 14,3 1,4 1, 1,91 12, ,601 yes , ,881 yes ,9 7, ,76 yes , ,10 yes ,1 4, ,1 yes , 9, ,2 yes ,8 14, ,678 yes 6,0,64 6,01,9 0,82 14, ,6 yes 7 1 4,2 7 6,8 3,68 6, ,743 yes 3,77 2 3,42 3,71 3,7 0,877 24, ,761 yes 16,3 2 14,8 16,2 16,4 1,92 11, ,32 yes 97,7 92, 97,7 97,6 6,31 6, ,143 yes 91,1 92,4 91,9 90,8 7,66 8, ,700 yes 4,86 2 4,44 4,97 4,8 0,731 1, ,409 yes 0,66 0,633 0,628 0,634 0, , ,188 yes 6,4 1 6,31 6,41 6,44 0,426 6, ,093 yes 0,81 0,802 0,797 0,80 0,073 9, ,766 yes 0,71 2 0,642 0,701 0,712 0,119 16, ,1 yes 30,1 1 29,8 29,8 30,3 2,24 7, ,088 yes 30,3 1 30, 30,1 30,1 1,93 6, ,284 yes 2,82 1 2,76 2,8 2,83 0,241 8, ,314 yes 2,71 2,63 2,7 2,68 0,299 11, ,32 yes 47 4,8 46,8 46, 2,37, ,048 yes 3,12 3,1 3,1 3,09 0,176, ,402 yes 16,9 2 16,1 16,9 17,2 2,46 14, ,364 yes 40,3 1 39,2 40,6 40,3 2, ,16 yes 40, ,8 40, 1,77 4, ,129 yes 1, 1 1,4 1, 1,4 1,32 8, ,060 yes 2,04 1,62 2,06 2,03 0,24 11, ,987 yes 79 7,1 78,2 78, 4,8 6, ,89 yes,3 9,41,4,3 0,938 9, ,763 yes 6 2 8,8 6,7 63,8 9,07 14, ,1 yes ,43 4, ,333 yes ,6, ,00 yes 8,37 7,49 8,6 8,48 0,99 11, ,480 yes 2,28 1,71 2,3 2,21 0,31 1, ,0 yes 7 4,1 6,3 6,1 3, ,273 yes 12,2 1 12,4 12,3 12,2 1,06 8, ,470 yes 40 34,1 40,2 39,8,16 12, ,344 yes 83,4 1 81, ,1 4,09 4, ,919 yes 8,6 1 79,7 8,3 8,6 3,6 4, ,440 yes 9,92 8,49 9,8 9,91 1,02, ,186 yes,2 30 9,91 9,91 9,64 2,93 30, ,340 yes ,9, ,240 yes , ,0 yes , ,648 yes ,9 yes , 6, ,683 yes , ,330 yes 0,83 0,72 0,766 0,78 0,118 1, ,800 H 0,17 2 1,9 0,163 0,164 0, , ,230 yes 0,13 2 0,1 0,134 0,126 0,023, ,982 yes 2, ,3 2,3 0,6 23, ,33 yes 3,9 2 3,64 3,86 3,8 0,37 9, ,380 yes 90 83,8 92,3 91,9 7,04 7, ,180 yes 44,2 1 40,3 44,8 44,4 3,42 7, ,160 yes , ,180 yes ,2 4, ,0 yes ,7 4, ,180 yes ,4, ,990 H , , ,78 yes 6,24,7,84, , ,804 yes 69 63, 67,4 67 4, ,7 yes 6,17,81 6,22 6,14 0,61 9, ,060 yes 38,3 34, ,8 4,37 11, ,600 yes ,92 4, ,732 yes ,92 4, Outlier test failed: C Cohcran, G1 Grubbs(1outlier algorithm), G2 Grubbs(2outliers algorithm), H Hampel, M manual SYKE Interlaboratory comparison test 3/

101 99 LIITE APPENDIX 8 / 27 Analyte Unit Sample zgraphics Z value Outl Assigned test OK value 2* Targ SD% Lab's result Md. Mean SD SD% Passed Outl. failed Missing Num of labs 0,804 yes 11,2, ,1 1,26 11, Laboratory 31 P S6M 9,990 H 120 1, , Pb 0,603 yes 1,99 1,87 1,98 2,01 0,363 18, ,7 yes 92,9 89,6 92,8 93,2,66 6, ,730 yes 6,12 1,79,96 6,02 0,4 9, ,731 yes 46, 43,1 46,3 4,4 6 13, ,799 yes 67,6 62,2 67,4 67,2 4,89 7, ,061 yes 6,6 66 6, 64,7,03 7, ,370 yes 3,32 2,87 3,16 3,2 0,37 11, S S6M 0,667 yes , Se 0,98 yes 1,2 1,08 1,1 1,14 0,237, ,217 yes ,7 44,7 4 3,18 7, ,131 yes 2,67 2,63 2,71 2,3 0,22, yes 0,62 0,924 1,6 1,9 1, ,48 yes 30,1 28,4 29,9 30,3 2,9 9, ,08 yes 29,3 29, 29, 29,1 3,79 13, ,62 yes 6,72 6,3 6,7 6,66 0,709, TC S6M yes V 1,280 yes 3,79 1 3,42 3,6 3,6 0,332 9, ,384 yes 86 84,3 84,7 84,6 4,04 4, ,69 yes 4,83 4, 4,78 4,7 0,449 9, ,87 yes 70,3 64,2 69,7 70,3 8,34 11, ,016 yes 82,8 1 82,7 82,8 82,3 4,0 4, ,186 yes 82,4 1 81,3 82,3 82,3 3,96 4, ,9 yes 12,6 11,9 12,6 12,7 1,17 9, Zn 0,2 yes 7,8 2 7,6 8,1 8,1 1,94 22, ,932 yes ,84, ,633 yes 1,8 2 14,6 1,9 1,9 2,41 1, ,330 yes ,2, ,73 yes ,6 8, ,060 yes ,27 3, ,130 yes 2,3 46,4 3,1 2,3,42, Laboratory 32 Al 0,14 yes 1,6 2 1,9 1,4 1, 1,91 12, ,1 yes , ,267 yes ,9 7, ,140 yes , ,11 yes , 9, ,734 yes ,8 14, As 0,488 yes 6,0 6,3 6,01,9 0,82 14, , yes 7 1 6, 7 6,8 3,68 6, ,021 yes 3,77 2 3,78 3,71 3,7 0,877 24, ,049 yes 16,3 2 16,2 16,2 16,4 1,92 11, ,939 yes 91,1 99,7 91,9 90,8 7,66 8, ,889 yes 4,86 2,4 4,97 4,8 0,731 1, Cd 0,04 yes 0,66 0,663 0,628 0,634 0, , ,0 yes 6,4 1 6,41 6,41 6,44 0,426 6, ,130 yes 0,81 0,8 0,797 0,80 0,073 9, ,1 yes 0,71 2 0,701 0,701 0,712 0,119 16, ,066 yes 30,3 1 30,4 30,1 30,1 1,93 6, ,473 yes 2,82 1 2,92 2,8 2,83 0,241 8, Co 0,28 yes 2,71 2,78 2,7 2,68 0,299 11, ,128 yes 47 46,7 46,8 46, 2,37, ,337 yes 3,12 3,22 3,1 3,09 0,176, ,82 yes 16,9 2 18,7 16,9 17,2 2,46 14, ,68 yes 40, 1 42, 40,8 40, 1,77 4, ,4 yes 1, 1 17,1 1, 1,4 1,32 8, Cr 0,343 yes 2,04 2,11 2,06 2,03 0,24 11, ,772 yes 79 7,9 78,2 78, 4,8 6, ,194 yes,3,,4,3 0,938 9, ,308 yes , 6,7 63,8 9,07 14, ,278 yes ,6, ,681 yes 8,37 8,94 8,6 8,48 0,99 11, Cu 0,04 yes 2,28 2,4 2,3 2,21 0,31 1, ,03 yes 7 6,9 6,3 6,1 3, ,273 yes 12,2 1 12,4 12,3 12,2 1,06 8, ,42 yes 40 38,3 40,2 39,8,16 12, Outlier test failed: C Cohcran, G1 Grubbs(1outlier algorithm), G2 Grubbs(2outliers algorithm), H Hampel, M manual SYKE Interlaboratory comparison test 3/

102 LIITE 8 / 28 0 APPENDIX Analyte Unit Sample zgraphics Z value Outl Assigned test OK value 2* Targ SD% Lab's result Md. Mean SD SD% Passed Outl. failed Missing Num of labs 0,078 yes 8,6 1 8,1 8,3 8,6 3,6 4, Laboratory 32 Cu 1,740 yes 9,92 11,6 9,8 9,91 1,02, Fe 0,48 yes,2 30,9 9,91 9,64 2,93 30, ,309 yes ,9, ,72 yes , ,060 yes , ,604 yes , 6, ,241 yes , Hg A1Hg 0,392 yes 0,83 0,798 0,766 0,78 0,118 1, N3Hg 0,024 yes 0,17 2 0,17 0,163 0,164 0, , S6M 1,230 yes 0,13 2 0,1 0,134 0,126 0,023, THg 0,930 yes 2,28 2 2,02 2,3 2,3 0,6 23, Mn 0,379 yes 3,9 2 3,71 3,86 3,8 0,37 9, ,030 yes 90 8,3 92,3 91,9 7,04 7, ,694 yes 44,2 1 41,9 44,8 44,4 3,42 7, ,99 yes , ,1 yes ,7 4, ,39 yes ,4, N S6M 0,400 yes , Ni 0,497 yes 6,24 6,,84, , ,01 yes 69 68,9 67,4 67 4, ,794 yes 6,17 6,66 6,22 6,14 0,61 9, ,170 yes 38,3 37, ,8 4,37 11, ,163 yes ,92 4, ,6 yes 11, ,1 1,26 11, P S6M 0,160 yes , Pb 0,21 yes 1,99 2,04 1,98 2,01 0,363 18, ,237 yes 92, ,8 93,2,66 6, ,21 yes 6,12 1 6,24,96 6,02 0,4 9, ,333 yes 46, 48 46,3 4,4 6 13, ,617 yes 6,6 69,7 6, 64,7,03 7, ,840 yes 3,32 3,93 3,16 3,2 0,37 11, S S6M 0, yes , Se 0,292 yes 1,2 1,17 1,1 1,14 0,237, ,667 yes ,2 44,7 4 3,18 7, ,187 yes 2,67 2,72 2,71 2,3 0,22, yes 0,774 0,924 1,6 1,9 1, ,137 yes 29,3 29,7 29, 29,1 3,79 13, ,186 yes 6,72 6,6 6,7 6,66 0,709, V 0,422 yes 3,79 1 3,67 3,6 3,6 0,332 9, ,477 yes 86 83,9 84,7 84,6 4,04 4, ,4 yes 4,83 4,78 4,78 4,7 0,449 9, ,477 yes 70,3 73,7 69,7 70,3 8,34 11, ,291 yes 82,4 1 80,6 82,3 82,3 3,96 4, ,37 yes 12,6 13,1 12,6 12,7 1,17 9, Zn 0,622 yes 7,8 2 8,46 8,1 8,1 1,94 22, ,323 yes ,84, ,076 yes 1,8 2 1,9 1,9 1,9 2,41 1, ,968 yes ,2, ,602 yes ,27 3, ,16 yes 2,3 3,1 2,3,42, Outlier test failed: C Cohcran, G1 Grubbs(1outlier algorithm), G2 Grubbs(2outliers algorithm), H Hampel, M manual SYKE Interlaboratory comparison test 3/

