Proficiency Test SYKE 3/2011

Transkriptio

1 REPORTS OF FINNISH ENVIRONMENT INSTITUTE Proficiency Test SYKE 3/2011 Metals in water and sludge Mirja Leivuori, Kaija KorhonenYlönen, Timo SaraAho, Teemu Näykki, Keijo Tervonen, Sari Lanteri and Markku Ilmakunnas Finnish Environment Institute

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3 REPORTS OF FINNISH ENVIRONMENT INSTITUTE Proficiency Test SYKE 3/2011 Metals in water and sludge Mirja Leivuori, Kaija KorhonenYlönen, Timo SaraAho, Teemu Näykki, Keijo Tervonen, Sari Lanteri and Markku Ilmakunnas Helsinki 2011 Finnish Environment Institute

4 REPORTS OF FINNISH ENVIRONMENT INSTITUTE 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 5 2 ORGANIZING THE PROFICIENCY TEST Responsibilities Participants Samples and delivery Homogeneity studies Feedback from the pro ciency test Processing of the data Testing of normality of data, outliers and replicate results Assigned value Standard deviation for pro ciency assessment and z score 7 3 RESULTS AND CONCLUSIONS Results Analytical methods and status to the results Uncertainties of the results 16 4 EVALUATION OF PERFORMANCE 17 5 SUMMARY 18 6 YHTEENVETO 18 REFERENCES 19 APPENDICES Appendix 1 Participants in the pro ciency test 3/ Appendix 2 Preparation of the samples 21 Appendix 3 Testing of homogeneity 23 Appendix 4 Feedback from the pro ciency test 24 Appendix 5 Evaluation of the assigned values and their uncertainties 25 Appendix 6 Terms in the result tables 28 Appendix 7 Results of each participant 29 Appendix 8 Summary of the z scores 55 Appendix 9.1 Analytical methods 59 Appendix 9.2 Signi cant differences in the results reported using different sample digestion 61 Appendix 9.3 Signi cant differences in the results reported using different measurement 62 methods Appendix 9.4 Results grouped according to the methods 63 Appendix 10 Examples of measurement uncertainties reported by the laboratories 98 DOCUMENTATION PAGE 109 KUVAILULEHTI 110 PRESENTATIONS BLAD 111

6 ALKUSANAT 4 Suomen ympäristökeskus (SYKE) on toiminut ympäristöalan kansallisena vertailulaboratoriona vuodesta 2001 lähtien. Toiminta perustuu ympäristöministeriön määräykseen, mikä on annettu ympäristönsuojelulain (86/2000) nojalla. Vertailulaboratorion tarjoamista palveluista yksi tärkeimmistä on pätevyyskokeiden ja muiden vertailumittausten järjestäminen. SYKEn laboratoriot on FINASakkreditointipalvelun akkreditoima testauslaboratorio T003 (SFSEN ISO/IEC 17025) ja vertailumittausten järjestäjä Proftest SYKE PT01 (SFSEN ISO/IEC 17043, 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 (86/2000) since 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 SYKE laboratories has been accredited by the Finnish Accreditation service as the testing laboratory T003 (EN ISO/IEC 17025) and as the pro ciency testing provider Proftest SYKE PT01 (EN ISO/IEC 17043, 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 X tammikuuta 2012 / Helsinki X January 2012 Laboratorionjohtaja / Chief of Laboratory

7 1 Introduction 5 Proftest SYKE carried out the pro ciency test (PT) for analysis of elements in waters and sludge in April August The measurements were: Al, As, B, Cd, Co, Cr, Cu, Fe, Hg, Mn, Mo, Ni, Pb, Sb, Se, Sn, V and Zn. The sample types were: arti cial water, municipal and industrial waste water and sludge. A total of 39 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 [1], ISO [2] and IUPAC Recommendations [3]. The SYKE laborato ry has been accredited by the Finnish Accreditation Service as a pro ciency testing provider (PT01, ISO/IEC 17043, 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: Proftest SYKE, Finnish Environment Institute (SYKE), Laboratories, Hakuninmaantie 6, Helsinki, Finland, Phone: , Fax: Subcontractors in this pro ciency test were: Centre for Economic Devel opment, T ransport and the Environment in South Ostrobot hnia, 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 drying, sieving and dividing of sludge 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: Timo SaraAho heavy metal analyses (ICPOES, ICPMS, IDICPMS) Teemu Näykki Hganalyses, IDICPMS 2.2 Participants 39 laboratories from Finland, Sweden, Greece and Uruguay participated in the PT (Appendix1). 23 of the Finnish parti cipating laboratories provide data for use of the Finnish envir onmental authorities. About 60 % of the participating laboratories used accredited analytical methods for at least a part of the measurements. The organizing laboratory (SYKE) has the code 8 in the result tables. For lead the metrologically traceable assigned value has been measured by IDICPMS in SYKE laboratory and the laboratory

8 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 w ere de livered. The samples and A2M were prepared using single element Merck CertiPUR Reference material solutions to the concentration levels for FAAS, ICPOES or ICPMS measurements. The Merck Certipur RMs were traceable to the several NIST SRMs. The sample A1Hg was diluted from the Romil PrimAg plus CRM Hgsolution (traceable to SI unit via ultrapure primary reference silver). The arti cial samples were acidi ed with nitric acid. The sample was municipal waste water with additions of single element standard solutions except for B, Cu, Fe and Ni (Appendix 2). The forth samples were industrial waste water T4Hg for Hg measurements and the sample TN/ for measurements of other metals. These samples were prepared with additions of single element standard solutions with the exceptions for Fe and Mn (Appendix 2). The water samples were acidi ed with nitric acid (Appendix 2). The purity of the laboratory ve ssels used in t he sample prepar ation was checked. According to the t est the used sample vessels ful lled the purity requirements. The tested sludge was from the s ewage treatment plan from the southern Finland. B asically, no addition of metals was needed with the exceptions for Cd, M o, Pb, Sb and Se (Appendix 2). The addition was done with the Merck CertiPUR solution of metals. After homogenisation the wet sludge was air dried, homogenized and divided into subsamples using a vibrating feeder distributor. The samples were delivered 23 May Mercury was requested to be measured 27 May 2011 at the latest. All the samples were requested to be analysed and reported 24 August 2011 at the latest. 2.4 Homogeneity studies The homogeneity of the samples was studied by measuring Cd, Cu, Mn, Zn (waters and sediment) and Hg (water and sludge). According to the homogeneity test results the samples were considered to be homogenous. More detailed information of homogeneity studies is in Appendix Feedback from the pro ciency test The comments from the participants are in Appendix 4. The comments mainly deal with the errors with reporting of the results. The comments from the provider to the participants are also shown in Appendix 4. These are mainly focused to the lacking conversancy to the given information with the samples. 2.6 Processing of the data Testing of normality of data, outliers and replicate results Before the statistic al treatment, the data was tested according to the Kolmogor ovsmirnov normality test and the possibl e extreme values w ere rejec ted as the outliers ac cording 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 50 %. The replicate results were tested using the Cochran test. In case that the result had been reported to be lower than detection limit, it had not been included in the statistical calc ulation 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 Proftest pro ciency testing schemes

9 ( /syke/proftest) Assigned value The assigned values and their uncertainties are presented in Appendix 5. The calculated concentrations were used as the assigned values for most measurands in the arti cial samples. 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, A2M and A1Hg the calculated concentrations were used as the assigned value with exceptions of antimony, vanadium and mercury A1Hg samples. The assigned values based on the calculated concentrations are traceable to several NIST SRMs or primary re ference silver (Ag). For lead the metrologically traceable assigned value has been used for samples, (nonaccredited) and (nonaccredited). 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 t he scope of calibration laboratory (K054; www. nas. ). For the other samples and measurements the robust mean of the participant's res ults was used as the assigned value. For the robust mean metrological traceability is not available. In the calculation of robust mean single r esults were e xcluded as replicate results were requested (i.e. Labs 2, 19 ()). The uncertainty of the assigned value was calculated using the robust standard deviation of the reported results using the formula presented in Appendix 5. 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 0.3 and 3 %. When using the robus t mean of the participant results as the assigned value, the uncertainties of the a ssigned values varied between 0.5 % and 26 % (Appendix 5). After reporting of the preliminary results some minor corrections to the assigned values have been done. The results of one participant w ere only partly transported to the statistical programme in the preliminary handling. This error in the electronic data transportation corrected to the nal data handling. The assigned value of the following samples and parameters has been changed: : Cr, Cu, Mn, Mo, Pb : Fe, Mn, Mo, Sb, Se, V L5M: Hg : Sn, V The changes in t he as signed va lue in uenced to the performance evaluati on o f the following laboratories' results: Lab 2: Cr Lab 8: Mn Lab 9: L5M Hg Lab 18: Pb For the other laboratories no in uence in the performance evaluation was noticed Standard deviation for pro ciency assessment and z score The performance evaluation was ca rried out by using z scores (Appendix 6). 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.

10 8 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 7. 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: : As, B, Co, Fe, Hg, Mo, Pb, Sn LO5: Co, Mo, Ni, Pb : Se : Mo, Sb, Se 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 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 in the following cases: : As, B, Mo, Sn LO5: Mo, Ni, Pb : Se : Mo, Sb, Se Due to this the e valuation of performance is only informative for the metals and sa mples listed above. For the several measurements in the samples LO5, LT5 or the evaluation of performance has not been carried out due to the low number of participants (below 6). However, in some cases the assigned values were reported as informative with the p reliminary results of the PT. In the nal reporting the performance evaluation of Se in the sample has withdrawn due to the difference of results between the ICPOES and ICPMS measurements causing low number of results for the robust calculation of the assigned value. 3 Results and conclusions 3.1 Results The results and the performance of each laboratory are presented in Appendix 7 and the summary of the results in Table 1. The summary of z scores is shown in Appendix 8. The reported results and their uncertainties are presented graphically in Appendix 9.4. The robust standard deviation of results was lower than 10 % for 62 % of the results and lower than 20 % for 86 % of the results (Table 1). Standard deviations higher than 20 % apply mainly to the sludge sample (, LO6, LT5) with a low number of participants. The robust standard deviations of the results in this PT were approximately in the same range as in the previous comparable

11 9 PT SYKE 6/2008 [4], where the deviations varied mainly from 1.5 % to 40.3 %. The increased variability of the results can be caused by the sensitivity differences among the used analytical instruments. Alternatively, 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 r equested to report duplicate r esults for a ll measurements. The participants reported the replicates with the exception of two laborator ies (Labs 2, 19 (sample )). The results of the replicate determinations based on the ANOVA statistical handling are presented in Table 2. The withinlaboratory standard deviation, s w, describes the repeatability of measurements. While the betweenlaboratory standard deviation, s b, describes the reproducibilit y of mea surements. In this PT the reproducibility (s b ) was an average from 2 to 9 times higher than the repeatability (s w ). For the robust methods the robustness of the method, the ratio s b /s w, should not exceed 3 (table 2).

12 10 Table 1. Summary of the results in the pro ciency test 3/2011.

13 11 Table 1. Summary of the results in the pro ciency test 3/2011. where Ass. val. the assigned value Mean the mean value Mean rob the robust mean Md the median value SD rob the robust standard deviation SD rob % the robust standard deviation as percents Num of Labs the number of the participants 2*Targ. SD% the total standard deviation for pro ciency assessment at the 95% 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 Analytical methods and status to the results It was allowed to us e different analytica l methods for the mea surements in the PT. The used analytical methods of the participants are shown in more detail in Appendix 9.1. In Appendix 9.4 is shown the results grouped acording to the methods. Mercury KBr/KBrO 3, KBr, KMnO 4, HNO 3 /KMnO 4 or KMnO 4 /K 2 S 2 O 8 solutions w ere typically used as the oxidant in mercury a nalyses from waters at room tempe rature, in water bath (95 C), in autoclave ( C) or in microwave oven. Additionally for mercury analyses in sludge also oxygen, nitric acid or aqua regia was used. T he sludge sample was digested using a water bath, autoclave, microwave oven or the s amples were measured using direct combu stion with oxygen ow. Mercury was measured mostly using cold va por CVAAS or CVAFS instruments. Other methods were for example FIMS ( ow injection mercury system based on atomic absor ption), ICPMS or direct combustion (O2 ow + AAS). Other elements The industrial waste water was measured without pretreatment (TN5) or after nitric acid digestion (TY5). The results of these samples were evaluated separately. The sludge sample L5M was digested by ni tric acid (+ hydrogen peroxide) (), by aqua regia (LO5) or by nitric and hydro uoric acids (LT5). The results of these diferently pretreated sediment samples were treated separately. Heavy metals were mainly measure d using FAAS, GAAS, ICPOES or I CPMStechniques. Arsenic was meas ured mainly using GA AS, ICP OES or ICPMSi nstruments. Only one laboratory used hydride techniques for measurements of As. 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 (TN5/TY5). An average about one ha lf of the l aboratories measured t he ac idi ed in dustrial wa ste water without sample pr etreatment (), while the second half of the participants measured the industrial waste water after nitric acid digestion (). The difference between t he average con centrations of e lements measured by different sample preparation methods was tested us ing the t test. The results of the ttest are shown in Appendix 9.2. There was statistically signi cant difference between aluminium, manganese and antimony results gained using no pretreatment method () and nitric acid digested results (). Effect of sample pretreatment on elemental concentrations in sludge Elements in the sludge sample were measured mainly after nitric acid or nitric acid and hydrogen peroxide digestion (). As the number of participants using aqua regia digestion (LOT5) was low for some measure ments (number lower than 6) a more detailed comparison of the sample pretreatment methods is not possible. Only two participants reported the results using nitric and hydro uoric acids digestion and the comparison is not possible. The robust mean values of the different sample pretreatment methods are shown in Table 1. There was a statistically signi cant difference (ttest) between chromium, molybdenum, antimony and selenium results gained using nitric acid digestion () and aqua regia digestion (LO5, Appendix 9.2).