103 1 LIITE APPENDIX 8 / 29 Analyte Unit Sample zgraphics Z value Outl Assigned test OK value 2* Targ SD% Lab's result Md. Mean SD SD% Passed Outl. failed Missing Num of labs Laboratory 33 Al 0,3 yes 1,6 2 1,8 1,4 1, 1,91 12, As 1,60 yes 6,0,0 6,01,9 0,82 14, ,0 yes 7 1 2,7 7 6,8 3,68 6, ,823 yes 91,1 83,6 91,9 90,8 7,66 8, Cd 0,20 yes 0,66 0,643 0,628 0,634 0, , ,646 yes 6,4 1 6,09 6,41 6,44 0,426 6, ,037 yes 0,81 0,807 0,797 0,80 0,073 9, ,022 yes 30,3 1 30,3 30,1 30,1 1,93 6, Cr 2,00 yes 79 70,9 78,2 78, 4,8 6, ,340 yes,3,6,4,3 0,938 9, ,06 yes ,6, Cu 2,370 yes 7 0,3 6,3 6,1 3, ,30 yes 12,2 1,8 12,3 12,2 1,06 8, ,304 yes 8,6 1 83,7 8,3 8,6 3,6 4, Fe 0,993 yes ,9, ,236 yes , ,00 yes , 6, Hg A1Hg 0,024 yes 0,83 0,828 0,766 0,78 0,118 1, N3Hg 0,23 yes 0,17 2 0,16 0,163 0,164 0, , THg 1,1 yes 2,28 2 1,96 2,3 2,3 0,6 23, Mn 2,670 yes ,3 91,9 7,04 7, ,440 yes 44,2 1 36,1 44,8 44,4 3,42 7, ,130 H ,7 4, Ni 1,70 yes 6,24,1,84, , ,9 yes 69 69,8 67,4 67 4, ,000 yes 6,17, 6,22 6,14 0,61 9, ,244 yes ,92 4, Pb 1,470 yes 92,9 86,1 92,8 93,2,66 6, ,70 yes 6,12 1,4,96 6,02 0,4 9, ,34 yes 6,6 62,1 6, 64,7,03 7, Zn 0,21 yes ,84, ,130 yes 1,8 2 1,9 1,9 2,41 1, ,301 yes ,27 3, Laboratory 34 As 0,83 yes 6,0 6, 6,01,9 0,82 14, ,86 yes ,7 7 6,8 3,68 6, ,20 yes 3,77 2 4,36 3,71 3,7 0,877 24, ,260 yes 97,7 1 97,7 97,6 6,31 6, ,0 yes 4,86 2 6,13 4,97 4,8 0,731 1, Cd H 0,66 <1,0 0,628 0,634 0, , ,719 yes 6,4 1 6,7 6,41 6,44 0,426 6, H 0,81 <1,0 0,797 0,80 0,073 9, ,7 yes 30, ,8 30,3 2,24 7, ,91 yes 2,82 1 2,7 2,8 2,83 0,241 8, Co H 2,71 <4,0 2,7 2,68 0,299 11, ,470 yes 47 43, 46,8 46, 2,37, H 3,12 <4,0 3,1 3,09 0,176, ,612 yes 40,3 1 38, 40,6 40,3 2, ,9 yes 1, 1 16,1 1, 1,4 1,32 8, Cr H 2,04 <3,0 2,06 2,03 0,24 11, ,4 yes 79 84, 78,2 78, 4,8 6, ,0 yes,3 8,22,4,3 0,938 9, ,0 yes ,43 4, ,630 yes 8,37 7 8,6 8,48 0,99 11, Cu H 2,28 <3,0 2,3 2,21 0,31 1, ,370 yes 7 3,1 6,3 6,1 3, ,10 yes 12,2 1 11,2 12,3 12,2 1,06 8, ,807 yes 83,4 1 78, ,1 4,09 4, ,696 yes 9,92 9,23 9,8 9,91 1,02, Mn 0,287 yes 3,9 2 4,04 3,86 3,8 0,37 9, ,2 yes ,3 91,9 7,04 7, ,603 yes 44,2 1 46,2 44,8 44,4 3,42 7, ,790 C ,2 4, ,060 H ,4, Ni 1,900 yes 6,24,0,84, , ,826 yes 69 63,3 67,4 67 4, ,390 yes 6,17,31 6,22 6,14 0,61 9, Outlier test failed: C Cohcran, G1 Grubbs(1outlier algorithm), G2 Grubbs(2outliers algorithm), H Hampel, M manual SYKE Interlaboratory comparison test 3/

104 LIITE 8 / 30 2 APPENDIX Analyte Unit Sample zgraphics Z value Outl Assigned test OK value 2* Targ SD% Lab's result Md. Mean SD SD% Passed Outl. failed Missing Num of labs 0,247 yes ,92 4, Laboratory 34 Ni 1,630 yes 11,2 9, ,1 1,26 11, Pb H 1,99 <4,0 1,98 2,01 0,363 18, ,040 yes 92, ,8 93,2,66 6, ,294 yes 6,12 1,98,96 6,02 0,4 9, ,873 yes 67,6 61,7 67,4 67,2 4,89 7, H 3,32 <4,0 3,16 3,2 0,37 11, Zn H 7,8 2 <40 8,1 8,1 1,94 22, ,180 yes ,84, H 1,8 2 <40 1,9 1,9 2,41 1, ,900 yes ,6 8, ,8 yes 2,3 42,8 3,1 2,3,42, Laboratory 3 Al 1,2 yes , Cd 3,080 H 30,3 1 37,3 30,1 30,1 1,93 6, Co 0,781 yes 16,9 2 18, 16,9 17,2 2,46 14, Cr 0,160 yes ,3 6,7 63,8 9,07 14, Cu 0,063 yes 40 40,3 40,2 39,8,16 12, Fe 1,480 yes ,9, ,2 yes , ,099 yes , ,0 yes , 6, Hg A1Hg 2,1 yes 0,83 0,6 0,766 0,78 0,118 1, THg 3,740 yes 2,28 2 1,21 2,3 2,3 0,6 23, Mn 0,634 yes , , yes ,7 4, N S6M 0,703 yes , Ni 0,770 yes 38,3 41, ,8 4,37 11, ,7 H ,92 4, P S6M 1,400 yes , Pb 2,1 yes 46, 36,6 46,3 4,4 6 13, S S6M,00 H , Zn 1, yes ,2, ,181 yes ,27 3, Laboratory 36 Al As Cd Co Cr Cu 0, yes 1,6 2 1,2 1,4 1, 1,91 12, ,0 yes , ,0 yes ,9 7, ,7 yes , ,780 yes , 9, ,9 yes ,8 14, ,90 yes 6,0,47 6,01,9 0,82 14, ,270 yes 7 1 1, 7 6,8 3,68 6, ,6 yes 3,77 2 3,01 3,71 3,7 0,877 24, ,330 yes 16,3 2 13,6 16,2 16,4 1,92 11, ,922 yes 91,1 82,7 91,9 90,8 7,66 8, ,160 yes 4,86 2 3, 4,97 4,8 0,731 1, ,0 yes 0,66 0,7 0,628 0,634 0, , ,480 yes 6,4 1,69 6,41 6,44 0,426 6, ,1 yes 0,81 0,72 0,797 0,80 0,073 9, ,7 yes 0,71 2 0,8 0,701 0,712 0,119 16, ,880 yes 30,3 1 28,3 30,1 30,1 1,93 6, ,61 yes 2,82 1 2,69 2,8 2,83 0,241 8, ,443 C 2,71 2,9 2,7 2,68 0,299 11, ,0 yes 47 44,6 46,8 46, 2,37, ,224 C 3,12 3,0 3,1 3,09 0,176, ,300 yes 16,9 2 12,1 16,9 17,2 2,46 14, ,230 yes 40, 1 39,8 40,8 40, 1,77 4, ,080 yes 1, 1 14,3 1, 1,4 1,32 8, ,00 yes 2,04 2,34 2,06 2,03 0,24 11, ,924 yes 79 82,7 78,2 78, 4,8 6, ,00 yes,3 11,9,4,3 0,938 9, ,400 yes ,3 6,7 63,8 9,07 14, ,170 C ,6, ,4 yes 8,37 9, 8,6 8,48 0,99 11, ,180 yes 7 3,6 6,3 6,1 3, Outlier test failed: C Cohcran, G1 Grubbs(1outlier algorithm), G2 Grubbs(2outliers algorithm), H Hampel, M manual SYKE Interlaboratory comparison test 3/

105 3 LIITE APPENDIX 8 / 31 Analyte Unit Sample zgraphics Z value Outl Assigned test OK value 2* Targ SD% Lab's result Md. Mean SD SD% Passed Outl. failed Missing Num of labs 0,0 yes 12,2 1 12,1 12,3 12,2 1,06 8, Laboratory 36 Cu 1,230 yes 40 44,9 40,2 39,8,16 12, ,7 yes 8,6 1 80,8 8,3 8,6 3,6 4, ,877 yes 9,92 9,0 9,8 9,91 1,02, Fe 0,46 yes ,9, ,00 yes , ,380 yes , ,042 yes , 6, ,1 yes , Hg A1Hg 4,280 yes 0,83 0,47 0,766 0,78 0,118 1, S6M 0,14 yes 0,13 2 0,133 0,134 0,126 0,023, THg 2,180 yes 2,28 2 2,9 2,3 2,3 0,6 23, Mn 2,080 yes 90 80,7 92,3 91,9 7,04 7, ,460 C 44,2 1 39,4 44,8 44,4 3,42 7, ,99 yes , ,684 yes ,7 4, ,390 yes ,4, N S6M 9,990 H , , Ni 0,313 yes 6,24 6,04,84, , ,326 yes 69 71,3 67,4 67 4, ,486 yes 6,17 6,47 6,22 6,14 0,61 9, ,87 yes 38,3 41, ,8 4,37 11, ,813 yes ,92 4, ,62 yes 11,2 11, ,1 1,26 11, P S6M 9,990 H 120 1, , Pb 1,730 yes 1,99 1,6 1,98 2,01 0,363 18, ,70 H 92,9 7, 92,8 93,2,66 6, ,190 yes 6,12 1,12,96 6,02 0,4 9, ,60 yes 46, 8,4 46,3 4,4 6 13, ,680 yes 6,6 4, 6, 64,7,03 7, ,80 yes 3,32 2,46 3,16 3,2 0,37 11, Se 1,160 yes ,3 44,7 4 3,18 7, ,80 yes 2,67 1,98 2,71 2,3 0,22, yes 0,47 0,924 1,6 1,9 1, ,2 yes 29,3 2,8 29, 29,1 3,79 13, ,90 yes 6,72 4,98 6,7 6,66 0,709, V 0,47 yes 3,79 1 3,66 3,6 3,6 0,332 9, ,060 yes 86 77,2 84,7 84,6 4,04 4, ,176 yes 4,83 4,92 4,78 4,7 0,449 9, ,292 yes 70,3 68,3 69,7 70,3 8,34 11, ,190 yes 82, ,3 82,3 3,96 4, ,238 yes 12,6 12,9 12,6 12,7 1,17 9, Zn,8 H 7,8 2 13,6 8,1 8,1 1,94 22, ,21 yes ,84, ,06 yes 1,8 2 14,8 1,9 1,9 2,41 1, ,8 yes ,2, ,301 yes ,27 3, ,449 yes 2,3 0 3,1 2,3,42, Outlier test failed: C Cohcran, G1 Grubbs(1outlier algorithm), G2 Grubbs(2outliers algorithm), H Hampel, M manual SYKE Interlaboratory comparison test 3/

106 LIITE 8 / 32 4 APPENDIX Analyte Unit Sample zgraphics Z value Outl Assigned test OK value 2* Targ SD% Lab's result Md. Mean SD SD% Passed Outl. failed Missing Num of labs Laboratory Al Cu Fe Mn Zn Laboratory Ni Laboratory Al As Cd Co Cr Cu Fe 37 H 1,6 2 <70 1,4 1, 1,91 12, ,34 yes , ,867 yes ,9 7, ,128 yes ,1 4, ,00 yes ,8 14, H 2,28 < 2,3 2,21 0,31 1, ,316 yes 7 7,9 6,3 6,1 3, H 12,2 1 < 12,3 12,2 1,06 8, ,016 yes 83,4 1 83, ,1 4,09 4, H 9,92 < 9,8 9,91 1,02, ,2 30 <40 9,91 9,64 2,93 30, ,782 yes ,9, ,69 yes , ,3 yes ,482 yes , H 3,9 2 < 3,86 3,8 0,37 9, ,680 yes 90 97,6 92,3 91,9 7,04 7, ,780 yes 44,2 1 0,1 44,8 44,4 3,42 7, ,976 yes ,2 4, ,482 yes ,4, H 7,8 2 < 8,1 8,1 1,94 22, ,824 yes ,84, H 1,8 2 < 1,9 1,9 2,41 1, ,190 yes ,6 8, ,49 yes 2,3 4,7 3,1 2,3,42, ,89 yes ,92 4, ,64 C 1,6 2 14, 1,4 1, 1,91 12, ,298 yes , ,06 yes ,9 7, SO6 yes , ,13 yes ,1 4, ,678 yes ,8 14, ,440 H 6,0,6 6,01,9 0,82 14, ,400 yes ,8 3,68 6, ,660 yes 3,77 2 1,1 3,71 3,7 0,877 24, SO6 H 6,9 17,4 16,9 1, ,23 yes 97,7 0 97,7 97,6 6,31 6, ,0 H 4, ,97 4,8 0,731 1, ,98 yes 0,66 0,72 0,628 0,634 0, , ,36 yes 6,4 1 6,22 6,41 6,44 0,426 6, ,270 H 0,81 1,08 0,797 0,80 0,073 9, SO6 yes 1,04 0,748 0,793 0,162, ,443 yes 30,1 1 31,1 29,8 30,3 2,24 7, ,638 yes 2,82 1 2,69 2,8 2,83 0,241 8, ,990 yes 2,71 3,2 2,7 2,68 0,299 11, ,426 yes ,8 46, 2,37, ,00 C 3,12 3,9 3,1 3,09 0,176, SO6 yes 22,3 18,8 19,1 1,82 9, 0 0 0,62 yes 40, ,6 40,3 2, ,290 yes 1, , 1,4 1,32 8, ,060 yes 2,04 1,62 2,06 2,03 0,24 11, ,886 yes 79 7, 78,2 78, 4,8 6, ,60 yes,3 8,6,4,3 0,938 9, SO6 yes 80,6 77, 73,2 8,61 11, ,1 yes ,43 4, ,230 C 8,37 6, 8,6 8,48 0,99 11, ,360 yes 2,28 1,29 2,3 2,21 0,31 1, ,17 yes 7 6, 6,3 6,1 3, ,76 yes 12,2 1 11, 12,3 12,2 1,06 8, SO6 yes 42,1 39, 39,9 2,91 7, ,496 yes 83,4 1 86, 83 83,1 4,09 4, ,0 yes 9,92 12,4 9,8 9,91 1,02, ,48 yes,2 30 9, 9,91 9,64 2,93 30, ,130 yes ,9, Outlier test failed: C Cohcran, G1 Grubbs(1outlier algorithm), G2 Grubbs(2outliers algorithm), H Hampel, M manual SYKE Interlaboratory comparison test 3/

107 LIITE APPENDIX 8 / 33 Analyte Unit Sample zgraphics Z value Outl Assigned test OK value 2* Targ SD% Lab's result Md. Mean SD SD% Passed Outl. failed Missing Num of labs 0,02 yes , Laboratory 39 Fe SO6 yes , ,672 yes ,763 yes , Hg A1Hg 2,170 yes 0,83 0,6 0,766 0,78 0,118 1, N3Hg 1,4 yes 0,17 2 0,2 0,163 0,164 0, , S6M 0,61 yes 0,13 2 0,12 0,134 0,126 0,023, THg 0,246 yes 2,28 2 2,3 2,3 2,3 0,6 23, Mn 8,8 H 3,9 2 8,2 3,86 3,8 0,37 9, ,222 yes ,3 91,9 7,04 7, ,99 yes 44,2 1 47, 44,8 44,4 3,42 7, SO6 yes ,1 2, ,621 yes ,2 4, ,321 yes ,4, Ni 2,900 yes 6,24 4,43,84, , ,290 yes ,4 67 4, ,930 yes 6,17 4,98 6,22 6,14 0,61 9, SO6 yes 48,2 38,6 38,2 6,44 16, ,370 yes ,92 4, ,10 yes 11,2 9, ,1 1,26 11, Pb 0,1 yes 1,99 1,9 1,98 2,01 0,363 18, ,30 yes 92,9 0 92,8 93,2,66 6, ,414 yes 6,12 1 6,31,96 6,02 0,4 9, SO6 H 63,4 47,3 47,3 0,40 0, ,240 yes 67, ,4 67,2 4,89 7, ,633 yes 3,32 3,11 3,16 3,2 0,37 11, Se 1,670 yes 1,2 1,4 1,1 1,14 0,237, ,70 yes ,6 44,7 4 3,18 7, ,300 yes 2,67 1,2 2,71 2,3 0,22, SO6 < 0,938 0,98 1, 17, ,282 yes 30,1 30,9 29,9 30,3 2,9 9, ,4 H 6,72 1,74 6,7 6,66 0,709, V 1,090 yes 3,79 1 4,1 3,6 3,6 0,332 9, ,349 yes 86 87, 84,7 84,6 4,04 4, ,32 yes 4,83 4,78 4,7 0,449 9, SO6 C 7 80,6 80,3 14,7 18, ,96 yes 82,8 1 86, 82,8 82,3 4,0 4, ,1 yes 12, ,6 12,7 1,17 9, Zn,20 yes 7, ,1 8,1 1,94 22, ,287 yes ,84, ,130 yes 1,8 2 1,9 1,9 2,41 1, SO6 yes ,4 11, ,982 yes ,6 8, ,090 yes 2,3 8 3,1 2,3,42, Outlier test failed: C Cohcran, G1 Grubbs(1outlier algorithm), G2 Grubbs(2outliers algorithm), H Hampel, M manual SYKE Interlaboratory comparison test 3/

108 LIITE 8 / 34 6 APPENDIX Analyte Unit Sample zgraphics Z value Outl Assigned test OK value 2* Targ SD% Lab's result Md. Mean SD SD% Passed Outl. failed Missing Num of labs Laboratory Al As Cd Co Cr Cu Fe Hg Mn Ni Pb Se Zn Laboratory Cr Fe Ni Zn Laboratory Co Cr Fe Zn A1Hg THg 0,982 yes , ,424 yes , 9, ,187 yes 7 1 6,2 7 6,8 3,68 6, ,099 yes 91, ,9 90,8 7,66 8, ,290 yes 6,4 1 7, 6,41 6,44 0,426 6, ,72 yes 30,3 1 31,6 30,1 30,1 1,93 6, ,81 yes ,8 46, 2,37, ,214 yes 40, 1 41,2 40,8 40, 1,77 4, ,696 yes 79 81,8 78,2 78, 4,8 6, ,339 yes ,6, ,700 yes 7 64,7 6,3 6,1 3, ,14 yes 8,6 1 88,9 8,3 8,6 3,6 4, ,30 yes ,9, ,364 yes , 6, ,3 yes 0,83 0,8 0,766 0,78 0,118 1, ,614 yes 2,28 2 2,46 2,3 2,3 0,6 23, ,260 C 90 9,7 92,3 91,9 7,04 7, ,41 yes ,7 4, ,94 yes 69 73,1 67,4 67 4, ,634 yes ,92 4, ,409 yes 92,9 94,8 92,8 93,2,66 6, ,473 yes 6,6 62, 6, 64,7,03 7, ,403 yes ,7 44,7 4 3,18 7, ,614 yes 29,3 27, 29, 29,1 3,79 13, ,480 C ,84, ,4 yes ,27 3, ,770 yes ,2 78, 4,8 6, ,496 yes ,43 4, ,440 yes ,9, ,411 yes ,80 yes ,4 67 4, ,494 yes ,92 4, ,64 yes ,84, ,286 yes ,6 8, ,638 C 47 4, 46,8 46, 2,37, ,3 H 40, 1 44, 40,8 40, 1,77 4, ,300 H 79 14, 78,2 78, 4,8 6, ,670 H ,6, ,244 yes ,9, ,881 yes , 6, ,8 yes ,84, ,723 yes ,27 3, Outlier test failed: C Cohcran, G1 Grubbs(1outlier algorithm), G2 Grubbs(2outliers algorithm), H Hampel, M manual SYKE Interlaboratory comparison test 3/