17 15 Effect of measurement methods on elemental results The most com monly us ed analytical method was ICPOES a nd ICPMS, followed by GAAS, while FAAS was used only in a few cases (Appendices 9.1, 9.3 and 9.4). 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 9.3. There were some statistically signi cant differences between the results obtained using different methods from some samples. These were as follows: Measurement methods FAAS/ICPOES FAAS/ICPMS GAAS/ ICPOES GAAS/ ICPMS ICPOES/ICPMS Metal/Sample Al, Cu, Mn ; Cr, Zn ; Fe;, Mn, ; Zn Al, Cu ; Cr, Zn As, Ni Cd ; Cr, Cu As, Ni, Se ; B, Mn ; Mo ; Mo, Zn ; Se ; Zn The signi cant di fferences w ere m ost abundant be tween F AAS and ICPOES and be tween ICPOES and ICP MS me asurements. There were s igni cant differences in FAAS and GAAS measurements between ICPMS measurements. In the most case FAAS results were lower than ICPOES/MS results, w ith the exceptions of Al, Cu, Fe and Zn (Appendix 9.3). GAAS results were lower than ICPMS results for all m easurements and s ample types. ICPOES results were higher than ICPMS results, with the exceptions for Mo (, ), Ni () Se () and Zn (). For Se a statistically signi cant difference was found between the ICPOES and ICPMS results in the samples and (Appendix 9.2). Obtaining accurate Se results at this low concentration level is clearly a rather demanding task. Volatilization during sample pretreatment may cause loss of analyte, which might explai n low recoveries. Howeve r, numerous reasons may caus e results that are er roneously high. Selenium is poorly ionized in an induc tively coupled plasm a which limits sensitivity even if I CPMS is used. High carbon concentr ations increase the sensitivity of Se in ICPMS, but this problem is usually encountered in the a nalysis of or ganic matrices like biological tissue sa mples, when measured against aqueous calibration standards low in carbon. This int erference canno t be overcome by us ing collision or reaction ce ll instruments s ince it occurs in the plas ma, even if the use of s aid instrumentation is otherwise very bene cial in the determination of Se. In ICPMS measu rements internal standardiza tion is oft en used to impr ove the reproducibility and accuracy since any uctuations in the sam ple 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 spe ctrally interfere with the a nalyte or vice versa. It should a lso be kept in mind that spectral interfe rences cannot be corrected for by internal standardization. In addition, the emission lines of the inter nal 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 standardiz ation is not a prerequisite to reach good results in environmental samples.

18 16 ICP techniques have a longer linear working range compared to AAS. In AAS multiple dilutions may be necess ary, which might incre ase measuring uncertainties. Dil ution can be used in ICP 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 pre treatment (e.g. volatiliza tion during acid diges tion) or measurement (e. g. GAAS analysis). It may also be caused by incorrect background correction (ICPOES) or matrix effects. Recoveries that are t oo high may be caused by s pectral interferences (overlapping wavelengths in em ission spectrometry, polyatomic or is obaric in terferences in mass s pectrometry), m atrix 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 analytical methods (Appendix 9.1). Only a bout half of the par ticipants reported their methods, due to this the comparison of methods is only informative. From water samples mercury was mainly measured by CVAFS and CVAAS, followed by ICPMS method (Appendix 9.4). No signi cance difference between the used measuring methods was found. 3.3 Uncertainties of the results At maximum about 77 % of participants reported the expanded uncertainties w ith their re sults for some measurements (Table 4, Appendix 10). 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 appr oaches were us ed for estimating of measurement uncert ainty ( Appendix 10). The approach based on existing IQC data (Meth 2), validation da ta (Meth 3), CRM data (Meth 4) or IQC data and results of the pro ciency test were the most common. Generally, the approach for estimating measurement uncertainty has not made a de nite impact on the uncertainty estimates. Thus, harmonization in the estimating of uncertainties should be continued.

19 Table The range of the expanded measurement uncertainties reported with the results by the participants in the PT3/ 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 7 and the summary of z scores is presented in Appendix 8. The total number of laboratories participating in this PT was 39. The robust standard deviation of the results was mostly (86 % of the results) lower than 20 %. In the arti cial sample the conc entrations were fairly high a nd 86 % of the results were satisfactory, when accepting deviations of % f rom the assigned values. There were some more dif culties in the measurement of Cu and Sb, where less than 80 % of results were satisfactory. The results of the sludge sample LT5 was not evaluate d due to the low number of participants. The same applies to some metals in the s amples LO5 and LT5 as well. The result of Se was not evaluated due to the high deviation between the r esults or too low number of res ults. For the sludge sample deviations of % from the assigned value were accepted. 80 % of the results obtained after nitric acid digestion () we re satisfactory. The most dif cult elements to be measured seemed to be Al, Fe, Sn and Zn from the sludge sample after nitric acid digestion, where less than 80 % of the results were s atisfactory. I n the previous pro ciency test of sludge 74% of results were acceptance after nitric acid di gestion, when the deviations of 2025 % fr om the assigned value were acceptable [4]. For the was te water s amples ( and /) 89 % of the results were satisfactory, when deviations of % from the as signed value were accepted. In meas urements of Al, Cd and Sb from the municipal wate r sample () were s ome dif culties as less than 80 % of r esults were satisfactory. For the indus trial waste water TN5 without sa mple pretreatment 92 % of the results were satisfactory. After sample pretreatment for the sample TY5 94 % of the results were satisfactory. On average the satisfactory results were gained for Hg from all sample types (81 90 % ), when accepting deviations of % from the asigned value. The variety of measuring and pretreatment

20 18 techniques used by the laboratories creates differences in analysis results especially for the sludge sample (L5M). In total, 90 % of the results in this pro ciency test were satisfactory. About 60 % of the participants used accredited methods and 92 % of their results were satisfactory. 85 % of the results measured using nonaccredited methods were satisfactory. SYKE arranged a similar pro ciency test in 2008 and then 80 % of the results were satisfactory [4]. 5 SUMMARY Proftest SYKE carried out the pro ciency test for analysis of eleme nts in waters and sludge in April August The measured analytes were: Al, As, B, Cd, Co, Cr, Cu, Fe, Hg, Mn, Mo, Ni, Pb, Sb, Se, Sn, V and Zn. In total 39 laboratories participated in the pro ciency test. The sample types were: arti cial water, municipal and industrial waste water and sludge. The calculated concentrations or the robust mean of the results reported by the part icipants were used as the assigned values for me asurands, with the exception of Pb in water samples. For Pb metrologically traceable assigned values were used for samples A2M, N3M, and. The uncertainties of the calculat ed assigned valu es and metrologica lly traceable values were 3 % or less. The uncertainties of the consensus assigned values (the robust mean) varied from 2.1 % to 26 %. 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 pa rticipants. In total, 90 % of the results in this pro ciency test were satisfactory when deviations of % from the assigned values were accepted. Over half of the participants used accredited methods and 92 % of their results were satisfactory. 6 YHTEENVETO Proftest SYKE jä rjesti pätevyys kokeen ympäristönä ytteitä analysoivi lle laboratorioille kes ällä Pätevyyskokeessa m äritettiin synteettisestä näytteestä, kolmesta erityyppisestä vesinäytteestä sekä lietenäytteestä seuraavat alkuaineet: Al, As, B, Cd, Co, Cr, Cu, Fe, Hg, Mn, Mo, Ni, Pb, Sb, Se, Sn, V ja Zn. Pätevyyskokeeseen os allistui yhtee nsä 39 laboratoriota. L aboratorioiden pätevyyde n arviointi tehtiin zarvon avulla ja sen laskemi sessa käytetyn kokonaishajonnan tavoitearvot olivat välil lä %. Mittauss uureen ver tailuarvona käytettiin pä äsääntöisesti laskennallista pitoisuut ta tai osa llistujien ilmoi ttamien tuloste n robustia kes kiarvoa. L yijylle käytettiin metrologisesti jäljitettävää tavoit earvoa. Tavoitearvon epäv armuus synte ettisille n äytteille ja metr ologisesti jäljitettävälle arvolle oli pie nempi kuin 3 % ja robust ia kes kiarvoa käytettäes sä tavoitearvon epävarmuus vaihteli 2.1 % ja 26 % välillä. Lietenäytteen 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 90 %, kun vertailuarvosta salli ttiin %:n poikkeama. Yli puolet osallistujista käytti akkreditoituja määritysmenetelmiä ja näistä tuloksista oli hyväksyttäviä 92 %.

21 REFERENCES ISO/IEC 17043, Conformity assessment General requirements for pro ciency testing. 2. ISO 13528, Statistical methods for use in pro ciency testing by interlaboratory comparisons. 3. Thompson, M., Ellison, S. L. R., Wood, R., 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. 4. Korhonen K., Järvinen, O., Näykki, T., SaraAho, T., Ivalo, R., Tervonen, K., and Ilmakunnas, M Laboratorioiden välinen pätevyyskoe 6/2008. Suomen ympäristökeskuksen raportteja 9/2009. Helsinki. ( /download.asp?contentid=101746&lan= )

22 APPENDIX 1 PARTICIPANTS IN THE PROFICIENCY TEST 3/2011 ALS Scandinavia AB, Luleå, Sweden Boliden Harjavalta Oy, Harjavalta, Finland Danisco Sweeteners Oy, Kotka, Finland Ekokem Oy Ab, Riihimäki, Finland Enas Oy, Jyväskylä, Finland EteläPohjanmaan Vesitutkijat Oy, Ilmajoki, Finland Eurofins Scientic Finland Oy, Tampere, Finland FCG Finnish Consulting Group Oy, Helsinki, Finland FNsteel Oy Ab, Lapppohja, Finland Hortilab Oy Ab, Närpes, Finland HSY, Vesihuolto, Jätevesilaboratorio, Espoo, Finland ITM, Stockholm University, Stockholm, Sweden Jyväskylän ympäristötoimen laboratorio, Jyväskylä, Finland KCL Kymen laboratorio Oy, Kuusankoski, Finland Kokemäenjoen vesistön vesiensuojeluyhdistys ry, Tampere, Finland Laboratorio Ambiental DINAMA, Montevideo, Uruguay Labtium Oy, Espoo, Finland Lapin Vesitutkimus Oy, Rovaniemi, Finland LounaisSuomen vesi ja ympäristötutkimus Oy, Turku, Finland Maintpartner Oy, Laboratorio ja ympäristöpalvelut, Kokkola, Finland MetropoliLab, Helsinki, Finland Nablabs Oy, Oulu, Finland National Technical University of Athens, Athens, Greece Norilsk Nickel Harjavalta Oy, Harjavalta, Finland Novalab Oy, Karkkila, Finland Outokumpu Tornio Works, Tornio, Finland Porilab, Pori, Finland Ramboll Analytics, Lahti, Finland Ruukki Metals Oy, prosessilaboratorio, Hämeenlinna, Finland Rautaruukki OYJ, Ruukki Metals, Raahe, Finland SavoKarjalan ympäristötutkimus Oy, Kuopio, Finland StoraEnso Oyj, Tutkimuskeskus, vesi ja h ivenainelaboratorio, Imatra, Finland Suomen ympäristöpalvelu Oy, Oulu, Finland Sweden Recycling, Hovmantorp, Sweden SYKE, Laboratoriot, Helsinki, Finland UPM Tervasaari, Valkeakoski, Finland UPM Tutkimuskeskus, Lappeenranta, Finland Viljavuuspalvelu Oy, Mikkeli, Finland 20