109 7 LIITE APPENDIX 8 / 3 Analyte Unit Sample zgraphics Z value Outl Assigned test OK value 2* Targ SD% Lab's result Md. Mean SD SD% Passed Outl. failed Missing Num of labs Laboratory 43 Al 0,308 yes 1, ,4 1, 1,91 12, ,6 yes , ,783 yes ,9 7, SO6 yes , ,0 yes , 9, ,339 yes ,8 14, As H 6,0 <11 6,01,9 0,82 14, ,31 yes 7 1 8, 7 6,8 3,68 6, H 3,77 2 < 3,71 3,7 0,877 24, SO6 yes 17,1 17,4 16,9 1, ,467 yes 91,1 9,3 91,9 90,8 7,66 8, H 4,86 2 <13 4,97 4,8 0,731 1, Cd 6,670 H 0,66 1,1 0,628 0,634 0, , ,396 yes 6,4 1 6,9 6,41 6,44 0,426 6, H 0,81 <1,0 0,797 0,80 0,073 9, SO6 yes 0,9 0,748 0,793 0,162, ,374 yes 30,3 1 29,4 30,1 30,1 1,93 6, , yes 2,82 1 3,3 2,8 2,83 0,241 8, Co 0,037 yes 2,71 2,7 2,7 2,68 0,299 11, ,81 yes ,8 46, 2,37, ,26 yes 3,12 3,2 3,1 3,09 0,176, SO6 yes 19 18,8 19,1 1,82 9, 0 0 0,346 yes 40, 1 39, 40,8 40, 1,77 4, ,344 yes 1, 1 1,9 1, 1,4 1,32 8, Cr H 2,04 <11 2,06 2,03 0,24 11, ,06 yes ,2 78, 4,8 6, ,170 yes,3 11,,4,3 0,938 9, SO6 yes 81 77, 73,2 8,61 11, ,222 yes ,6, H 8,37 <13 8,6 8,48 0,99 11, Cu H 2,28 <11 2,3 2,21 0,31 1, ,000 yes 7 7 6,3 6,1 3, ,874 yes 12, ,3 12,2 1,06 8, SO6 yes 39, 39, 39,9 2,91 7, ,40 yes 8,6 1 88,2 8,3 8,6 3,6 4, ,370 H 9,92 1,3 9,8 9,91 1,02, Fe 1,180 yes, ,91 9,64 2,93 30, ,033 yes ,9, ,0 yes , SO6 yes , ,62 yes , 6, ,1 yes , Hg A1Hg 1,690 yes 0,83 0,69 0,766 0,78 0,118 1, N3Hg 1,880 yes 0,17 2 0,13 0,163 0,164 0, , S6M 1,40 yes 0,13 2 0,1 0,134 0,126 0,023, THg 2,190 yes 2,28 2 1,6 2,3 2,3 0,6 23, Mn H 3,9 2 <11 3,86 3,8 0,37 9, ,000 yes 90 8, 92,3 91,9 7,04 7, ,664 yes 44, ,8 44,4 3,42 7, SO6 yes ,1 2, ,221 yes ,7 4, ,229 yes ,4, Ni H 6,24 <11,84, , ,290 yes ,4 67 4, H 6,17 < 6,22 6,14 0,61 9, SO6 yes 3,3 38,6 38,2 6,44 16, ,32 yes ,92 4, H 11,2 < ,1 1,26 11, Pb H 1,99 <11 1,98 2,01 0,363 18, ,624 yes 92, ,8 93,2,66 6, H 6,12 1 <,96 6,02 0,4 9, SO6 H 2, 47,3 47,3 0,40 0, ,899 yes 6,6 71, 6, 64,7,03 7, H 3,32 <13 3,16 3,2 0,37 11, S S6M 0,09 yes , Se H 1,2 <21 1,1 1,14 0,237, ,46 yes , 44,7 4 3,18 7, Outlier test failed: C Cohcran, G1 Grubbs(1outlier algorithm), G2 Grubbs(2outliers algorithm), H Hampel, M manual SYKE Interlaboratory comparison test 3/

110 LIITE 8 / 36 8 APPENDIX Analyte Unit Sample zgraphics Z value Outl Assigned test OK value 2* Targ SD% Lab's result Md. Mean SD SD% Passed Outl. failed Missing Num of labs H 2,67 < 2,71 2,3 0,22, Laboratory 43 Se SO6 yes 2,33 0,938 0,98 1, 17, ,180 yes 29,3 32,8 29, 29,1 3,79 13,0 0 0 H 6,72 <2 6,7 6,66 0,709, V H 3,79 1 <11 3,6 3,6 0,332 9, ,930 yes ,7 84,6 4,04 4, H 4,83 < 4,78 4,7 0,449 9, SO6 yes 99,3 80,6 80,3 14,7 18, ,793 yes 82,4 1 87,3 82,3 82,3 3,96 4,8 0 0 H 12,6 <13 12,6 12,7 1,17 9, Zn 0,01 yes 7,8 2 7,9 8,1 8,1 1,94 22, ,430 yes ,84, ,40 yes 1, ,9 1,9 2,41 1, SO6 yes ,4 11, ,422 yes ,27 3, ,717 yes 2,3 6 3,1 2,3,42, Laboratory 44 As 0,760 yes 91, ,9 90,8 7,66 8, Cd 0,946 yes 30,3 1 32, 30,1 30,1 1,93 6, Co 0,069 yes 40, 1 40,7 40,8 40, 1,77 4, Cr 0,611 yes ,6, Cu 0,148 yes 8,6 1 84,7 8,3 8,6 3,6 4, Fe 1,3 yes , 6, Hg THg 0,47 yes 2,28 2 2,44 2,3 2,3 0,6 23, Mn 0,611 yes ,7 4, Ni 0,813 yes ,92 4, Pb 0,877 yes 6,6 71,3 6, 64,7,03 7, Se 0,4 yes 29,3 30, 29, 29,1 3,79 13,0 0 0 V 0,024 yes 82,4 1 82,3 82,3 82,3 3,96 4,8 0 0 Zn 0,060 yes ,27 3, Laboratory 4 Al 0,464 yes , ,123 yes , ,140 yes ,1 4, ,70 yes ,8 14, As 0,000 yes ,8 3,68 6, ,600 H 16,3 2 8,96 16,2 16,4 1,92 11, ,241 yes 97,7 9,3 97,7 97,6 6,31 6, H 4,86 2 < 4,97 4,8 0,731 1, Cd 0,833 yes 6,4 1 6,8 6,41 6,44 0,426 6, ,300 H 0,71 2 2,69 0,701 0,712 0,119 16, ,377 yes 30, ,8 30,3 2,24 7, H 2,82 1 <6 2,8 2,83 0,241 8, Cr 0,684 yes 79 76,3 78,2 78, 4,8 6, ,680 yes ,2 6,7 63,8 9,07 14, ,0 yes ,43 4, H 8,37 <6 8,6 8,48 0,99 11, Cu 4,3 yes 7 44,7 6,3 6,1 3, ,22 yes 40 40,9 40,2 39,8,16 12, ,330 yes 83, ,1 4,09 4, H 9,92 <6 9,8 9,91 1,02, Fe 0,06 yes ,9, ,42 yes , ,013 yes ,418 yes , Mn 1,780 yes ,3 91,9 7,04 7, ,989 yes , ,2 yes ,2 4, ,677 yes ,4, N S6M 0,141 yes , Ni 0,36 yes 69 6,3 67,4 67 4, ,0 yes 38,3 34, ,8 4,37 11, ,18 yes ,92 4, ,340 yes 11,2 12, ,1 1,26 11, P S6M 0,164 yes , Pb 0,42 yes 92,9 9 92,8 93,2,66 6, Outlier test failed: C Cohcran, G1 Grubbs(1outlier algorithm), G2 Grubbs(2outliers algorithm), H Hampel, M manual SYKE Interlaboratory comparison test 3/

111 9 LIITE APPENDIX 8 / 37 Analyte Unit Sample zgraphics Z value Outl Assigned test OK value 2* Targ SD% Lab's result Md. Mean SD SD% Passed Outl. failed Missing Num of labs 0,409 yes 46, 48,4 46,3 4,4 6 13, Laboratory 4 Pb 0,436 yes 67,6 70, 67,4 67,2 4,89 7, H 3,32 < 3,16 3,2 0,37 11, S S6M 0,086 yes , Se 2,430 yes ,8 44,7 4 3,18 7, <6 0,924 1,6 1,9 1, ,233 yes 30,1 29,4 29,9 30,3 2,9 9, H 6,72 < 6,7 6,66 0,709, V 0,233 yes ,7 84,6 4,04 4, ,612 yes 70,3 74,6 69,7 70,3 8,34 11, ,242 yes 82,8 1 81,3 82,8 82,3 4,0 4, ,040 yes 12,6 12,6 12,6 12,7 1,17 9, Zn 1,330 yes ,84, ,080 yes ,2, ,760 yes ,6 8, ,040 yes 2,3 7,8 3,1 2,3,42, Laboratory 46 Al As Cd Co Cr Cu Fe Mn Ni Pb V Zn 0,09 yes , ,446 yes ,1 4, ,164 yes 7 1 6,3 7 6,8 3,68 6, ,2 yes 97,7 9,7 97,7 97,6 6,31 6, ,260 yes 6,4 1 6,3 6,41 6,44 0,426 6, ,066 yes 30, ,8 30,3 2,24 7, ,787 yes 47 4,1 46,8 46, 2,37, ,017 yes 40,3 1 40,4 40,6 40,3 2, ,46 yes 79 77,2 78,2 78, 4,8 6, ,34 yes ,43 4, ,140 yes 7 7,4 6,3 6,1 3, ,232 yes 83, ,1 4,09 4, ,147 yes ,9, ,98 yes ,178 yes 90 89,2 92,3 91,9 7,04 7, ,7 yes ,2 4, ,312 yes 69 66,8 67,4 67 4, ,444 yes ,92 4, ,8 yes 92,9 92,4 92,8 93,2,66 6, ,21 yes 67,6 69,3 67,4 67,2 4,89 7, ,477 yes 86 83,9 84,7 84,6 4,04 4, ,88 yes 82,8 1 86,4 82,8 82,3 4,0 4, ,803 yes ,84, ,724 yes ,6 8, Outlier test failed: C Cohcran, G1 Grubbs(1outlier algorithm), G2 Grubbs(2outliers algorithm), H Hampel, M manual SYKE Interlaboratory comparison test 3/

112 LIITE 8 / 38 1 APPENDIX Analyte Unit Sample zgraphics Z value Outl Assigned test OK value 2* Targ SD% Lab's result Md. Mean SD SD% Passed Outl. failed Missing Num of labs Laboratory Al As Cd Co Cr Cu Fe Mn Ni Pb Zn Laboratory Al Cu Fe Mn Zn ,68 yes , ,69 yes ,9 7, ,72 yes , 9, ,30 yes ,8 14, ,670 yes ,2 7 6,8 3,68 6, ,2 H 3,77 2 6,7 3,71 3,7 0,877 24, ,89 yes 91,1 99,3 91,9 90,8 7,66 8, ,400 H 4, ,6 4,97 4,8 0,731 1, ,312 yes 6,4 1 6, 6,41 6,44 0,426 6, ,30 C 0,81 1 0,797 0,80 0,073 9, ,000 yes 30,3 1 30,3 30,1 30,1 1,93 6, ,030 yes 2,82 1 3,2 2,8 2,83 0,241 8, ,74 yes 47 48,3 46,8 46, 2,37, ,470 H 3,12 1,1 3,1 3,09 0,176, ,93 yes 40, 1 42,3 40,8 40, 1,77 4, ,817 yes 1, 1 14,6 1, 1,4 1,32 8, ,696 yes 79 76,3 78,2 78, 4,8 6, ,194 yes,3,1,4,3 0,938 9, ,311 yes ,6, ,62 yes 8,37 7,9 8,6 8,48 0,99 11, ,90 yes 7 6,4 6,3 6,1 3, ,370 yes 12,2 1 13,4 12,3 12,2 1,06 8, ,740 yes 8,6 1 90,3 8,3 8,6 3,6 4, ,232 yes 9,92,2 9,8 9,91 1,02, ,490 yes ,9, ,3 yes , ,126 yes , 6, ,337 yes , ,1 yes ,3 91,9 7,04 7, ,87 yes 44,2 1 47,1 44,8 44,4 3,42 7, ,843 yes ,7 4, ,234 yes ,4, ,9 H 69 21,4 67,4 67 4, ,170 H ,92 4, ,790 C 92,9 84,6 92,8 93,2,66 6, ,300 H 6, ,96 6,02 0,4 9, ,130 H 6,6 86,2 6, 64,7,03 7, ,300 H 3, ,16 3,2 0,37 11, ,07 yes ,84, ,12 yes 1,8 2 1, 1,9 1,9 2,41 1, ,23 yes ,27 3, ,048 yes 2,3 2 3,1 2,3,42, ,000 yes , ,06 yes ,9 7, ,612 yes ,1 4, ,877 yes 7 4, 6,3 6,1 3, ,3 C 12, ,3 12,2 1,06 8, ,016 yes 83,4 1 83, 83 83,1 4,09 4, ,163 yes ,9, ,286 yes , ,772 yes ,2 yes 90 84, 92,3 91,9 7,04 7, ,13 yes 44,2 1 42, 44,8 44,4 3,42 7, ,067 yes ,2 4, ,38 yes ,84, ,4 H 1,8 2 24, 1,9 1,9 2,41 1, ,270 yes ,6 8, Outlier test failed: C Cohcran, G1 Grubbs(1outlier algorithm), G2 Grubbs(2outliers algorithm), H Hampel, M manual SYKE Interlaboratory comparison test 3/

113 111 LIITE APPENDIX 8 / 39 Analyte Unit Sample zgraphics Z value Outl Assigned test OK value 2* Targ SD% Lab's result Md. Mean SD SD% Passed Outl. failed Missing Num of labs Laboratory 49 Al 0,262 yes , ,783 yes ,9 7, ,240 yes , ,702 yes ,1 4, As 1,0 yes ,4 7 6,8 3,68 6, H 3,77 2 < 3,71 3,7 0,877 24, ,299 yes 16,3 2 16,9 16,2 16,4 1,92 11, ,21 yes 97,7 99,8 97,7 97,6 6,31 6, Cd 0,000 yes 6,4 1 6,4 6,41 6,44 0,426 6, H 0,81 <2 0,797 0,80 0,073 9, ,800 H 0,71 2,93 0,701 0,712 0,119 16, ,8 yes 30,1 1 28,8 29,8 30,3 2,24 7, Co 0,191 yes 47 47, 46,8 46, 2,37, ,78 yes 3,12 2,88 3,1 3,09 0,176, ,80 yes 16,9 2 1,7 16,9 17,2 2,46 14, ,00 yes 40,3 1 40,1 40,6 40,3 2, Cr 0,12 yes 79 79,6 78,2 78, 4,8 6, ,146 yes,3,1,4,3 0,938 9, ,20 yes 6 2 4,8 6,7 63,8 9,07 14, ,16 yes ,43 4, Cu 0,03 yes 7 7,1 6,3 6,1 3, ,79 yes 12,2 1 11,7 12,3 12,2 1,06 8, ,190 yes 40 3,2 40,2 39,8,16 12, ,8 yes 83,4 1 82, ,1 4,09 4, Fe 0,70 yes ,9, ,00 yes , ,270 yes , ,087 yes Hg N3Hg 1,480 yes 0,17 2 0,139 0,163 0,164 0, , S6M H 0,13 2 <0,3 0,134 0,126 0,023, THg 2,680 yes 2,28 2 1,2 2,3 2,3 0,6 23, Mn 0,91 yes 90 92,7 92,3 91,9 7,04 7, ,08 yes 44,2 1 43,9 44,8 44,4 3,42 7, ,330 yes , ,000 H 41 44, ,2 4, Ni 0,099 yes 69 69,7 67,4 67 4, ,770 yes 6,17,7 6,22 6,14 0,61 9, ,3 yes 38,3 33, ,8 4,37 11, ,099 yes ,92 4, P S6M 0,783 yes , Pb 0,01 yes 92,9 92,7 92,8 93,2,66 6, H 6,12 1 <,96 6,02 0,4 9, ,40 yes 46, 3,1 46,3 4,4 6 13, ,412 yes 67,6 64,8 67,4 67,2 4,89 7, S S6M 1,030 yes , Se 0,033 yes ,9 44,7 4 3,18 7, H 2,67 <30 2,71 2,3 0,22, yes 1,38 0,924 1,6 1,9 1, ,2 yes 30,1 26,4 29,9 30,3 2,9 9, V 0,6 yes 86 86, 84,7 84,6 4,04 4, ,393 yes 4,83 4,64 4,78 4,7 0,449 9, ,800 yes 70,3 7,7 69,7 70,3 8,34 11, ,298 yes 82, ,8 82,3 4,0 4, Zn 0,143 yes ,84, ,29 yes 1,8 2 14,8 1,9 1,9 2,41 1, ,8 yes ,2, ,160 yes ,6 8, Laboratory 0 Hg A1Hg 3,80 yes 0,83 0,33 0,766 0,78 0,118 1, N3Hg 0,18 yes 0,17 2 0,181 0,163 0,164 0, , Outlier test failed: C Cohcran, G1 Grubbs(1outlier algorithm), G2 Grubbs(2outliers algorithm), H Hampel, M manual SYKE Interlaboratory comparison test 3/

114 LIITE 8 / APPENDIX Analyte Unit Sample zgraphics Z value Outl Assigned test OK value 2* Targ SD% Lab's result Md. Mean SD SD% Passed Outl. failed Missing Num of labs Laboratory Al As Cd Cr Cu Fe Hg Mn Ni Pb V Zn 1 0,487 yes 1,6 2 14,6 1,4 1, 1,91 12, ,470 yes , ,0 yes ,9 7, ,689 yes ,1 4, ,4 yes ,8 14, ,62 yes 6,0 6,39 6,01,9 0,82 14, ,246 yes ,8 3,68 6, ,89 yes 3,77 2 4,17 3,71 3,7 0,877 24, ,297 yes 97,7 94,8 97,7 97,6 6,31 6, ,00 yes 4,86 2, 4,97 4,8 0,731 1, ,370 yes 0,66 0,7 0,628 0,634 0, , ,917 yes 6,4 1 6,84 6,41 6,44 0,426 6, ,330 yes 0,81 0,917 0,797 0,80 0,073 9, ,630 yes 30, ,8 30,3 2,24 7, ,890 yes 2,82 1 3,22 2,8 2,83 0,241 8, ,0 yes 2,04 2,29 2,06 2,03 0,24 11, ,4 yes 79 88,6 78,2 78, 4,8 6, ,777 yes,3 11,1,4,3 0,938 9, ,1 yes ,43 4, ,0 yes 8,37 8,83 8,6 8,48 0,99 11, H 2,28 <,0 2,3 2,21 0,31 1, ,330 yes 7 3,2 6,3 6,1 3, ,7 yes 12,2 1 11,6 12,3 12,2 1,06 8, ,67 yes 83,4 1 79, ,1 4,09 4, ,10 yes 9,92 8,78 9,8 9,91 1,02, ,4 yes,2 30 8,03 9,91 9,64 2,93 30, ,600 yes ,9, ,970 yes , , yes ,490 yes , A1Hg 0,241 yes 0,83 0,8 0,766 0,78 0,118 1, N3Hg 0,16 yes 0,17 2 0,167 0,163 0,164 0, , THg 0,140 yes 2,28 2 2,24 2,3 2,3 0,6 23, ,061 yes 3,9 2 3,93 3,86 3,8 0,37 9, ,622 yes 90 87,2 92,3 91,9 7,04 7, ,483 yes 44,2 1 4,8 44,8 44,4 3,42 7, ,99 yes ,2 4, ,298 yes ,4, ,369 yes 6,24 6,47,84, , ,072 yes 69 69, 67,4 67 4, ,211 yes 6,17 6,3 6,22 6,14 0,61 9, ,1 yes ,92 4, ,04 yes 11,2 11, ,1 1,26 11, ,080 yes 1,99 2,21 1,98 2,01 0,363 18, ,6 yes 92,9 0 92,8 93,2,66 6, ,04 yes 6,12 1 6,09,96 6,02 0,4 9, ,096 yes 67,6 68,3 67,4 67,2 4,89 7, ,663 yes 3,32 3,1 3,16 3,2 0,37 11, H 3,79 1 < 3,6 3,6 0,332 9, ,140 yes 86 86,6 84,7 84,6 4,04 4, H 4,83 < 4,78 4,7 0,449 9, ,233 yes 82,8 1 84,3 82,8 82,3 4,0 4, ,992 yes 12,6 11,4 12,6 12,7 1,17 9, ,290 yes 7,8 2,1 8,1 8,1 1,94 22, ,21 yes ,84, ,962 yes 1,8 2 17,7 1,9 1,9 2,41 1, ,082 yes ,6 8, , yes 2,3 2,8 3,1 2,3,42, Outlier test failed: C Cohcran, G1 Grubbs(1outlier algorithm), G2 Grubbs(2outliers algorithm), H Hampel, M manual SYKE Interlaboratory comparison test 3/

115 113 LIITE APPENDIX 8 / 41 Analyte Unit Sample zgraphics Z value Outl Assigned test OK value 2* Targ SD% Lab's result Md. Mean SD SD% Passed Outl. failed Missing Num of labs Laboratory 2 Al As Cd Cr Cu Fe Mn Ni Pb Zn Laboratory 3 Al As Cd Co Cr Cu Fe Hg Mn Ni Pb V Zn S6M THg 0,674 yes 1,6 2 14,3 1,4 1, 1,91 12, ,140 yes , ,080 yes ,9 7, ,260 yes 6,0 8,02 6,01,9 0,82 14, ,130 H ,4 7 6,8 3,68 6, ,43 yes 3,77 2 3,97 3,71 3,7 0,877 24, ,880 yes 0,66 0,8 0,628 0,634 0, , ,800 yes 6,4 1 7,27 6,41 6,44 0,426 6, ,470 yes 0,81 1,01 0,797 0,80 0,073 9, ,96 yes 2,04 2,23 2,06 2,03 0,24 11, ,1 yes 79 74,6 78,2 78, 4,8 6, ,602 yes,3,9,4,3 0,938 9, ,790 H 7 73, 6,3 6,1 3, ,370 yes, ,8 9,91 9,64 2,93 30, ,340 yes ,9, ,180 yes , ,40 yes 3,9 2 4,61 3,86 3,8 0,37 9, ,660 H ,3 91,9 7,04 7, ,00 H 44,2 1 92,3 44,8 44,4 3,42 7, ,0 yes 6,24 7,21,84, , ,213 yes 69 67, 67,4 67 4, ,240 yes 6,17 7, 6,22 6,14 0,61 9, ,84 yes 1,99 2,16 1,98 2,01 0,363 18, , yes 92,9 92,8 93,2,66 6, ,0 yes 6,12 1 7,29,96 6,02 0,4 9, ,681 yes ,84, ,613 yes 1, ,9 1,9 2,41 1, ,003 yes , ,080 yes , 9, ,24 yes 16,3 2 1,8 16,2 16,4 1,92 11, ,1 yes 91,1 90,1 91,9 90,8 7,66 8, ,390 yes 0,71 2 0,498 0,701 0,712 0,119 16, ,088 yes 30,3 1 30,1 30,1 30,1 1,93 6, ,237 yes 16,9 2 16,4 16,9 17,2 2,46 14, ,379 yes 40, 1 41,6 40,8 40, 1,77 4, ,049 yes ,6 6,7 63,8 9,07 14, ,389 yes ,6, ,00 yes 40 39,8 40,2 39,8,16 12, ,327 yes 8,6 1 83, 8,3 8,6 3,6 4, ,87 yes , ,377 C , 6, ,923 yes 0,13 2 0,14 0,134 0,126 0,023, ,877 yes 2,28 2 2,3 2,3 2,3 0,6 23, ,423 yes , ,066 yes ,7 4, ,9 yes 38,3 39, ,8 4,37 11, ,081 yes ,92 4, ,3 yes 46, 44,8 46,3 4,4 6 13, ,038 yes 6,6 6,8 6, 64,7,03 7, ,064 yes 70,3 69,8 69,7 70,3 8,34 11, ,041 yes 82,4 1 82,7 82,3 82,3 3,96 4, ,824 yes ,2, ,422 yes ,27 3, Outlier test failed: C Cohcran, G1 Grubbs(1outlier algorithm), G2 Grubbs(2outliers algorithm), H Hampel, M manual SYKE Interlaboratory comparison test 3/