23 PREPARATION OF THE SAMPLES 21 APPENDIX 2/1 The artificial samples and A2M were prepared by mixing some separate Merck CertiPUR Reference material solutions ( traceable to v arious N IST SRM s) and d iluting w ith acidified w ater. Th e ar tificial sample A 1Hg was prepared b y dil uting the Romil PrimAg plus Hg CRM solution (traceable to SI unit via ultrapure primary reference silver) with acid ified wa ter. T he water samples, T 4M, (/T Y4) and T 4Hg were prep ared b y adding some separate metal solutions into the original water sample. The sludge sample L5M ( /LO5/LT5) was prepared from the sludge of sewage treatment plant. The addition of single metals was done using Merck CertiPUR Merck solutions (1000 mg/l) to th e wet slu dge. This was we ll homogenated and pretested before the proficiency test. The spiked sludge was air dried, homogenated and divided into subsamples. Al As B Cd Co Cr Cu Fe Hg Mn Mo Ni Pb Sb Analyte Original Dilution Additon Ass. value Original Dilution Additon Ass. value Original Dilution Additon Ass. value Original Dilution Additon Ass. value Original Dilution Additon Ass. value Original Dilution Additon Ass. value Original Dilution Additon Ass. value Original Dilution Additon Ass. value Original Dilution Additon Ass. value Original Dilution Additon Ass. value Original Dilution Additon Ass. value Original Dilution Additon Ass. value Original Dilution Additon Ass. value Original Dilution Additon Ass. value A2M / / / / / / / / / / / / / /90.1 A1Hg T5Hg < / LO5/LT /9309/ /5.51/ // /33.8/ /10.3/ /54.1/ /318/ /135700/ /431/ / /28.7/ /126/ /18.6/

24 APPENDIX 2/2 PREPARATION OF THE SAMPLES 22 Se Sn V Zn Analyte Original Dilution Additon Ass. value Original Dilution Additon Ass. value Original Dilution Additon Ass. value Original Dilution Additon Ass. value A2M / / / /152 A1Hg T5Hg / LO5/LT /56.4/ /46.3/ /702/695 Original = the original concentration Dilution = the ratio of dilution Addition = the addition concentration Ass. value = the assigned value

25 TESTING OF HOMOGENEITY 23 APPENDIX 3 Measurement/ sample Concentration (µg l 1 or mg kg 1 ) s p % s p s a s a /s p Is s a /s p <0.5? s bb s bb 2 c Is s bb 2 <c? Cd/ YES YES Cu/ YES YES Mn/ YES YES Zn/ YES YES Cd/T4M YES YES Cu/T4M YES YES Hg/T4Hg NO YES Mn/T4M YES YES Zn/T4M YES YES Cd/L5M YES YES Cu/L5M YES YES Hg/L5M YES YES Mn/L5M YES YES Zn/L5M 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 the 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 10 The analytical deviation filled up the criteria s a /s p <0.5 for each sample and measurement with the exception for Hg in the sample T4Hg. Also in the each case the s bb 2 was smaller than the criteria c. Conclusion: The samples could be regarded as homogenous. For mercury in the sludge sample, T4Hg, the analytical deviation did not fullfilled the criteria. The testing laboratory reported analytical problems with their measurements, which might have influenced to the results. Thus the sample was regarded to be homogenous as well. The results of participants support the conclusion.

26 APPENDIX 4 24 FEEDBACK FROM THE PROFICIENCY TEST COMMENTS SENT BY THE PARTICIPANTS Laboratory Comments on samples Action/Proftest 21 There is a wish to collect the results This will take account in the future PTs. for Sn and Hg according to the different sample pretreatment methods (e.g. sludge, soil, sediment). 23 The participants informed that from the result sheet was missing the sample AM2. The sample was in the result sheet, but as only Sn measured from it the participant was not noticed the line. Laboratory Comments on results Action/Proftest 4 The laboratory asked about the delivery time of the preliminary results after sending them. To the participants informed the delivery day of their preliminary results and at the same time results were resent. There was error in the reporting of the replicate result of Al in the sample. The right results were: 8057 and 8090 mg kg The data of laboratory were only partly transferred to the statistical program in the preliminary data handling. 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 ( This error corrected to the final data handling. COMMENTS TO THE PARTICIPANTS Laboratory Comments on results 2, 9 Laboratories reported only one result in their whole dataset or partly of it, though replicate results were requested. These results were not included in the calculation of assigned values. 38 The laboratory is accredited, but it did not r eport the total measuring uncertainty of their measurements. 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.

27 25 APPENDIX 5/1 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 714 Calculated value 0.3 % 8268 Robust mean 7.3 % LO Robust mean 8.1 % LT5 397 Robust mean 4.1 % 438 Robust mean 8.8 % 125 Robust mean 6.9 % As 85.9 Calculated value 0.7 % 4.01 Robust mean 22 % LO5 LT5 201 Robust mean 3.4 % 193 Robust mean 6.1 % 7.38 Robust mean 7.6 % B 70.1 Calculated value 0.7 % 16.9 Robust mean 26 % LO5 LT5 187 Robust mean 5.0 % 95 Robust mean 6.4 Cd 9.74 Calculated value 0.7 % 35 Robust mean 8.3 % LO Robust mean 6.9 % LT Robust mean 2.8 % 65.0 Robust mean 5.5 % 5.17 Robust mean 4.3 % Co 35.8 Calculated value 0.5 % 9.95 Robust mean 12 % LO Robust mean 8.7 % LT Robust mean 3.1 % 53.4 Robust mean 5.6 % 13.3 Robust mean 4.0 % Cr 45.7 Calculated value 0.7 % 46.9 Robust mean 9.2 % LO Robust mean 5.1 % LT5 134 Robust mean 2.1 % 134 Robust mean 4.1 % 13.9 Robust mean 2.4 %

28 APPENDIX 5/2 EVALUATION OF THE ASSIGNED VALUES AND THEIR UNCERTAINTIES Analyte Sample Assigned value Evaluation of the assigned value Expanded uncertainty of the assigned value, U Cu 71.4 Calculated value 0.5 % 305 Robust mean 5.8 % LO5 318 Robust mean 5.8 % LT5 146 Robust mean 4.5 % 152 Robust mean 3.6 % 8.91 Robust mean 6.1 % Fe 685 Robust mean 0.3 % Robust mean 15 % LO Robust mean LT5 665 Robust mean 2.9 % 679 Robust mean 4.0 % 801 Robust mean 3.3 % Hg A1Hg 0.82 Robust mean 7.1 % L5M 0.62 Robust mean 15 % T4Hg 3.82 Robust mean 5.4 % Mn 214 Calculated value 0.3 % 423 Robust mean 3.6 % LO5 431 Robust mean 4.4 % LT5 108 Robust mean 2.8 % 112 Robust mean 3.5 % 462 Robust mean 2.8 % Mo 47.1 Calculated value 0.4 % 30.7 Robust mean 16 % LO Robust mean 13 % LT5 102 Robust mean 2.4 % 106 Robust mean 6.2 % 28.9 Robust mean 3.7 % Ni 48.5 Calculated value 0.4 % 27.0 Robust mean 11 % LO Robust mean 10 % LT5 110 Robust mean 2.8 % 113 Robust mean 5.5 % 10.4 Robust mean 4.8 % Pb IDICPMS 3.0 % 127 Robust mean 11 % LO5 126 Robust mean 11 % LT IDICPMS 3.0 % 42.6 Robust mean 7.1 % IDICPMS 3.0 % 26

29 27 APPENDIX 5/3 EVALUATION OF THE ASSIGNED VALUES AND THEIR UNCERTAINTIES Analyte Sample Assigned value Evaluation of the assigned value Expanded uncertainty of the assigned value, U Sb 45.8 Robust mean 7.0 % LO Robust mean 7.5 % LT Robust mean 6.7 % 90.1 Robust mean 5.7 % 6.52 Robust mean 9.3 % Se 64.4 Calculated value 0.7 % LO5 LT Robust mean 9.6 % 32.0 Robust mean 16 % 8.6 Robust mean 8.6 % Sn A2M 25.1 Robust mean 11 % 34.7 Robust mean 18 % V 58.4 Robust mean 2.1 % 45.5 Robust mean 6.8 % LO5 LT Robust mean 3.5 % 96.3 Robust mean 4.2 % 10.8 Robust mean 4.6 % Zn 229 Calculated value 0.3 % 701 Robust mean 5.0 % LO5 702 Robust mean 5.0 % LT5 154 Robust mean 2.5 % 152 Robust mean 3.7 % 37.3 Robust mean 3.7 % 1. Samples and A2M 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: 100 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

30 APPENDIX 6 TERMS IN THE RESULT TABLES 28 Results of each participants Sample the code of the sample zgraphics z score the graphical presentation z value calculated as follows: z = (x i X)/s p, where x i = the result of the individual laboratory X = t he reference value (the assigned value) s p = t he target value of the standard deviation for proficiency assessment Outl test OK yes t he 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 95 % 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 SD Standard deviation SD% Standard deviation, % Passed The results passed the outlier test Outl. failed The results not passed the outlier test Missing i.e. < DL Num of labs the total number of the participants Summary on the z scores S satisfactory ( 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: X * = median of x i s * = median of (i = 1, 2, p) x i x* (i = 1, 2, p) 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 * 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].

31 29 LIITE APPENDIX 7 / 1 LIITE 7. RESULTS OF EACH PARTICIPANTS APPENDIX 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 1 Al 0,714 yes ,9 47,52 6, ,119 yes , ,3 40,48 9, ,760 yes ,5 121,5 124,5 13,69 10, As 1,040 yes 85, ,2 83,45 83,74 5,423 6, ,414 yes ,4 15,82 8, ,667 yes 7, ,765 7,345 7,291 0, , B 1,027 yes 70, ,3 72,5 71,74 8,309 11, yes 196, ,6 21,5 11, ,158 yes ,5 95,3 95,18 9,791 10, Cd 0,643 yes 9, ,27 9,7 9,573 0,7089 7, ,851 yes ,85 65,75 65,08 4,367 6, ,090 yes 5, ,205 5,285 5,197 0,4364 8, Co 1,927 yes 35, ,25 35,27 35,38 1,805 5, ,348 yes 53, ,8 52,4 53,41 3,604 6, ,258 H 13, ,55 13,2 13,28 0,805 6, Cr 1,182 yes 45, ,4 45,4 45,73 2,523 5, ,895 yes ,8 7,89 5, ,440 H 13, ,1 13,95 13,91 0,7707 5, Cu 0,784 yes 71, ,2 71,85 71,25 4,565 6, ,132 yes ,5 153,5 151,8 7,476 4, ,567 yes 8, ,415 9,03 8,957 1,015 11, Fe 1,197 yes ,5 682,6 24,96 3, ,825 yes ,7 43,35 6, ,265 yes ,3 52,41 6, Mn 0,561 yes ,1 8,528 4, ,357 yes ,9 5,161 4, ,274 yes ,5 467, ,75 5, Mo 1,040 yes 47, ,55 45,5 45,75 1,61 3, ,132 yes ,5 105,5 5,635 5, ,292 yes 28, ,7 29,2 29,15 1,396 4, Ni 1,103 yes 48, ,85 48,45 48,19 3,004 6, ,944 yes ,4 7,009 6, ,885 yes 10, ,4 10,35 10,35 1,155 11, Pb 0,746 yes 66, ,3 66,78 66,28 3,867 5, ,798 yes 42, ,2 42,75 43,47 5,069 11, ,080 yes 6, ,64 5,71 5,712 0,531 9, Sb 0,873 yes 45, ,8 46,75 45,74 5,057 11, ,207 yes 90, ,5 92,3 90,14 4,332 4, ,147 yes 6, ,4 6,63 6,702 1,204 17, Se 2,661 yes 65, ,35 64,1 64,55 4,599 7, ,863 yes ,45 32,7 31,76 4,941 15, ,163 yes 8,6 25 7,35 8,305 8,663 1,002 11, Sn A2M 1,004 yes 25, ,95 25,65 25,08 3,346 13, V 0,308 yes 58, ,3 58,05 58,53 2,215 3, ,263 yes 96, ,2 95,6 96,58 4,505 4, ,278 yes 10, ,1 10,65 10,78 0,6983 6, Zn 1,310 yes , ,7 12,69 5, ,645 yes ,5 153,3 152,9 9,046 5, ,241 yes 37, , ,57 5,083 13, Laboratory 2 As 1,679 yes 4, ,02 3,98 3,887 1,027 26, Cd 0,389 yes ,7 35,4 34,21 4,308 12, Co 2,710 yes 9, ,58 10,1 9,803 1,515 15, Cr 1,990 yes 46, ,9 45,23 44,11 7,983 18, Cu 0,623 yes ,5 31,44 10, Mo 1,068 yes 30, ,8 31,1 30,84 4,328 14, Ni 2,222 yes ,0 25,6 25,21 5,143 20, Pb 0,252 yes ,9 19,45 15, V 0,088 yes 45, ,1 45,1 43,98 3,665 8, Zn 1,046 yes ,7 31,97 4, Outlier test failed: C Cohcran, G1 Grubbs(1outlier algorithm), G2 Grubbs(2outliers algorithm), H Hampel, M manual SYKE Interlaboratory comparison test 3/2011

32 LIITE 7 / 2 30 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 3 Al 0,168 yes ,9 47,52 6, ,249 yes , ,566 yes ,3 40,48 9, ,200 yes ,5 121,5 124,5 13,69 10, As 2,592 yes 85, ,2 83,45 83,74 5,423 6, ,538 yes 4, ,935 3,98 3,887 1,027 26, ,155 yes , ,4 15,82 8, ,409 yes 7, ,08 7,345 7,291 0, , B 0,143 yes 70, ,1 72,5 71,74 8,309 11, ,690 yes 16, ,65 17,7 15,86 4,146 26, yes 204, ,6 21,5 11, ,789 yes ,5 95,3 95,18 9,791 10, Cd 1,198 yes 9, ,865 9,7 9,573 0,7089 7, ,766 yes ,35 35,4 34,21 4,308 12, ,103 yes ,5 65,75 65,08 4,367 6, ,928 yes 5, ,53 5,285 5,197 0,4364 8, Co 1,006 yes 35, ,27 35,38 1,805 5, ,965 yes 9, ,15 10,1 9,803 1,515 15, ,237 yes 53, ,35 52,4 53,41 3,604 6, ,401 yes 13, ,7 13,2 13,28 0,805 6, Cr 0,088 yes 45, ,5 45,4 45,73 2,523 5, ,043 yes 46, ,2 45,23 44,11 7,983 18, ,298 yes ,8 7,89 5, ,048 yes 13, ,95 13,95 13,91 0,7707 5, Cu 0,840 yes 71, ,4 71,85 71,25 4,565 6, ,902 yes , ,5 31,44 10, ,965 yes ,5 151,8 7,476 4, ,410 yes 8, ,275 9,03 8,957 1,015 11, Fe 0,394 yes ,5 681,5 682,6 24,96 3, ,816 yes , ,619 yes , ,7 43,35 6, ,107 yes , ,3 52,41 6, Hg A1Hg 0,457 yes 0, ,7825 0,8145 0,8106 0, , L5M 1,521 yes 0, ,785 0,5965 0,5919 0, , T4Hg 1,134 yes 3, ,495 3,79 3,772 0,3658 9, Mn 0,047 yes , ,1 8,528 4, ,536 yes ,4 19,17 4, ,000 yes ,9 5,161 4, ,068 yes , ,75 5, Mo 1,040 yes 47, ,65 45,5 45,75 1,61 3, ,725 C 37, ,5 37,2 35,88 2,958 8, ,377 yes ,5 105,5 5,635 5, ,531 yes 28, ,05 29,2 29,15 1,396 4, Ni 0,144 yes 48, ,8 48,45 48,19 3,004 6, ,815 yes ,3 25,6 25,21 5,143 20, ,118 yes ,4 7,009 6, ,240 yes 10, ,65 10,35 10,35 1,155 11, Pb 1,315 yes 66, ,4 66,78 66,28 3,867 5, ,260 yes ,9 19,45 15, ,364 yes 42, ,05 42,75 43,47 5,069 11, ,624 yes 6, ,85 5,71 5,712 0,531 9, Sb 0,906 yes 45, ,65 46,75 45,74 5,057 11, ,753 yes 18, ,85 18,2 18,92 2,045 10, ,547 yes 90, ,4 92,3 90,14 4,332 4, ,245 yes 6, ,32 6,63 6,702 1,204 17, Se 0,143 yes 65, ,7 64,1 64,55 4,599 7, yes 62,65 50,9 42,9 16,03 37, ,263 yes ,05 32,7 31,76 4,941 15, ,735 yes 8,6 25 7,81 8,305 8,663 1,002 11, Sn A2M 0,366 yes 25, ,25 25,65 25,08 3,346 13, L5M 0,082 yes 34, ,2 36,1 34,65 4,869 14, V 0,188 C 58, ,95 58,05 58,53 2,215 3, ,538 yes 45, ,95 45,1 43,98 3,665 8, ,205 yes 96, ,6 96,58 4,505 4, ,046 yes 10, ,85 10,65 10,78 0,6983 6, Zn 0,844 C , ,7 12,69 5, ,732 yes , ,7 31,97 4, Outlier test failed: C Cohcran, G1 Grubbs(1outlier algorithm), G2 Grubbs(2outliers algorithm), H Hampel, M manual SYKE Interlaboratory comparison test 3/2011

33 31 LIITE APPENDIX 7 / 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 Zn Laboratory Al As B Cd Co Cr Cu Fe Mn Mo Ni Pb Sb 3 4 LO5 0,724 yes ,5 153,3 152,9 9,046 5, ,362 yes 37, , ,57 5,083 13, ,175 yes , ,9 47,52 6, ,711 H , ,588 yes ,5 394, ,87 6, ,457 yes ,3 40,48 9, ,480 yes ,5 124,5 13,69 10, ,202 yes 85, ,6 83,45 83,74 5,423 6, ,729 yes 4, ,97 3,98 3,887 1,027 26, ,697 yes ,54 6, ,399 yes , ,4 15,82 8, ,238 yes 7, ,16 7,345 7,291 0, , ,509 H 70, ,5 72,5 71,74 8,309 11, ,316 yes 16, ,7 17,7 15,86 4,146 26, ,086 yes , ,5 11,85 6, ,947 yes ,3 95,18 9,791 10, ,014 yes 9, ,75 9,7 9,573 0,7089 7, ,651 yes ,15 35,4 34,21 4,308 12, ,093 yes 64, ,3 64,4 64,67 3,481 5, ,831 yes ,95 65,75 65,08 4,367 6, ,593 yes 5, ,4 5,285 5,197 0,4364 8, ,173 yes 35, ,7 35,27 35,38 1,805 5, ,579 yes 9, ,23 10,1 9,803 1,515 15, ,843 yes 52, ,36 2,647 5, ,837 yes 53, ,05 52,4 53,41 3,604 6, ,802 yes 13, ,5 13,2 13,28 0,805 6, ,044 yes 45, ,8 45,4 45,73 2,523 5, ,334 yes 46, ,55 45,23 44,11 7,983 18, ,448 yes ,4 134,2 7,154 5, ,522 yes , ,8 7,89 5, ,000 yes 13, ,9 13,95 13,91 0,7707 5, ,700 yes 71, ,9 71,85 71,25 4,565 6, ,049 yes ,5 31,44 10, ,959 yes , ,7 11, ,307 yes ,5 153,5 151,8 7,476 4, ,146 yes 8, ,04 9,03 8,957 1,015 11, ,365 yes ,5 681,5 682,6 24,96 3, ,253 H , ,226 yes ,5 664,5 664,8 35,53 5, ,609 yes ,7 43,35 6, ,075 yes , ,3 52,41 6, ,280 yes ,1 8,528 4, ,662 yes ,4 19,17 4, ,185 yes ,6 5,244 4, ,625 yes , ,9 5,161 4, ,433 yes , ,75 5, ,786 yes 47, ,25 45,5 45,75 1,61 3, ,902 yes 30, ,4 31,1 30,84 4,328 14, ,412 yes , ,5 3,982 3, ,377 yes ,5 105,5 5,635 5, ,346 yes 28, ,65 29,2 29,15 1,396 4, ,175 yes 48, ,35 48,45 48,19 3,004 6, ,346 yes ,6 25,6 25,21 5,143 20, ,273 yes , ,2 6,365 5, ,177 yes , ,4 7,009 6, ,481 yes 10, ,9 10,35 10,35 1,155 11, ,273 yes 66, ,7 66,78 66,28 3,867 5, ,165 yes , ,9 19,45 15, ,232 yes 43, ,5 41,9 41,12 2,908 7, ,232 yes 42, ,35 42,75 43,47 5,069 11, ,514 yes 6, ,44 5,71 5,712 0,531 9, ,262 yes 45, ,75 45,74 5,057 11, ,344 yes 18, ,4 18,2 18,92 2,045 10, ,245 yes 88, , ,41 12,32 14, ,043 yes 90, ,05 92,3 90,14 4,332 4, ,270 yes 6, ,74 6,63 6,702 1,204 17, Outlier test failed: C Cohcran, G1 Grubbs(1outlier algorithm), G2 Grubbs(2outliers algorithm), H Hampel, M manual SYKE Interlaboratory comparison test 3/2011

34 LIITE 7 / 4 32 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 Se 0,051 yes 65, ,65 64,1 64,55 4,599 7, Laboratory 4 Se yes 22,4 50,9 42,9 16,03 37, ,039 yes 36, ,35 36,45 36,18 4,631 12, ,762 yes ,95 32,7 31,76 4,941 15, ,535 yes 8,6 25 8,025 8,305 8,663 1,002 11, Sn A2M 0,351 yes 25, ,65 25,08 3,346 13, V 0,120 yes 58, ,05 58,05 58,53 2,215 3, ,209 yes 45, ,1 43,98 3,665 8, ,392 yes 95, ,4 95,35 95,33 4, ,305 yes 96, ,1 95,6 96,58 4,505 4, ,278 yes 10, ,5 10,65 10,78 0,6983 6, Zn 0,728 yes , ,7 12,69 5, ,694 yes , ,7 31,97 4, ,195 yes ,5 154,3 153,9 7,502 4, ,789 yes ,3 152,9 9,046 5, ,046 yes 37, , ,57 5,083 13, Laboratory 5 Al As B Cd Co Cr Cu Fe Hg Mn Mo Ni Pb Sb V 1,483 yes , ,9 47,52 6, yes ,7 6, ,359 yes ,3 394, ,87 6, ,432 yes ,4 121,5 124,5 13,69 10, ,605 yes 85, ,45 83,74 5,423 6, yes 6,015 5,65 5,509 0, , ,443 yes , ,54 6, ,623 C 7, ,8 7,345 7,291 0, , yes 11,65 15,4 15,2 2,881 18, ,971 yes 9, ,3 9,7 9,573 0,7089 7, ,503 yes 33, ,1 33,1 33,82 1,974 5, ,805 yes 64, ,4 64,67 3,481 5, ,275 H 5, ,9 5,285 5,197 0,4364 8, ,726 yes 35, ,5 35,27 35,38 1,805 5, ,913 yes 10,3 20 8,33 10,53 10,19 0,965 9, ,268 yes 52, , ,36 2,647 5, ,802 yes 13, ,5 13,2 13,28 0,805 6, ,306 yes 45, ,4 45,73 2,523 5, ,070 yes 54, ,9 54,45 52,88 4,893 9, ,448 yes ,4 134,2 7,154 5, ,096 yes 13, ,95 13,91 0,7707 5, ,513 yes 71, ,85 71,25 4,565 6, ,252 yes ,5 317,6 16,5 5, ,187 yes ,7 11, ,021 yes 8, ,03 8,957 1,015 11, ,131 yes ,5 681,5 682,6 24,96 3, yes , ,361 yes ,5 664,8 35,53 5, ,133 yes ,3 52,41 6, L5M 0,014 yes 0, ,6185 0,5965 0,5919 0, , ,187 yes ,1 8,528 4, ,015 yes ,5 427,5 431,2 17, ,648 yes , ,6 5,244 4, ,346 yes , ,75 5, ,712 yes 37, ,75 37,2 35,88 2,958 8, ,412 yes 48, ,5 48,45 48,19 3,004 6, ,418 yes 28, ,9 28,7 28,71 2,54 8, ,364 yes ,2 6,365 5, ,962 yes 10,4 20 9,4 10,35 10,35 1,155 11, ,285 yes 66, ,5 66,78 66,28 3,867 5, ,908 yes ,95 126,5 124,3 14,77 11, ,538 yes 43, ,5 41,9 41,12 2,908 7, ,208 yes 6, ,2 5,71 5,712 0,531 9, ,760 H 45, ,75 45,74 5,057 11, ,086 yes 18, ,4 18,2 18,92 2,045 10, ,779 yes 88, , ,41 12,32 14, ,515 C 6, ,1 6,63 6,702 1,204 17, ,993 yes 58, ,5 58,05 58,53 2,215 3, yes 39,45 46,1 46,28 5,17 11, ,798 yes 95, ,5 95,35 95,33 4, Outlier test failed: C Cohcran, G1 Grubbs(1outlier algorithm), G2 Grubbs(2outliers algorithm), H Hampel, M manual SYKE Interlaboratory comparison test 3/2011