116 LIITE 8 / APPENDIX Analyte Unit Sample zgraphics Z value Outl Assigned test OK value 2* Targ SD% Lab's result Md. Mean SD SD% Passed Outl. failed Missing Num of labs Laboratory 4 Al Cd Cu Fe Hg Mn Pb Zn Laboratory As Cd Cu Hg Ni Pb Zn S6M A1Hg N3Hg THg 0,197 yes 1, ,4 1, 1,91 12, ,424 yes , ,198 yes ,9 7, ,163 yes ,1 4, ,78 yes ,8 14, ,712 yes 0,66 0,613 0,628 0,634 0, , ,01 yes 6,4 1 6,16 6,41 6,44 0,426 6, ,00 yes 0,81 0,77 0,797 0,80 0,073 9, ,60 yes 30,1 1 28,8 29,8 30,3 2,24 7, ,070 yes 2,82 1 2,9 2,8 2,83 0,241 8, ,21 yes 2,28 2,33 2,3 2,21 0,31 1, ,03 yes 7 7,1 6,3 6,1 3, ,311 yes 12,2 1 12, 12,3 12,2 1,06 8, ,460 yes 83,4 1 80, 83 83,1 4,09 4, ,02 yes 9,92 9,42 9,8 9,91 1,02, ,690 H,2 30,4 9,91 9,64 2,93 30, ,79 yes ,9, ,4 yes , ,309 yes ,390 yes , ,228 yes 0,13 2 0,134 0,134 0,126 0,023, ,033 yes 3,9 2 3,88 3,86 3,8 0,37 9, ,312 yes 90 91,4 92,3 91,9 7,04 7, ,137 yes 44,2 1 44,7 44,8 44,4 3,42 7, ,29 yes ,2 4, ,6 yes ,4, ,688 yes 1,99 1,8 1,98 2,01 0,363 18, ,727 yes 92,9 89, 92,8 93,2,66 6, ,292 yes 6,12 1,99,96 6,02 0,4 9, ,070 yes 67,6 67,1 67,4 67,2 4,89 7, ,48 yes 3,32 3,17 3,16 3,2 0,37 11, ,677 yes 7,8 2 7,19 8,1 8,1 1,94 22, ,13 yes ,84, ,739 yes 1,8 2 14,3 1,9 1,9 2,41 1, ,826 yes ,6 8, ,330 yes 2,3 4,3 3,1 2,3,42, ,744 yes 6,0,6 6,01,9 0,82 14, ,8 yes 7 1 4, 7 6,8 3,68 6, ,6 yes 3,77 2 3,71 3,7 0,877 24, ,287 yes 97,7 1 97,7 97,6 6,31 6, ,889 yes 4,86 2,4 4,97 4,8 0,731 1, ,606 C 0,66 0,7 0,628 0,634 0, , ,8 yes 6,4 1 6, 6,41 6,44 0,426 6, ,1 yes 0,81 0,9 0,797 0,80 0,073 9, ,044 yes 30, ,8 30,3 2,24 7, ,090 yes 2,82 1 3,0 2,8 2,83 0,241 8, ,0 C 2,28 1, 2,3 2,21 0,31 1, ,702 yes 7 9 6,3 6,1 3, ,874 yes 12, ,3 12,2 1,06 8, ,304 yes 83,4 1 81, 83 83,1 4,09 4, ,8 yes 9,92, 9,8 9,91 1,02, ,301 yes 0,83 0,80 0,766 0,78 0,118 1, ,471 yes 0,17 2 0,16 0,163 0,164 0, , ,330 yes 2,28 2 1,9 2,3 2,3 0,6 23, ,77 yes 6,24 6,6,84, , ,072 yes 69 68, 67,4 67 4, ,211 yes 6,17 6,3 6,22 6,14 0,61 9, ,123 yes ,92 4, ,62 yes 11,2, 11 11,1 1,26 11, ,2 yes 1,99 1,7 1,98 2,01 0,363 18, ,667 yes 92, ,8 93,2,66 6, ,260 yes 6,12 1 6,7,96 6,02 0,4 9, ,03 yes 67, ,4 67,2 4,89 7, ,270 yes 3,32 2,9 3,16 3,2 0,37 11, ,1 yes 7,8 2 8,9 8,1 8,1 1,94 22, ,143 yes ,84, Outlier test failed: C Cohcran, G1 Grubbs(1outlier algorithm), G2 Grubbs(2outliers algorithm), H Hampel, M manual SYKE Interlaboratory comparison test 3/

117 11 LIITE APPENDIX 8 / 43 Analyte Unit Sample zgraphics Z value Outl Assigned test OK value 2* Targ SD% Lab's result Md. Mean SD SD% Passed Outl. failed Missing Num of labs Laboratory Zn Laboratory 6 Pb 1,160 yes 1,8 2 13, 1,9 1,9 2,41 1, ,082 yes ,6 8, ,3 yes 2,3 49, 3,1 2,3,42, ,01 yes 1,99 1,99 1,98 2,01 0,363 18, ,006 yes 92,9 92,9 92,8 93,2,66 6, ,0 yes 6,12 1 6,12,96 6,02 0,4 9, ,004 yes 67,6 67,6 67,4 67,2 4,89 7, ,011 yes 3,32 3,32 3,16 3,2 0,37 11, Outlier test failed: C Cohcran, G1 Grubbs(1outlier algorithm), G2 Grubbs(2outliers algorithm), H Hampel, M manual SYKE Interlaboratory comparison test 3/

118 LIITE APPENDIX 9 / LIITE 9. SUMMARY OF THE z SCORES APPENDIX 9. Summary of the z scores Analyte Sample\Lab Al S.... S q S.. Q. S u S S Q. S U. S. S S... S. S S. S S S u S S S. S S S q. S S... S u S S. S. S u S S S. S S. S U.. U.... S..... S S SO S S... S. S.. S S S. S. S. S U. S S.... S S S... S u S.. S. S u S S Q. S U. S. As S u... S S S.. U. S S. u S. S.. S. S S... S S S.. S S S S S S S. S. S S. S S.... S S.... S S. u S. S.. S u.. S.... S.... S S S SO S S... S. S.. S S S. S. S. S S.... S..... S. S S... S S S.... S S. u S. S.. S. Cd S q.. S S S S.. S. S S S S S. S S. S. S q.. U U S S S. S S S S S S S. S S S S. S S.. S S S S.... S S S S.. S S. S Q.. S.... S.... S S S SO S S.. S S. S.. S S S. S. S. S S. S S q.... S S S.. S S S S.. S. S S S S S. S S. S. Co S Q.. S S. S.. S. S S. S S. S S. U. S S.. Q S. S.. S S S S S S S. S q S Q. S S.. U S. S.... S S S S S. S S. U Q.. S.... S.... S S S SO S S.. S S. S.. S S S. S. S. S S. S S.... S S S.. S S. S.. S. S S S S S. S u. U. Cr S S.. S S q u S. S. S S S S S. S S. S. S S.. Q S u S S. S S S S S S S. S Q q q. S S.. Q S u S S. S. S S S S S. S S. S S. S S.... S.... S S S SO S S.. S S. S.. S S S. S. S. S S S.... S..... S. S S.. S S u S.. S. S S S S S. S S. q. Cu S S.. S q S S.. Q. S S S S S. Q S. U. U S.. Q S S S S. S S S S S S S. S S S S. q S.. S u S S S. S. S S S S S. S S. S S. S S.... S.... S S S SO U S.. S S. S.. S S S. S. S. S S S S.... S..... S. S S.. S S S S.. S. S S S S S. S Q. S. Fe S S. U U S. S q. S. S u S S S. u S. S. S S. S Q S. S S q S S S u S q S. S S S q. S S. S S S. S S. S. S u S S S. S S. S Q.. S.... S..... S q SO S S.. S S. S.. S S S. S. S. S S. q S.... S S Q.. S S. S.. S. S u S S S. S S. S. Hg A1Hg S. S. u.. S.. S.... S S q S.. S. N3Hg S. S. u.. S.. Q.. S. S S. S.. S. S6M S. u u S. S. q. U.. U S S THg S. U. S.... u U S... U S S S.. S. Mn S S. U S S S u S. S. S u S S S. S S. U. S q. Q U S. S S Q S S S u S q Q. S Q. S. S S. S Q S u S S. S. S u S S S. S S. S S. S S.... S..... S S SO S q.. U S. S.. S S S. S. S. S S. S S S.... S..... S. S S.. S S u S.. S. S u S S S. S S. S. N S6M S..... S S S Ni S U.. u U S S.. S. S S S S S. S S. q SYKE Interlaboratory comparison test 3/

119 117 LIITE APPENDIX 9 / 2 Analyte Sample\Lab S S.. S S S S S. S S S S S S S. S q S S. S S.. u S U S.. S. S S S S S. S S. S S. S S.... S.... S S S SO S S.. S S. S.. S S S. S. S. S S. S S.... S S S.. u S S S.. S. S S S S S. S S. S. P S6M S..... S S S Pb S U.. Q Q U q.... S S. S S. S u. S. S S.. U S S S S. S S Q S Q S S. S u S S. S S.. S Q u q.... S S S S S. S S. S S. S S.... S.... q S S SO S S.. S S. S.. S S S. S. S. S S. S S.... S S S.. S S U S.... S S. S S. S S. u. S S6M U..... S S Se S U..... u..... q. S S S... S. u.. S S. S. S S. S.... S S..... U..... S. S SO S S... S. u.. S S.... Q. S S.... S S u... S. u..... S. S.. S.... TC S6M V S S..... q.. S.. S. S S. S q... S u... S. S.. S S. S S S S. S u S.. S S... S. S..... S. S S. S q Q.. S.... S.... S. S SO S S... S. S.. S S.. S. S. S u S.... S S S... S. S.. S.. S. S Q. S u... Zn S S.. S U. S S. q. U S U S S. S.... S S.. Q S. S S S u S S S S S S. S q S.. S S.. S S. S S. q. U S Q S S. S S. S q.... S.... u S S SO S S.. Q S. S.. q S S. S. S. S q S u.... S S S.. S S. S.. q. S S S S S. S u... % Accredited yes yes yes yes yes yes yes yes yes yes yes yes yes yes yes yes yes yes Analyte Sample\Lab Al. S S. S S S S S S.. S.. S... S.... S S. S S S S S... S S. S S.. S. S S. S S. q S S S S... S S. S... S.... Q S. S S S S S.. S S S. SO S... q S S..... S. S..... S S.. S. U. S S S... S... S.. S.... S S. S S S S S... S S. S... S. S. As. S S. S S S S S S S. S.. U S S. S S S S S S S. S.. S S.. S. S S. S S. S S S S S. S. S.. u S S. S S S S S... S u. SO S... S S S.. S.... S..... S S.. S. S. S S S S.. S... S.. S S... S S. S S S S S. Q. q.. U Cd U S S. S S S S S S.. S.. S... U... u S S. S S S S S S S. S.. S Q.. S. S S. S S. S S S S S S.. S.. U S S. S S S S S... S U. SO u S... S S S.. S.... S..... S S.. S S S. S S S S. U S... S.. S S... S S. S S S S S. S. S.. S... Q... Co. S S. S S S S S... S.. S... S... u S S. S q S S S. S. S.. S S. S S.. S. S S. S S S S S... S.. Q... S.... S S. q S S S S.. S q SO SYKE Interlaboratory comparison test 3/