35 33 LIITE APPENDIX 7 / 5 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 5 Zn Laboratory 6 Cu Ni Pb Laboratory 7 Al As B Cd Co Cr Cu Fe Hg Mn Mo Ni Pb V Zn LO5 A1Hg 1,204 yes 10,8 20 9,5 10,65 10,78 0,6983 6, ,524 yes ,7 12,69 5, ,199 yes ,5 704, ,18 6, ,039 yes ,3 153,9 7,502 4, ,751 yes 37, , ,57 5,083 13, ,738 yes ,5 31,44 10, ,901 yes ,25 25,6 25,21 5,143 20, ,976 yes , ,9 19,45 15, ,497 yes , ,9 47,52 6, ,117 yes ,5 394, ,87 6, ,680 yes ,5 121,5 124,5 13,69 10, ,194 yes 85, ,65 83,45 83,74 5,423 6, ,249 yes , ,54 6, ,461 yes 7, ,805 7,345 7,291 0, , ,043 yes 70, ,8 72,5 71,74 8,309 11, ,160 yes , ,5 11,85 6, ,221 yes ,4 95,3 95,18 9,791 10, ,055 yes 9, ,7 9,7 9,573 0,7089 7, ,217 yes 64, ,9 64,4 64,67 3,481 5, ,309 yes 5, ,05 5,285 5,197 0,4364 8, ,251 yes 35, ,25 35,27 35,38 1,805 5, ,460 yes 52, , ,36 2,647 5, ,100 yes 13, ,2 13,2 13,28 0,805 6, ,241 yes 45, ,25 45,4 45,73 2,523 5, ,224 yes ,5 132,4 134,2 7,154 5, ,048 yes 13, ,85 13,95 13,91 0,7707 5, ,611 yes 71, ,15 71,85 71,25 4,565 6, ,502 yes , ,7 11, ,606 yes 8, ,45 9,03 8,957 1,015 11, ,234 yes ,5 682,6 24,96 3, ,436 yes ,5 664,5 664,8 35,53 5, ,158 yes , ,3 52,41 6, ,341 yes 0, ,93 0,8145 0,8106 0, , ,327 yes , ,1 8,528 4, ,185 yes ,6 5,244 4, ,447 yes ,5 467, ,75 5, ,127 C 47, ,4 45,5 45,75 1,61 3, ,098 yes , ,5 3,982 3, ,507 yes 28, ,8 29,2 29,15 1,396 4, ,536 yes 48, ,1 48,45 48,19 3,004 6, ,727 yes ,2 6,365 5, ,048 yes 10, ,45 10,35 10,35 1,155 11, ,782 yes 66, ,4 66,78 66,28 3,867 5, ,404 yes 43, ,2 41,9 41,12 2,908 7, ,298 yes 6, ,71 5,712 0,531 9, ,514 yes 58, ,9 58,05 58,53 2,215 3, ,014 yes 95, ,3 95,35 95,33 4, ,417 yes 10, ,35 10,65 10,78 0,6983 6, ,437 yes , ,7 12,69 5, ,000 yes ,3 153,9 7,502 4, ,255 yes 37, , ,57 5,083 13, Outlier test failed: C Cohcran, G1 Grubbs(1outlier algorithm), G2 Grubbs(2outliers algorithm), H Hampel, M manual SYKE Interlaboratory comparison test 3/2011

36 LIITE 7 / 6 34 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 8 Al 0,266 yes ,9 47,52 6, ,359 yes , ,554 yes ,5 394, ,87 6, ,080 yes ,5 124,5 13,69 10, As 0,078 yes 85, ,4 83,45 83,74 5,423 6, ,324 yes 4, ,205 3,98 3,887 1,027 26, ,453 yes , ,54 6, ,287 yes 7, ,645 7,345 7,291 0, , B 0,692 yes 70, ,95 72,5 71,74 8,309 11, ,848 yes 16, ,05 17,7 15,86 4,146 26, ,535 yes ,5 11,85 6, ,142 yes ,65 95,3 95,18 9,791 10, Cd 0,027 yes 9, ,72 9,7 9,573 0,7089 7, ,754 yes ,3 35,4 34,21 4,308 12, ,663 yes 64, ,2 64,4 64,67 3,481 5, ,799 yes 5, ,48 5,285 5,197 0,4364 8, Co 0,279 yes 35, ,3 35,27 35,38 1,805 5, ,126 yes 9, ,35 10,1 9,803 1,515 15, ,261 yes 52, , ,36 2,647 5, ,752 yes 13, ,05 13,2 13,28 0,805 6, Cr 0,022 yes 45, ,75 45,4 45,73 2,523 5, ,230 yes 46, ,55 45,23 44,11 7,983 18, ,866 yes ,5 132,4 134,2 7,154 5, ,391 yes 13, ,35 13,95 13,91 0,7707 5, Cu 0,294 yes 71, ,45 71,85 71,25 4,565 6, ,754 yes ,5 31,44 10, ,233 yes , ,7 11, ,560 yes 8, ,3 9,03 8,957 1,015 11, Fe 0,657 yes ,5 681,5 682,6 24,96 3, ,554 yes , ,504 yes ,5 664,8 35,53 5, ,632 yes ,3 52,41 6, Hg A1Hg 1,878 yes 0, ,974 0,8145 0,8106 0, , Mn 0,467 yes ,1 8,528 4, ,371 yes , ,4 19,17 4, ,852 yes ,6 5,244 4, ,635 yes , ,75 5, Mo 0,021 yes 47, ,05 45,5 45,75 1,61 3, ,638 yes 30, ,15 31,1 30,84 4,328 14, ,373 yes ,5 3,982 3, ,830 yes 28, ,7 29,2 29,15 1,396 4, Ni 0,010 yes 48, ,55 48,45 48,19 3,004 6, ,086 yes ,4 25,6 25,21 5,143 20, ,364 yes ,2 6,365 5, ,433 yes 10, ,85 10,35 10,35 1,155 11, Pb 0,243 yes 66, ,6 66,78 66,28 3,867 5, ,134 yes ,9 19,45 15, ,438 yes 43, ,95 41,9 41,12 2,908 7, ,278 yes 6, ,265 5,71 5,712 0,531 9, Sb 0,207 yes 45, ,75 46,75 45,74 5,057 11, yes 0,19 7,435 7,047 5,834 82, ,318 yes 88, , ,41 12,32 14, ,638 yes 6, ,04 6,63 6,702 1,204 17, Se 0,479 yes 65, ,05 64,1 64,55 4,599 7, yes 51,5 50,9 42,9 16,03 37, ,828 yes 36, ,7 36,45 36,18 4,631 12, ,186 yes 8,6 25 8,4 8,305 8,663 1,002 11, Sn A2M 1,004 yes 25, ,25 25,65 25,08 3,346 13, L5M 5,606 H 34,7 35 0,66 36,1 34,65 4,869 14, V 0,291 yes 58, ,25 58,05 58,53 2,215 3, ,494 yes 45, ,75 45,1 43,98 3,665 8, ,162 yes 95, ,5 95,35 95,33 4, ,278 yes 10, ,1 10,65 10,78 0,6983 6, Zn 0,495 yes , ,7 12,69 5, ,751 yes , ,7 31,97 4, ,299 yes ,3 153,9 7,502 4, ,268 yes 37, , ,57 5,083 13, Outlier test failed: C Cohcran, G1 Grubbs(1outlier algorithm), G2 Grubbs(2outliers algorithm), H Hampel, M manual SYKE Interlaboratory comparison test 3/2011

37 35 LIITE APPENDIX 7 / 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 1,513 yes ,9 47,52 6, ,569 yes , ,087 yes , ,3 40,48 9, ,040 H ,5 124,5 13,69 10, As 0,970 yes 85, ,65 83,45 83,74 5,423 6, ,103 yes 4, ,275 3,98 3,887 1,027 26, ,155 yes , ,4 15,82 8, ,997 yes 7, ,46 7,345 7,291 0, , Cd 0,246 yes 9, ,92 9,7 9,573 0,7089 7, ,914 yes ,4 34,21 4,308 12, ,991 yes 64, ,8 64,4 64,67 3,481 5, ,470 yes 5, ,6 5,285 5,197 0,4364 8, Co 0,197 yes 9, ,2 10,1 9,803 1,515 15, ,567 H 52, , ,36 2,647 5, ,017 H 53, ,50 52,4 53,41 3,604 6, ,288 H 13, ,57 13,2 13,28 0,805 6, Cr 1,050 yes 45, ,3 45,4 45,73 2,523 5, ,739 yes 46, ,7 45,23 44,11 7,983 18, ,970 yes , ,8 7,89 5, ,966 yes 13, ,85 13,95 13,91 0,7707 5, Cu 8,403 H 71, ,4 71,85 71,25 4,565 6, ,043 yes , ,5 31,44 10, ,785 H , ,7 11, H 8,91 20 <100 9,03 8,957 1,015 11, Fe 0,663 yes ,3 681,5 682,6 24,96 3, ,041 yes , ,295 yes ,5 664,8 35,53 5, ,969 yes , ,3 52,41 6, Hg A1Hg 1,890 yes 0, ,665 0,8145 0,8106 0, , L5M 2,023 yes 0, ,4005 0,5965 0,5919 0, , T4Hg 0,140 yes 3, ,86 3,79 3,772 0,3658 9, Mn 0,065 yes , ,1 8,528 4, ,096 yes ,4 19,17 4, ,370 yes , ,6 5,244 4, ,732 yes , ,9 5,161 4, ,030 yes ,9 467, ,75 5, Ni 0,990 yes 48, ,7 48,45 48,19 3,004 6, ,518 yes ,9 25,6 25,21 5,143 20, ,918 yes , ,2 6,365 5, ,346 yes 10, ,04 10,35 10,35 1,155 11, Pb 1,884 yes 66, ,5 66,78 66,28 3,867 5, ,466 yes , ,9 19,45 15, ,273 yes 43, ,1 41,9 41,12 2,908 7, ,888 yes 6, ,268 5,71 5,712 0,531 9, Zn 0,163 yes , ,7 12,69 5, ,159 yes , ,7 31,97 4, ,253 yes ,1 154,3 153,9 7,502 4, H 37,3 20 < ,57 5,083 13, Outlier test failed: C Cohcran, G1 Grubbs(1outlier algorithm), G2 Grubbs(2outliers algorithm), H Hampel, M manual SYKE Interlaboratory comparison test 3/2011

38 LIITE 7 / 8 36 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 10 Al 0,294 yes ,9 47,52 6, yes ,7 6, ,151 yes ,5 394, ,87 6, ,560 yes ,5 121,5 124,5 13,69 10, As 0,497 yes 85, ,1 83,45 83,74 5,423 6, yes 5,65 5,65 5,509 0, , ,497 yes ,54 6, H 7,38 25 <15 7,345 7,291 0, , B 0,371 yes 70, ,7 72,5 71,74 8,309 11, yes 16,8 15,4 15,2 2,881 18, ,535 yes ,5 11,85 6, ,426 yes ,95 95,3 95,18 9,791 10, Cd 0,219 yes 9, ,9 9,7 9,573 0,7089 7, ,399 yes 33, ,15 33,1 33,82 1,974 5, ,093 yes 64, ,9 64,4 64,67 3,481 5, ,077 C 5, ,2 5,285 5,197 0,4364 8, Co 0,140 yes 35, ,05 35,27 35,38 1,805 5, ,437 yes 10,3 20 9,85 10,53 10,19 0,965 9, ,287 yes 52, , ,36 2,647 5, ,003 yes 13, ,3 13,2 13,28 0,805 6, Cr 0,722 yes 45, ,35 45,4 45,73 2,523 5, ,231 yes 54, ,85 54,45 52,88 4,893 9, ,224 yes ,5 132,4 134,2 7,154 5, ,240 yes 13, ,15 13,95 13,91 0,7707 5, Cu 0,392 yes 71, ,8 71,85 71,25 4,565 6, ,335 yes ,5 317,6 16,5 5, ,000 yes ,7 11, ,213 yes 8, ,1 9,03 8,957 1,015 11, Fe 0,657 yes ,5 681,5 682,6 24,96 3, yes , ,827 yes ,5 664,5 664,8 35,53 5, ,191 yes , ,3 52,41 6, Hg A1Hg 1,037 yes 0, ,735 0,8145 0,8106 0, , L5M 0,018 yes 0, ,622 0,5965 0,5919 0, , T4Hg 0,558 yes 3, ,98 3,79 3,772 0,3658 9, Mn 0,467 yes ,1 8,528 4, ,913 yes ,5 427,5 431,2 17, ,741 yes ,6 5,244 4, ,260 yes , ,75 5, Mo 0,403 yes 47, ,05 45,5 45,75 1,61 3, ,081 yes 37, ,4 37,2 35,88 2,958 8, ,392 yes ,5 3,982 3, ,046 yes 28, ,8 29,2 29,15 1,396 4, Ni 0,299 yes 48, ,95 48,45 48,19 3,004 6, ,000 yes 28, ,7 28,7 28,71 2,54 8, ,545 yes ,2 6,365 5, ,096 yes 10, ,3 10,35 10,35 1,155 11, Pb 0,078 yes 66, ,05 66,78 66,28 3,867 5, ,318 yes ,5 124,3 14,77 11, ,389 yes 43, ,25 41,9 41,12 2,908 7, H 6, <15 5,71 5,712 0,531 9, Sb 0,710 yes 45, ,05 46,75 45,74 5,057 11, ,108 yes 18, ,5 18,2 18,92 2,045 10, ,172 yes 88, ,41 12,32 14, H 6,52 25 <15 6,63 6,702 1,204 17, Se 0,347 yes 65, ,7 64,1 64,55 4,599 7, yes 59,85 56,05 56,42 2,871 5, ,734 yes 36, ,45 36,45 36,18 4,631 12, H 8,6 25 <15 8,305 8,663 1,002 11, Sn A2M 1,052 yes 25, ,4 25,65 25,08 3,346 13, L5M 0,766 yes 34, ,35 36,1 34,65 4,869 14, V 0,856 yes 58, ,9 58,05 58,53 2,215 3, yes 46,55 46,1 46,28 5,17 11, ,224 yes 95, ,8 95,35 95,33 4, ,370 yes 10, ,4 10,65 10,78 0,6983 6, Zn 0,087 yes , ,7 12,69 5, ,180 yes ,5 704, ,18 6, Outlier test failed: C Cohcran, G1 Grubbs(1outlier algorithm), G2 Grubbs(2outliers algorithm), H Hampel, M manual SYKE Interlaboratory comparison test 3/2011

39 37 LIITE APPENDIX 7 / 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 0,130 yes ,3 153,9 7,502 4, Laboratory 10 Zn 0,402 yes 37, , ,57 5,083 13, Laboratory 11 Hg A1Hg 4,939 H 0, ,415 0,8145 0,8106 0, , L5M 3,041 yes 0, ,29 0,5965 0,5919 0, , T4Hg 1,449 yes 3, ,405 3,79 3,772 0,3658 9, Laboratory 12 Al 0,280 yes ,9 47,52 6, LT5 yes , ,310 yes , ,87 6, ,119 yes , ,3 40,48 9, ,160 yes ,5 121,5 124,5 13,69 10, As 0,504 yes 85, ,15 83,45 83,74 5,423 6, LT5 yes 5,295 5,28 5,287 0, , ,697 yes ,54 6, ,161 yes , ,4 15,82 8, ,607 yes 7, ,94 7,345 7,291 0, , B 2,939 yes 70, ,7 72,5 71,74 8,309 11, LT5 yes 23,2 40,38 40,46 19,93 49, ,925 yes ,5 11,85 6, yes 146, ,6 21,5 11, ,263 yes ,5 95,3 95,18 9,791 10, Cd 1,040 yes 9, ,5 9,7 9,573 0,7089 7, LT5 yes 33,75 32,09 32,33 1,701 5, ,882 yes 64, ,45 64,4 64,67 3,481 5, ,323 yes ,55 65,75 65,08 4,367 6, ,838 yes 5, ,495 5,285 5,197 0,4364 8, Co 0,279 yes 35, ,3 35,27 35,38 1,805 5, LT5 yes 11,75 10,9 10,95 0,9327 8, ,919 yes 52, , ,36 2,647 5, ,424 yes 53, ,7 52,4 53,41 3,604 6, ,752 yes 13, ,05 13,2 13,28 0,805 6, Cr 0,284 yes 45, ,05 45,4 45,73 2,523 5, LT5 yes 62,05 53,52 54,33 9,018 16, ,224 yes ,5 132,4 134,2 7,154 5, ,895 yes ,8 7,89 5, ,240 yes 13, ,15 13,95 13,91 0,7707 5, Cu 0,728 yes 71, ,85 71,25 4,565 6, LT5 yes ,1 313,7 9,769 3, ,091 yes ,7 11, ,833 yes ,5 153,5 151,8 7,476 4, ,404 yes 8, ,27 9,03 8,957 1,015 11, Fe 0,482 yes ,5 681,5 682,6 24,96 3, LT5 yes , ,241 yes ,5 664,5 664,8 35,53 5, ,098 yes ,7 43,35 6, ,265 yes ,3 52,41 6, Hg A1Hg 0,854 yes 0, ,75 0,8145 0,8106 0, , L5M 1,000 yes 0, ,7285 0,5965 0,5919 0, , T4Hg 0,454 yes 3, ,95 3,79 3,772 0,3658 9, Mn 0,514 yes , ,1 8,528 4, LT5 yes 483,5 435,7 436,7 54,1 12, ,093 yes , ,6 5,244 4, ,339 yes , ,9 5,161 4, ,289 yes , ,75 5, Mo 0,722 yes 47, ,4 45,5 45,75 1,61 3, LT5 yes 40,7 32,6 32,89 9,026 27, ,196 yes ,5 3,982 3, ,736 yes ,8 107,5 105,5 5,635 5, ,138 yes 28, ,6 29,2 29,15 1,396 4, Ni 0,041 yes 48, ,3 48,45 48,19 3,004 6, LT5 yes 31,9 27,37 27,65 4,932 17, ,091 yes , ,2 6,365 5, ,649 yes , ,4 7,009 6, ,192 yes 10, ,6 10,35 10,35 1,155 11, Pb 0,841 yes 66, ,6 66,78 66,28 3,867 5, Outlier test failed: C Cohcran, G1 Grubbs(1outlier algorithm), G2 Grubbs(2outliers algorithm), H Hampel, M manual SYKE Interlaboratory comparison test 3/2011

40 LIITE 7 / 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 LT5 yes ,4 121,5 11,29 9, Laboratory 12 Pb 0,389 yes 43, ,25 41,9 41,12 2,908 7, ,622 yes 42, ,25 42,75 43,47 5,069 11, ,776 yes 6, ,78 5,71 5,712 0,531 9, Sb 2,020 yes 45, ,05 46,75 45,74 5,057 11, LT5 yes 19,95 11,79 12,01 9,176 76, ,581 yes 88, , ,41 12,32 14, ,459 yes 90, ,2 92,3 90,14 4,332 4, ,043 yes 6, ,555 6,63 6,702 1,204 17, Se 1,458 yes 65, ,55 64,1 64,55 4,599 7, LT5 yes 67,1 50,25 50,63 19,03 37, ,803 yes 36, ,45 36,18 4,631 12, ,350 yes ,6 32,7 31,76 4,941 15, ,791 yes 8,6 25 9,45 8,305 8,663 1,002 11, Sn A2M 1,753 yes 25, ,6 25,65 25,08 3,346 13, L5M 0,239 yes 34, ,15 36,1 34,65 4,869 14, V 0,411 yes 58, ,6 58,05 58,53 2,215 3, LT5 yes 53,3 45,77 45,94 8,505 18, ,420 yes 95, ,2 95,35 95,33 4, ,381 yes 96, ,55 95,6 96,58 4,505 4, ,694 yes 10, ,55 10,65 10,78 0,6983 6, Zn 1,252 yes , ,7 12,69 5, LT5 yes 751,5 694,3 695,1 65,48 9, ,753 yes ,5 154,3 153,9 7,502 4, ,789 C ,3 152,9 9,046 5, ,657 yes 37, , ,57 5,083 13, Laboratory 13 Al 1,008 yes ,9 47,52 6, As 1,529 yes 85, ,05 83,45 83,74 5,423 6, ,000 yes ,54 6, Cd 0,835 yes 9, ,35 9,7 9,573 0,7089 7, ,619 yes 64, ,6 64,4 64,67 3,481 5, ,593 yes 5, ,4 5,285 5,197 0,4364 8, Cr 2,538 yes 45, ,9 45,4 45,73 2,523 5, ,440 yes ,6 132,4 134,2 7,154 5, ,624 yes 13, ,25 13,95 13,91 0,7707 5, Cu 1,443 yes 71, ,25 71,85 71,25 4,565 6, ,648 yes ,7 11, ,685 yes 8, ,3 9,03 8,957 1,015 11, Fe 0,949 yes ,5 681,5 682,6 24,96 3, ,511 yes ,5 664,5 664,8 35,53 5, ,874 yes , ,3 52,41 6, Hg A1Hg 0,250 yes 0, ,7995 0,8145 0,8106 0, , T4Hg 0,070 yes 3, ,84 3,79 3,772 0,3658 9, Mn 1,126 yes , ,1 8,528 4, ,963 yes , ,6 5,244 4, ,463 yes ,3 467, ,75 5, Ni 1,588 yes 48, ,8 48,45 48,19 3,004 6, ,827 yes , ,2 6,365 5, ,385 yes 10, ,35 10,35 1,155 11, Pb 0,656 yes 66, ,6 66,78 66,28 3,867 5, ,224 yes 43, ,25 41,9 41,12 2,908 7, Zn 0,285 yes , ,7 12,69 5, ,766 yes ,9 154,3 153,9 7,502 4, ,697 yes 37, , ,57 5,083 13, Outlier test failed: C Cohcran, G1 Grubbs(1outlier algorithm), G2 Grubbs(2outliers algorithm), H Hampel, M manual SYKE Interlaboratory comparison test 3/2011

41 39 LIITE APPENDIX 7 / 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 0,308 yes ,9 47,52 6, ,297 yes , ,084 yes ,5 394, ,87 6, ,256 yes ,3 40,48 9, ,080 yes ,5 121,5 124,5 13,69 10, As 0,481 yes 85, ,8 83,45 83,74 5,423 6, ,166 yes 4, ,11 3,98 3,887 1,027 26, ,697 yes ,54 6, ,363 yes , ,4 15,82 8, ,108 yes 7, ,28 7,345 7,291 0, , B H 70,1 20 <100 72,5 71,74 8,309 11, ,9 30 <40 17,7 15,86 4,146 26, ,160 yes , ,5 11,85 6, yes ,6 21,5 11, H <100 95,3 95,18 9,791 10, Cd 0,219 yes 9, ,9 9,7 9,573 0,7089 7, ,480 yes ,9 35,4 34,21 4,308 12, ,635 yes 64, ,65 64,4 64,67 3,481 5, ,831 yes ,05 65,75 65,08 4,367 6, ,554 yes 5, ,385 5,285 5,197 0,4364 8, Co 0,335 yes 35, ,2 35,27 35,38 1,805 5, ,402 yes 9, ,45 10,1 9,803 1,515 15, ,785 yes 52, , ,36 2,647 5, ,524 yes 53, ,3 52,4 53,41 3,604 6, ,100 yes 13, ,2 13,2 13,28 0,805 6, Cr 0,109 yes 45, ,45 45,4 45,73 2,523 5, ,263 yes 46, ,75 45,23 44,11 7,983 18, ,373 yes ,5 132,4 134,2 7,154 5, ,298 yes ,8 7,89 5, ,336 yes 13, ,25 13,95 13,91 0,7707 5, Cu 0,280 yes 71, ,4 71,85 71,25 4,565 6, ,230 yes ,5 31,44 10, ,091 yes ,7 11, ,088 yes ,5 151,8 7,476 4, ,578 yes 8, ,395 9,03 8,957 1,015 11, Fe 0,029 yes ,5 682,6 24,96 3, ,534 yes , ,376 yes ,5 664,5 664,8 35,53 5, ,599 yes , ,7 43,35 6, ,233 yes ,3 52,41 6, Hg A1Hg 0,348 yes 0, ,8485 0,8145 0,8106 0, , L5M 0,415 yes 0, ,575 0,5965 0,5919 0, , T4Hg 1,815 yes 3, ,34 3,79 3,772 0,3658 9, Mn 0,327 yes , ,1 8,528 4, ,252 yes ,4 19,17 4, ,278 yes , ,6 5,244 4, ,357 yes ,9 5,161 4, ,087 yes , ,75 5, Mo 0,849 yes 47, ,1 45,5 45,75 1,61 3, ,147 yes 30, ,1 31,1 30,84 4,328 14, ,098 yes , ,5 3,982 3, ,038 yes ,5 107,5 105,5 5,635 5, ,300 yes 28, ,55 29,2 29,15 1,396 4, Ni 0,103 yes 48, ,45 48,19 3,004 6, ,062 yes ,3 25,6 25,21 5,143 20, ,182 yes , ,2 6,365 5, ,885 yes , ,4 7,009 6, ,457 yes 10,4 20 9,925 10,35 10,35 1,155 11, Pb 0,641 yes 66, ,65 66,78 66,28 3,867 5, ,346 yes , ,9 19,45 15, ,588 yes 43, ,6 41,9 41,12 2,908 7, ,082 yes 42, ,25 42,75 43,47 5,069 11, ,536 yes 6, ,43 5,71 5,712 0,531 9, Sb 0,983 yes 45, ,3 46,75 45,74 5,057 11, yes 13,95 7,435 7,047 5,834 82, ,599 yes 88, , ,41 12,32 14, ,636 yes 90, ,4 92,3 90,14 4,332 4, Outlier test failed: C Cohcran, G1 Grubbs(1outlier algorithm), G2 Grubbs(2outliers algorithm), H Hampel, M manual SYKE Interlaboratory comparison test 3/2011