120 LIITE APPENDIX 9 / Analyte Sample\Lab S... S S S.. S.... S S.. S. S. S S S... S... S. S S S... S S. S S S S S. S. S.. S... S... Cr. S S. S S S q S... S.. q S S. S q S S S q S. S.. S S S u S. S S. S S. S S S S S S q. S.. S... S.... S S. S S S S S.. S S q. SO S... S S S.. S.... S. S... S S.. S S S. S S S S.. Q... S. u S S... S S. U S S S S. S. S.. q Cu U S S. S S S q S u u S S. S q S S S q S. S S. S Q.. S. u S u S S. S S S S S S S. S.. S... S.... S S. q S S S S.. S S S. SO u S... S S S.. S.. S. S..... S S.. S Q S. S S S S.. S... S.. S S.. u S S. S S S S S. S. S.. Q... U... Fe. S Q. S S. S S S... S... S S S S S S S S S S. S S S. S S S S S. S S S S S. S S S S S S. S S S. S... S.... S S. S S S S S.. S Q S. SO S S... S S S..... S. S. S... S S.. S q S. S S S S. S S... S. S S S.. u S S u S S S S S... S S. S... S. S. Hg A1Hg. S S. S Q. S S S. q u.. q S.. S... N3Hg. S S. S U. U S S..... S... S... S6M.. S. S S. S S... S.. S... S... THg.. S. S S. S S S. u Q.. S S.. q S.. Mn. S S. S S. S S. S.... U S S. S S S S S Q Q. q S. S S.. S. S S. S S. S S S S S q S. S S. S... S.... S S. q S S S S.. S S S. SO S... q S S.. Q.. S. S..... S S.. Q S S. S S S U. S S... S.. S S... S S S S S S S S. U. S S. S... S. S. N S6M.... S S S u S.. S u S. Ni. S S. S S S S S S S. S.. q S S. S S S S S S S. S.. S S S. S. S S. S S. S S S S S S S. S.. S S S. q S S S S.. S S S. SO S... S S S.. S... S S. S... S S.. S S S. S S S S. U S... S.. S S... S S. S S S S S. S. S.. S..... S. P S6M. S S.. Q S u S.. S u S. Pb. S S. Q S S S S... S.. S u S S. q S S S S S S. u.. S S.. S. S S. S S. S S S S S S S. q.. S S S. S S S S S.. q Q S. SO u S... S S S.. S.... S..... S S.. S. S. S S S S.. S... S.. S S... S S. Q S S S S... q.. S S S6M. S S.. S. S S.. u S. S. Se. S S. S S. S S S S Q. S S. S S... S.. S S.. S. Q.. S S. S S. S S... q.. u SO S... S. S S..... S... S. q.. S S... S... S.. S S... S S. S S. S S... q.. u TC S6M V. S S. S q. S S... S.. S S S. S q. S S... q.. S... S. S S. S S. S S. S S... S.. S S S. q S. S S... S S. SO S... q. S S..... S S.. S. S.. S S... S S S SYKE Interlaboratory comparison test 3/

121 119 LIITE APPENDIX 9 / 4 Analyte Sample\Lab S S. S S. S S... S.. S..... S. Zn. S Q. S S. S S... U.. U... S... S S S S S S S S S S S. S S. S S S S S. S S. S S. S S S S S Q.. S.. Q... S.... S S. S S S S S.. S S S. SO S S... S S S.. S.. S. S. S... S S.. S S S. S S S S. S S... S. S S S.. q S S. S S S S S. S. S S. S... S. S. % Accredited yes yes yes yes yes yes yes yes yes yes yes yes yes yes yes Analyte Sample\Lab % Al.... S S. S.. 81 S S S. S S. S.. 94 S S S. S q. S S... S SO S S. S.. S.. 92 S..... S S... S.. S.. 86 As.... S U.. S. 81 S. S. S U.. S. 97 U... S S.. Q S... S SO S. S... S. 0 S..... S... 0 U... S... S. 79 Cd.... S Q. S S. 87 S. S. S S. S S. 88 Q... S Q. S S U... q SO S. Q.. S S. 92 S..... S Q... S.. S S. 93 Co S. S u. S S... S SO S S..... S... 0 S Cr.... S S S. S. Q S S. S. S S S... S... 9 SO S. S S..... S S... S Cu S u. 69 Q S S. S U. S S. 79 S S S. S.. S S S... S... 9 SO S S. S.. S S. 93 S..... S S... S.. S S. 87 Fe.... S Q. U.. 70 S S S. S Q. S.. 87 S S S. S Q. S S... S SO S S. S.. S.. 96 S..... S S... S.. S.. 87 Hg A1Hg... u S... S. 72 N3Hg.. S S S... S. 83 S6M S S.. 7 THg.. q. S. S. S. 70 Mn.... S S. S.. 82 S S S. S U. S.. 70 SYKE Interlaboratory comparison test 3/

122 LIITE APPENDIX 9 / 1 Analyte Sample\Lab S S S. S U. S S... S SO S u. S.. S.. 81 S..... S S... S.. S.. 91 N S6M Ni.... S S.. S. 83 u. S. S S.. S. 9.. S. S Q.. S S... S... 9 SO S. S... S. 0 u..... S S... S. 96 P S6M.. S Pb.... S S. S S S 74 S. S. S Q. S S S 80 U... S Q. S S S 81.. q... S SO S. S.. S S S 96 U..... S U... S.. S S S 81 S S6M.. S Se S SO S TC S6M V S. S S S... S SO S. S S S Zn.... Q.. S S. 68 S S S. S S. S S. 93 S U S. S S. S S q... S SO S S. S.. S S. 89 S..... S S... S.. S S. 90 % Accredited yes yes yes yes yes yes % %* percentage of satisfactory results Totally satisfactory, % In all: 87 In accredited: 87 In nonaccredited: 84 SYKE Interlaboratory comparison test 3/

123 121 APPENDIX APPENDIX. EXAMPLES OF MEASUREMENT UNCERTAINTIES REPORTED BY THE LABORATORIES For evaluation of the measurement uncertainty the participants have used the procedures as follows: In the figures the procedures have been presented using the same code number. 1. using the variation of the results in X chart (for the artificial samples) 2. using the variation of the results in X chart and the variation of the replicates (r% or R chart for real samples) 3. using the data obtained in method validation and IQC, see e.g. NORDTEST TR 37 1) 4. using the data obtained in the analysis of CRM (besides IQC data). see e.g.nordtest TR 37 1). using the IQC data and the results obtained in proficiency tests. see e.g. NORDTEST TR 37 1) 6. using the "modelling approach" (GUM Guide or EURACHEM Guide Quantifying Uncertainty in Analytical Measurements 2) 7. other procedure 8. no uncertainty estimation IQC= internal quality control 1) 2)

124 LIITE APPENDIX / LIITE. APPENDIX. Al Uncertainty, % Meth2 Meth3 Meth4 Meth Meth6 Meth7 Al 2 Uncertainty, % 1 Meth2 Meth3 Meth4 Meth Meth6 Meth7 Al 2 Meth2 Meth3 Meth4 Meth Uncertainty, % Meth6 Meth7 1 SYKE Interlaboratory comparison test 3/

125 123 LIITE APPENDIX / 2 Al 30 Uncertainty, % 2 1 Meth2 Meth3 Meth4 Meth Al 3 30 Uncertainty, % 2 1 Meth2 Meth3 Meth4 Meth Meth6 Meth7 Al 2 Meth2 Meth3 Meth4 Meth Uncertainty, % Meth6 Meth7 1 SYKE Interlaboratory comparison test 3/

126 LIITE APPENDIX / Al 3 30 Uncertainty, % 2 1 Meth2 Meth3 Meth4 Meth Meth6 Meth7 As Uncertainty, % Meth2 Meth3 Meth4 Meth Meth6 As 30 2 Uncertainty, % Meth2 Meth3 Meth4 Meth Meth6 1 SYKE Interlaboratory comparison test 3/

127 12 LIITE APPENDIX / 4 As Uncertainty, % Meth2 Meth3 Meth4 Meth Meth6 As 3 30 Uncertainty, % 2 1 Meth2 Meth3 Meth4 Meth Meth6 As Uncertainty, % Meth2 Meth3 Meth4 Meth Meth SYKE Interlaboratory comparison test 3/

128 LIITE APPENDIX / 126 As 30 2 Uncertainty, % 1 Meth2 Meth3 Meth4 Meth Meth6 As Uncertainty, % Meth2 Meth3 Meth4 Meth Meth6 Cd Uncertainty, % Meth2 Meth3 Meth4 Meth Meth6 Meth SYKE Interlaboratory comparison test 3/

129 127 LIITE APPENDIX / 6 Cd Uncertainty, % Meth2 Meth3 Meth4 Meth Meth6 Meth7 Cd Uncertainty, % Meth2 Meth3 Meth4 Meth Meth6 Meth7 Cd 3 30 Meth2 Meth3 Meth4 Uncertainty, % Meth Meth6 2 1 SYKE Interlaboratory comparison test 3/

130 LIITE APPENDIX / Cd 30 2 Uncertainty, % 1 Meth2 Meth3 Meth4 Meth Meth6 Meth7 Cd Uncertainty, % Meth2 Meth3 Meth4 Meth Meth6 Meth7 Cd Uncertainty, % Meth2 Meth3 Meth4 Meth Meth6 Meth SYKE Interlaboratory comparison test 3/

131 129 LIITE APPENDIX / 8 Co Uncertainty, % Meth2 Meth3 Meth4 Meth Meth6 Meth7 Co 30 2 Uncertainty, % 1 Meth2 Meth3 Meth4 Meth Meth6 Meth7 Co Uncertainty, % Meth2 Meth3 Meth4 Meth Meth6 Meth SYKE Interlaboratory comparison test 3/

132 LIITE APPENDIX / Co 30 2 Uncertainty, % 1 Meth2 Meth3 Meth4 Meth Meth6 Co 30 2 Uncertainty, % 1 Meth2 Meth3 Meth4 Meth Meth6 Meth7 Co Uncertainty, % 24 Meth2 Meth3 Meth4 Meth Meth6 Meth SYKE Interlaboratory comparison test 3/