42 LIITE 7 / 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 0,221 yes 6, ,7 6,63 6,702 1,204 17, Laboratory 14 Se 0,734 yes 65, ,8 64,1 64,55 4,599 7, yes 52,45 50,9 42,9 16,03 37, ,845 yes 36, ,05 36,45 36,18 4,631 12, ,087 yes ,35 32,7 31,76 4,941 15, ,572 yes 8,6 25 7,985 8,305 8,663 1,002 11, V 0,702 yes 58, ,35 58,05 58,53 2,215 3, ,099 yes 45, ,05 45,1 43,98 3,665 8, ,098 yes 95, ,9 95,35 95,33 4, ,332 yes 96, ,9 95,6 96,58 4,505 4, ,370 yes 10, ,4 10,65 10,78 0,6983 6, Zn 0,116 yes ,7 12,69 5, ,485 yes , ,7 31,97 4, ,000 yes ,3 153,9 7,502 4, ,592 yes ,5 153,3 152,9 9,046 5, ,335 yes 37, , ,57 5,083 13, Laboratory 15 Hg Laboratory As Cd Co Cr Cu Mn Ni Pb Sb Zn A1Hg 0,829 yes 0, ,888 0,8145 0,8106 0, , T4Hg 6,496 H 3, ,681 3,79 3,772 0,3658 9, ,598 yes 85, ,75 83,45 83,74 5,423 6, ,194 yes ,54 6, ,358 yes 7, ,71 7,345 7,291 0, , ,848 yes 9, ,39 9,7 9,573 0,7089 7, ,130 yes 64, ,95 64,4 64,67 3,481 5, ,734 yes 5, ,11 5,285 5,197 0,4364 8, ,117 yes 35, ,8 35,27 35,38 1,805 5, ,881 yes 52, , ,36 2,647 5, ,652 yes 13, ,95 13,2 13,28 0,805 6, ,510 yes 45, ,15 45,4 45,73 2,523 5, ,075 yes ,5 132,4 134,2 7,154 5, ,288 yes 13, ,6 13,95 13,91 0,7707 5, ,056 H 71, ,35 71,85 71,25 4,565 6, ,183 yes ,7 11, ,347 yes 8, ,11 9,03 8,957 1,015 11, ,402 yes ,1 8,528 4, ,231 yes , ,6 5,244 4, ,193 yes , ,75 5, ,361 yes 48, ,25 48,45 48,19 3,004 6, ,182 yes , ,2 6,365 5, ,048 yes 10, ,35 10,35 10,35 1,155 11, ,033 yes 66, ,78 66,28 3,867 5, ,313 yes 43, ,5 41,9 41,12 2,908 7, ,441 yes 6, ,34 5,71 5,712 0,531 9, ,271 yes 45, ,4 46,75 45,74 5,057 11, ,722 yes 88, , ,41 12,32 14, ,902 yes 6, ,7 6,63 6,702 1,204 17, ,204 yes , ,7 12,69 5, ,234 yes ,5 154,3 153,9 7,502 4, H 37,3 20 < ,57 5,083 13, Outlier test failed: C Cohcran, G1 Grubbs(1outlier algorithm), G2 Grubbs(2outliers algorithm), H Hampel, M manual SYKE Interlaboratory comparison test 3/2011

43 41 LIITE APPENDIX 7 / 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 17 Al 0,070 yes ,9 47,52 6, yes ,7 6, ,117 yes ,5 394, ,87 6, ,360 yes ,5 121,5 124,5 13,69 10, As 0,241 yes 85, ,35 83,45 83,74 5,423 6, ,886 yes ,54 6, ,791 yes 7, ,65 7,345 7,291 0, , B 0,442 yes 70, ,2 72,5 71,74 8,309 11, yes 18,45 15,4 15,2 2,881 18, ,160 yes , ,5 11,85 6, ,410 yes ,1 95,3 95,18 9,791 10, Cd 0,945 yes 9, ,05 9,7 9,573 0,7089 7, ,399 yes 33, ,45 33,1 33,82 1,974 5, ,238 yes 64, ,6 64,4 64,67 3,481 5, ,954 yes 5, ,8 5,285 5,197 0,4364 8, Co 1,285 yes 35, ,5 35,27 35,38 1,805 5, ,097 yes 10, ,4 10,53 10,19 0,965 9, ,345 yes 52, , ,36 2,647 5, ,752 yes 13, ,55 13,2 13,28 0,805 6, Cr 0,919 yes 45, ,6 45,4 45,73 2,523 5, ,111 yes 54, ,7 54,45 52,88 4,893 9, ,522 yes ,5 132,4 134,2 7,154 5, ,240 yes 13, ,15 13,95 13,91 0,7707 5, Cu 1,919 yes 71, ,55 71,85 71,25 4,565 6, ,237 yes ,5 322,5 317,6 16,5 5, ,142 yes , ,7 11, ,213 yes 8, ,1 9,03 8,957 1,015 11, Fe 0,146 yes ,5 682,6 24,96 3, Hg A1Hg 0,976 C 0, ,9 0,8145 0,8106 0, , L5M 0,876 yes 0, ,525 0,5965 0,5919 0, , T4Hg 0,768 yes 3, ,6 3,79 3,772 0,3658 9, Mn 1,355 yes , ,1 8,528 4, ,294 yes ,5 427,5 431,2 17, ,741 yes ,6 5,244 4, ,212 yes , ,75 5, Mo 1,805 yes 47, ,85 45,5 45,75 1,61 3, ,431 yes 37, ,7 37,2 35,88 2,958 8, ,108 yes , ,5 3,982 3, ,200 yes 28, ,3 29,2 29,15 1,396 4, Ni 0,010 yes 48, ,45 48,45 48,19 3,004 6, ,000 yes 28, ,7 28,7 28,71 2,54 8, ,909 yes ,2 6,365 5, ,442 yes 10, ,9 10,35 10,35 1,155 11, Pb 1,345 yes 66, ,3 66,78 66,28 3,867 5, ,254 yes ,5 124,3 14,77 11, ,124 yes 43, ,85 41,9 41,12 2,908 7, ,710 yes 6, ,35 5,71 5,712 0,531 9, Sb 1,659 yes 45, ,2 46,75 45,74 5,057 11, ,387 yes 18, ,7 18,2 18,92 2,045 10, ,453 yes 88, , ,41 12,32 14, ,926 yes 6, ,95 6,63 6,702 1,204 17, Se 0,693 yes 65, ,1 64,55 4,599 7, yes 52,6 56,05 56,42 2,871 5, ,346 yes 36, ,35 36,45 36,18 4,631 12, ,279 yes 8,6 25 8,3 8,305 8,663 1,002 11, Sn A2M 0,813 yes 25, ,55 25,65 25,08 3,346 13, V 0,154 yes 58, ,95 58,05 58,53 2,215 3, C 63,8 46,1 46,28 5,17 11, ,147 yes 95, ,25 95,35 95,33 4, ,139 yes 10, ,65 10,65 10,78 0,6983 6, Zn 0,640 yes ,7 12,69 5, ,418 yes , ,18 6, ,104 yes ,5 154,3 153,9 7,502 4, ,046 yes 37, , ,57 5,083 13, Outlier test failed: C Cohcran, G1 Grubbs(1outlier algorithm), G2 Grubbs(2outliers algorithm), H Hampel, M manual SYKE Interlaboratory comparison test 3/2011

44 LIITE 7 / 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 18 Al 0,616 yes ,9 47,52 6, ,804 yes , ,504 yes , ,87 6, ,480 yes ,5 124,5 13,69 10, As 0,116 yes 85, ,65 83,45 83,74 5,423 6, ,914 yes 4, ,46 3,98 3,887 1,027 26, ,846 yes , ,54 6, ,672 yes 7, ,345 7,291 0, , B 0,699 yes 70, ,5 71,74 8,309 11, ,738 yes 16,9 30 9,96 17,7 15,86 4,146 26, ,963 yes ,5 11,85 6, ,579 yes ,5 95,3 95,18 9,791 10, Cd 0,103 yes 9, ,665 9,7 9,573 0,7089 7, ,343 yes ,75 35,4 34,21 4,308 12, ,031 yes 64, ,7 64,4 64,67 3,481 5, ,761 yes 5, ,465 5,285 5,197 0,4364 8, Co 0,279 yes 35, ,3 35,27 35,38 1,805 5, ,504 yes 9, ,08 10,1 9,803 1,515 15, ,686 yes 52, , ,36 2,647 5, ,003 yes 13, ,3 13,2 13,28 0,805 6, Cr 0,766 yes 45, ,45 45,4 45,73 2,523 5, ,201 yes 46, ,45 45,23 44,11 7,983 18, ,761 yes ,5 132,4 134,2 7,154 5, ,295 yes 13, ,25 13,95 13,91 0,7707 5, Cu 2,017 yes 71, ,6 71,85 71,25 4,565 6, ,197 yes ,5 31,44 10, ,826 yes ,7 11, ,769 yes 8, ,595 9,03 8,957 1,015 11, Fe 1,489 yes ,5 682,6 24,96 3, ,494 yes , ,587 yes ,5 664,5 664,8 35,53 5, ,275 yes , ,3 52,41 6, Hg A1Hg 1,280 yes 0, ,925 0,8145 0,8106 0, , L5M 1,774 C 0, ,8125 0,5965 0,5919 0, , T4Hg 1,815 yes 3, ,34 3,79 3,772 0,3658 9, Mn 0,187 yes ,1 8,528 4, ,861 H , ,4 19,17 4, ,463 yes , ,6 5,244 4, ,548 yes , ,75 5, Mo 0,679 yes 47, ,5 45,5 45,75 1,61 3, ,026 yes 30, ,8 31,1 30,84 4,328 14, ,588 yes ,5 3,982 3, ,484 yes 28, ,95 29,2 29,15 1,396 4, Ni 0,072 yes 48, ,85 48,45 48,19 3,004 6, ,407 yes ,25 25,6 25,21 5,143 20, ,000 yes , ,2 6,365 5, ,433 yes 10, ,85 10,35 10,35 1,155 11, Pb 0,416 yes 66, ,4 66,78 66,28 3,867 5, ,994 yes , ,9 19,45 15, ,466 yes 43, ,9 41,12 2,908 7, ,634 yes 6, ,385 5,71 5,712 0,531 9, Sb 0,568 yes 45, ,2 46,75 45,74 5,057 11, ,795 yes 88, , ,41 12,32 14, ,503 yes 6, ,295 6,63 6,702 1,204 17, Se 0,999 yes 65, ,3 64,1 64,55 4,599 7, yes 50,1 50,9 42,9 16,03 37, ,277 yes 36, ,1 36,45 36,18 4,631 12, ,935 yes 8,6 25 9,605 8,305 8,663 1,002 11, Sn A2M 1,020 yes 25, ,9 25,65 25,08 3,346 13, V 1,301 yes 58, ,2 58,05 58,53 2,215 3, ,890 yes 45, ,9 45,1 43,98 3,665 8, ,303 yes 95, ,5 95,35 95,33 4, ,972 yes 10, ,85 10,65 10,78 0,6983 6, Zn 0,058 yes ,7 12,69 5, ,156 H , ,7 31,97 4, ,325 yes ,5 154,3 153,9 7,502 4, ,121 yes 37, , ,57 5,083 13, Outlier test failed: C Cohcran, G1 Grubbs(1outlier algorithm), G2 Grubbs(2outliers algorithm), H Hampel, M manual SYKE Interlaboratory comparison test 3/2011