133 131 LIITE APPENDIX / Co 30 2 Uncertainty, % 1 Meth2 Meth3 Meth4 Meth Meth6 Meth7 Cu Uncertainty, % Meth2 Meth3 Meth4 Meth Meth6 Meth7 Cu 3 30 Uncertainty, % 2 Meth2 Meth3 Meth4 Meth Meth6 Meth7 1 SYKE Interlaboratory comparison test 3/

134 LIITE APPENDIX / Cu Uncertainty, % Meth2 Meth3 Meth4 Meth Meth6 Meth7 Cu 3 30 Uncertainty, % 2 1 Meth2 Meth3 Meth4 Meth Meth6 Cu 3 30 Uncertainty, % 2 Meth2 Meth3 Meth4 Meth Meth6 Meth7 1 SYKE Interlaboratory comparison test 3/

135 133 LIITE APPENDIX / 12 Cu 2 Uncertainty, % 1 Meth2 Meth3 Meth4 Meth Meth6 Meth7 Cu Uncertainty, % Meth2 Meth3 Meth4 Meth Meth6 Meth7 Fe Uncertainty, % Meth2 Meth3 Meth4 Meth Meth6 Meth SYKE Interlaboratory comparison test 3/

136 LIITE APPENDIX / Fe 2 Uncertainty, % 1 Meth2 Meth3 Meth4 Meth Meth6 Meth7 Fe 2 Uncertainty, % 1 Meth2 Meth3 Meth4 Meth Meth6 Meth7 Fe 2 Meth2 Meth3 Meth4 Uncertainty, % Meth Meth6 1 SYKE Interlaboratory comparison test 3/

137 13 LIITE APPENDIX / 14 Fe 2 Uncertainty, % 1 Meth2 Meth3 Meth4 Meth Meth6 Meth7 Fe 2 Uncertainty, % 1 Meth2 Meth3 Meth4 Meth Meth6 Meth7 Fe 2 Meth2 Meth3 Meth4 Meth Uncertainty, % Meth6 Meth7 1 SYKE Interlaboratory comparison test 3/

138 LIITE APPENDIX / Hg A1Hg Uncertainty, % Meth2 Meth3 Meth Meth6 Hg N3Hg 3 30 Uncertainty, % 2 1 Meth2 Meth3 Meth Meth6 Hg S6M 4 40 Uncertainty, % Meth2 Meth3 Meth4 Meth Meth SYKE Interlaboratory comparison test 3/

139 137 LIITE APPENDIX / 16 Hg THg Uncertainty, % Meth2 Meth3 Meth4 Meth Meth6 N S6M 2 Uncertainty, % 1 Meth2 Meth3 Meth Meth7 Ni Uncertainty, % Meth2 Meth3 Meth4 Meth Meth6 Meth SYKE Interlaboratory comparison test 3/

140 LIITE APPENDIX / Ni 30 2 Uncertainty, % 1 Meth2 Meth3 Meth4 Meth Meth6 Meth7 Ni Uncertainty, % Meth2 Meth3 Meth4 Meth Meth6 Meth7 Ni 30 2 Uncertainty, % Meth2 Meth3 Meth4 Meth Meth6 1 SYKE Interlaboratory comparison test 3/

141 139 LIITE APPENDIX / 18 Ni Uncertainty, % Meth1 Meth2 Meth3 Meth4 Meth Meth6 Meth7 Ni Uncertainty, % Meth2 Meth3 Meth4 Meth Meth6 Meth7 Ni Uncertainty, % Meth2 Meth3 Meth4 Meth Meth6 Meth SYKE Interlaboratory comparison test 3/

142 LIITE APPENDIX / P S6M 2 Uncertainty, % 1 Meth2 Meth3 Meth Meth6 Meth7 Pb Uncertainty, % Meth2 Meth3 Meth4 Meth Meth6 Meth7 Pb 30 2 Meth2 Meth3 Uncertainty, % Meth4 Meth Meth6 Meth7 1 SYKE Interlaboratory comparison test 3/

143 141 LIITE APPENDIX / Pb Uncertainty, % Meth2 Meth3 Meth4 Meth Meth6 Meth7 Pb 3 30 Uncertainty, % 2 1 Meth2 Meth3 Meth4 Meth Meth6 Pb 30 2 Meth2 Meth3 Uncertainty, % Meth4 Meth Meth6 Meth7 1 SYKE Interlaboratory comparison test 3/

144 LIITE APPENDIX / Pb 2 Uncertainty, % 1 Meth2 Meth3 Meth4 Meth Meth6 Meth7 Pb Uncertainty, % Meth2 Meth3 Meth4 Meth Meth6 Meth7 S S6M 30 2 Meth2 Uncertainty, % Meth3 Meth Meth6 1 SYKE Interlaboratory comparison test 3/

145 143 LIITE APPENDIX / 22 Zn Uncertainty, % Meth2 Meth3 Meth4 Meth Meth6 Zn 3 30 Uncertainty, % 2 1 Meth2 Meth3 Meth4 Meth Meth6 Meth7 Zn Uncertainty, % Meth2 Meth3 Meth4 Meth Meth SYKE Interlaboratory comparison test 3/

146 LIITE APPENDIX / Zn 30 2 Uncertainty, % 1 Meth2 Meth3 Meth4 Meth Meth6 Zn Uncertainty, % Meth2 Meth3 Meth4 Meth Meth6 Meth7 Zn Uncertainty, % 24 Meth2 Meth3 Meth4 Meth Meth6 Meth SYKE Interlaboratory comparison test 3/

147 14 LIITE APPENDIX / 24 Zn 3 30 Uncertainty, % 2 Meth2 Meth3 Meth4 Meth Meth6 Meth7 1 SYKE Interlaboratory comparison test 3/

148 Documentation page 146 Publisher Finnish Environment Institute (SYKE) Date January 11 Author(s) Mirja Leivuori, Kaija Korhonen, Timo SaraAho, Teemu Näykki, Olli Järvinen, Keijo Tervonen, Sari Lanteri and Markku Ilmakunnas Title of publication Proficiency test SYKE 3/ Metals in water and sediment Parts of publication/ other project publications Abstract The publication is available only in the internet The Finnish Environment Institute (SYKE) carried out the proficiency test for analysis of metals in waters and soil in April August. The measured analytes were: Al, As, Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb, Se, V, Zn, N, P, S and TC. In total 4 laboratories participated in the proficiency test. The sample types were: artificial and natural water, municipal and industrial waste water and sediment. 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, 87 % of the total data in this proficiency test were satisfactory when the deviations of 30 % from the assigned values were accepted. Keywords Publication series and number Theme of publication water analysis, metals, Al, As, Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb, Se, V, Zn, N, P, S, TC, water, sediment, environmental laboratories, proficiency test, interlaboratory comparisons Reports of Finnish Environment Institute 1/11 Project name and number, if any Financier/ commissioner Project organization ISSN ISBN (online) (PDF) No. of pages Language 148 English Restrictions Public Price For sale at/ distributor Financier of publication Printing place and year Helsinki 11 Other information Finnish Environment Institute, Customer service [email protected] Phone Fax Finnish Environment Institute, P.O. Box 140, FI0021 Helsinki, Finland

149 Kuvailulehti Julkaisija Suomen ympäristökeskus (SYKE) Julkaisuaika Tammikuu Tekijä(t) Mirja Leivuori, Kaija Korhonen, Timo SaraAho, Teemu Näykki, Olli Järvinen, Keijo Tervonen, Sari Lanteri ja Markku Ilmakunnas Julkaisun nimi SYKE Proficiency Test 3/ Metals in waters and sediment Julkaisun osat/ muut saman projektin tuottamat julkaisut Tiivistelmä Julkaisu on saatavana vain internetistä. Suomen ympäristökeskuksen laboratorio järjesti pätevyyskokeen ympäristönäytteitä analysoiville laboratorioille kesällä. Pätevyyskokeessa määritettiin synteettisestä näytteestä, kolmesta erityyppisestä vesinäytteestä sekä sedimenttinäytteestä seuraavat metallit: Al, As, Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb, Se, V, ja Zn. Lisäksi sedimenttinäytteestä pyydettiin määrittämään N, P, S ja TC. Pätevyyskokeeseen osallistui yhteensä 4 laboratoriota, joista yksi raportoi kahdella eri menetelmällä analysoidut tulokset. Laboratorioiden pätevyyden arviointi tehtiin zarvon avulla. Mittaussuureen vertailuarvona käytettiin pääsääntöisesti laskennallista pitoisuutta tai osallistujien ilmoittamien tulosten robustia keskiarvoa. Koko tulosaineistossa hyväksyttäviä tuloksia oli 87 %, kun vertailuarvosta sallittiin 30 %:n poikkeama. Asiasanat Julkaisusarjan nimi ja numero Julkaisun teema vesianalyysi, metallit, Al, As, Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb, Se, V, Zn, N. P, S, TC, vesi ja ympäristölaboratoriot, pätevyyskoe, laboratorioiden välinen vertailumittaus Reports of Finnish Environment Institute 1/11 Projektihankkeen nimi ja projektinumero Rahoittaja/ toimeksiantaja Projektiryhmään kuuluvat organisaatiot ISSN ISBN (verkkoj.) (PDF) Sivuja Kieli 148 Englanti Luottamuksellisuus Julkinen Hinta Julkaisun myynti/ jakaja Julkaisun kustantaja Painopaikka ja aika Helsinki 11 Muut tiedot Suomen ympäristökeskus, asiakaspalvelu Sähköpostiosoite: [email protected] puh faksi Suomen ympäristökeskus, PL 140, 0021 Helsinki

150 Presentationsblad 148 Utgivare Finlands Miljöcentral (SYKE) Datum Januari 11 Författare Mirja Leivuori, Kaija Korhonen, Timo SaraAho, Teemu Näykki, Olli Järvinen, Keijo Tervonen, Sari Lanteri och Markku Ilmakunnas Publikationens titel Provningsjämförelse 3/ Metaller i vatten och sediment Publikationens delar/ andra publikationer inom samma projekt Sammandrag Publikationen finns tillgänglig på internet Under AprilAugusti genomförde Finlands Miljöcentral en provningsjämförelse, som omfattade bestämningen av Al, As, Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb, Se, V, Zn, N, P, S, TC i vatten och sedimenten. Tillsammans 4 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 zvärden. I jämförelsen var 87 % av alla resultaten tillfredsställande, när total deviation på 30 % från referensvärdet accepterades. Nyckelord Publikationsserie och nummer Publikationens tema vattenanalyser, metaller, Al, As, Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb, Se, V, Zn, N, P, S, TC, sediment, provningsjämförelse, vatten och miljölaboratorier Reports of Finnish Environment Institute 1/11 Projektets namn och nummer Finansiär/ uppdragsgivare Organisationer i projektgruppen ISSN ISBN (online) (PDF) Sidantal Språk 148 Engelska Offentlighet Offentlig Pris Beställningar/ distribution Förläggare Tryckeri/ tryckningsort och år Finlands miljöcentral, informationstjänsten [email protected] Tfn Fax Finlands Miljöcentral, PB 140, 0021 Helsingfors Helsingfors 11 Övriga uppgifter

151 SYKE PROFICIENCY TEST 1/11 ISBN (PDF) ISSN (online) FINNISH ENVIRONMENT INSTITUTE