45 43 LIITE APPENDIX 7 / 15 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 19 Al 4,006 H ,9 47,52 6, ,521 yes , H < ,3 40,48 9, Cd H 9,74 15 <15 9,7 9,573 0,7089 7, ,075 yes ,3 35,4 34,21 4,308 12, ,749 yes ,65 65,75 65,08 4,367 6, Co 1,889 yes 9, ,3 10,1 9,803 1,515 15, H 53,4 15 <80 52,4 53,41 3,604 6, Cr 0,306 C 46, ,05 45,23 44,11 7,983 18, H < ,8 7,89 5, Cu 3,193 yes 71, ,8 71,85 71,25 4,565 6, ,393 yes , ,5 31,44 10, ,044 yes ,5 153,5 151,8 7,476 4, Fe 1,051 yes ,5 682,6 24,96 3, ,956 yes , ,589 yes ,7 43,35 6, Hg A1Hg 0,195 yes 0, ,804 0,8145 0,8106 0, , L5M 0,783 yes 0, ,535 0,5965 0,5919 0, , T4Hg 0,000 yes 3, ,82 3,79 3,772 0,3658 9, Mn 0,935 yes ,1 8,528 4, ,079 yes , ,4 19,17 4, ,893 yes ,9 5,161 4, Ni H 48,5 20 <80 48,45 48,19 3,004 6, ,358 yes ,5 25,6 25,21 5,143 20, ,732 yes , ,4 7,009 6, Pb H 66,79 10 <150 66,78 66,28 3,867 5, ,008 yes ,9 19,45 15, H 42,6 20 <150 42,75 43,47 5,069 11, Zn 1,019 yes , ,7 12,69 5, ,004 H , ,7 31,97 4, ,447 yes ,3 152,9 9,046 5, Laboratory 20 Al 0,273 yes , ,9 47,52 6, ,067 yes , ,87 6, ,440 yes ,5 121,5 124,5 13,69 10, As 0,644 yes 85, ,75 83,45 83,74 5,423 6, ,045 yes , ,54 6, H 7,38 25 <10 7,345 7,291 0, , B 1,027 yes 70, ,3 72,5 71,74 8,309 11, ,749 yes ,5 11,85 6, ,237 yes ,25 95,3 95,18 9,791 10, Cd 0,055 yes 9, ,7 9,7 9,573 0,7089 7, ,882 yes 64, ,75 64,4 64,67 3,481 5, ,567 yes 5, ,95 5,285 5,197 0,4364 8, Co 0,587 yes 35, ,75 35,27 35,38 1,805 5, ,402 yes 52, , ,36 2,647 5, ,203 yes 13, ,1 13,2 13,28 0,805 6, Cr 0,503 yes 45, ,55 45,4 45,73 2,523 5, ,970 yes ,5 132,4 134,2 7,154 5, ,815 yes 13, ,05 13,95 13,91 0,7707 5, Cu 0,616 yes 71, ,2 71,85 71,25 4,565 6, ,685 yes , ,7 11, ,123 yes 8, ,8 9,03 8,957 1,015 11, Fe 1,007 yes ,5 681,5 682,6 24,96 3, ,827 yes ,5 664,5 664,8 35,53 5, ,707 yes , ,3 52,41 6, Mn 0,047 yes , ,1 8,528 4, ,093 yes , ,6 5,244 4, ,332 yes ,5 467, ,75 5, Mo 0,573 yes 47, ,75 45,5 45,75 1,61 3, ,539 yes , ,5 3,982 3, ,531 C 28, ,75 29,2 29,15 1,396 4, Ni 0,268 yes 48, ,2 48,45 48,19 3,004 6, ,818 yes , ,2 6,365 5, ,058 yes 10,4 20 9,3 10,35 10,35 1,155 11, Pb 0,827 yes 66, ,55 66,78 66,28 3,867 5, ,374 yes 43, ,3 41,9 41,12 2,908 7, Outlier test failed: C Cohcran, G1 Grubbs(1outlier algorithm), G2 Grubbs(2outliers algorithm), H Hampel, M manual SYKE Interlaboratory comparison test 3/2011

46 LIITE 7 / 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 6, <8 5,71 5,712 0,531 9, Laboratory 20 Sb 0,666 yes 45, ,85 46,75 45,74 5,057 11, ,059 yes 88, , ,41 12,32 14, H 6,52 25 <10 6,63 6,702 1,204 17, Se 0,764 yes 65, ,65 64,1 64,55 4,599 7, ,222 yes 36, ,3 36,45 36,18 4,631 12, ,000 yes 8, ,75 8,305 8,663 1,002 11, V 0,445 yes 58, ,1 58,05 58,53 2,215 3, ,609 yes 95, ,85 95,35 95,33 4, ,157 yes 10, ,05 10,65 10,78 0,6983 6, Zn 0,582 yes ,7 12,69 5, ,519 yes ,3 153,9 7,502 4, ,094 yes 37, , ,57 5,083 13, Laboratory 21 Al 0,203 yes , ,9 47,52 6, ,057 yes , yes ,7 6, ,470 yes , ,87 6, ,440 yes ,5 121,5 124,5 13,69 10, As 0,109 yes 85, ,2 83,45 83,74 5,423 6, ,737 yes 4, ,055 3,98 3,887 1,027 26, yes 5,115 5,65 5,509 0, , ,895 yes ,54 6, ,087 yes 7, ,46 7,345 7,291 0, , B 0,071 yes 70, ,6 72,5 71,74 8,309 11, ,933 yes 16, ,7 15,86 4,146 26, ,642 yes ,5 11,85 6, ,537 yes ,9 95,3 95,18 9,791 10, Cd 0,212 yes 9, ,895 9,7 9,573 0,7089 7, ,583 yes ,45 35,4 34,21 4,308 12, ,148 yes 33, ,3 33,1 33,82 1,974 5, ,836 yes 64, ,3 64,4 64,67 3,481 5, ,516 yes 5, ,37 5,285 5,197 0,4364 8, Co 0,670 yes 35, ,6 35,27 35,38 1,805 5, ,402 yes 9, ,45 10,1 9,803 1,515 15, ,534 yes 10, ,85 10,53 10,19 0,965 9, ,057 yes 52, , ,36 2,647 5, ,050 yes 13, ,25 13,2 13,28 0,805 6, Cr 0,635 yes 45, ,25 45,4 45,73 2,523 5, ,760 yes 46, ,25 45,23 44,11 7,983 18, ,065 yes 54, ,45 54,45 52,88 4,893 9, ,269 yes ,5 132,4 134,2 7,154 5, ,048 yes 13, ,85 13,95 13,91 0,7707 5, Cu 0,140 yes 71, ,9 71,85 71,25 4,565 6, ,738 yes , ,5 31,44 10, ,839 yes ,5 317,6 16,5 5, ,365 yes ,7 11, ,533 yes 8, ,385 9,03 8,957 1,015 11, Fe 0,759 yes ,5 682,6 24,96 3, ,788 yes , yes , ,602 yes ,5 664,8 35,53 5, ,300 yes ,3 52,41 6, Hg A1Hg 0,140 yes 0, ,8085 0,8145 0,8106 0, , L5M 0,576 yes 0, ,6825 0,5965 0,5919 0, , T4Hg 0,436 yes 3, ,695 3,79 3,772 0,3658 9, Mn 0,514 yes , ,1 8,528 4, ,221 yes ,4 19,17 4, ,247 yes ,5 431,2 17, ,093 yes , ,6 5,244 4, ,029 yes , ,75 5, Mo 1,062 yes 47, ,6 45,5 45,75 1,61 3, ,277 yes 30, ,6 31,1 30,84 4,328 14, ,067 yes 37, ,35 37,2 35,88 2,958 8, ,716 yes , ,5 3,982 3, ,208 yes 28, ,45 29,2 29,15 1,396 4, Ni 1,206 yes 48, ,65 48,45 48,19 3,004 6, Outlier test failed: C Cohcran, G1 Grubbs(1outlier algorithm), G2 Grubbs(2outliers algorithm), H Hampel, M manual SYKE Interlaboratory comparison test 3/2011

47 45 LIITE APPENDIX 7 / 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 0,840 yes ,4 25,6 25,21 5,143 20, Laboratory 21 Ni 0,871 yes 28, ,45 28,7 28,71 2,54 8, ,182 yes ,2 6,365 5, ,096 yes 10, ,5 10,35 10,35 1,155 11, Pb 0,527 yes 66, ,55 66,78 66,28 3,867 5, ,976 yes , ,9 19,45 15, ,825 yes ,5 124,3 14,77 11, ,267 yes 43, ,65 41,9 41,12 2,908 7, ,537 yes 6, ,89 5,71 5,712 0,531 9, Sb 0,218 yes 45, ,8 46,75 45,74 5,057 11, yes 10,45 7,435 7,047 5,834 82, ,473 yes 18, ,5 18,2 18,92 2,045 10, ,009 yes 88, , ,41 12,32 14, ,135 yes 6, ,63 6,63 6,702 1,204 17, Se 0,408 yes 65, ,4 64,1 64,55 4,599 7, yes 55,7 50,9 42,9 16,03 37, yes 57,2 56,05 56,42 2,871 5, ,593 yes 36, ,35 36,45 36,18 4,631 12, ,237 yes 8,6 25 8,345 8,305 8,663 1,002 11, Sn A2M 0,637 yes 25, ,1 25,65 25,08 3,346 13, L5M 1,449 yes 34, ,9 36,1 34,65 4,869 14, V 0,788 yes 58, ,1 58,05 58,53 2,215 3, ,088 yes 45, ,9 45,1 43,98 3,665 8, yes 46 46,1 46,28 5,17 11, ,490 yes 95, ,7 95,35 95,33 4, ,648 yes 10, ,1 10,65 10,78 0,6983 6, Zn 0,437 yes , ,7 12,69 5, ,276 yes , ,7 31,97 4, ,551 yes , ,18 6, ,390 yes ,3 153,9 7,502 4, ,308 yes 37, , ,57 5,083 13, Laboratory 22 Cd 1,684 yes 9, ,51 9,7 9,573 0,7089 7, ,223 yes 64, ,65 64,4 64,67 3,481 5, ,735 yes 5, ,885 5,285 5,197 0,4364 8, Cr 0,144 yes 45, ,37 45,4 45,73 2,523 5, ,276 yes ,5 132,4 134,2 7,154 5, ,494 yes 13, ,38 13,95 13,91 0,7707 5, Cu 1,078 yes 71, ,25 71,85 71,25 4,565 6, ,740 yes ,7 11, ,751 yes 8, ,35 9,03 8,957 1,015 11, Ni 0,756 yes 48, ,83 48,45 48,19 3,004 6, ,669 yes , ,2 6,365 5, ,841 yes 10,4 20 7,445 10,35 10,35 1,155 11, Pb 2,189 yes 66, ,1 66,78 66,28 3,867 5, ,097 yes 43, ,1 41,9 41,12 2,908 7, ,547 yes 6, ,885 5,71 5,712 0,531 9, Outlier test failed: C Cohcran, G1 Grubbs(1outlier algorithm), G2 Grubbs(2outliers algorithm), H Hampel, M manual SYKE Interlaboratory comparison test 3/2011

48 LIITE 7 / 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 23 Al As Cd Co Cr Cu Fe Mn Ni Pb Zn 0,140 yes ,9 47,52 6, ,094 yes , ,554 yes ,5 394, ,87 6, ,520 yes ,5 121,5 124,5 13,69 10, ,171 yes 85, ,45 83,74 5,423 6, ,993 yes 4, ,21 3,98 3,887 1,027 26, ,448 yes , ,54 6, ,259 yes , ,4 15,82 8, ,667 yes 7, ,765 7,345 7,291 0, , ,212 yes 9, ,585 9,7 9,573 0,7089 7, ,366 yes ,6 35,4 34,21 4,308 12, ,387 yes 64, ,85 64,4 64,67 3,481 5, ,851 yes ,15 65,75 65,08 4,367 6, ,271 yes 5, ,275 5,285 5,197 0,4364 8, ,486 yes 35, ,35 35,27 35,38 1,805 5, ,563 yes 9, ,65 10,1 9,803 1,515 15, ,245 yes 52, , ,36 2,647 5, ,587 yes 53, ,05 52,4 53,41 3,604 6, ,752 yes 13, ,55 13,2 13,28 0,805 6, ,138 yes 45, ,1 45,4 45,73 2,523 5, ,014 yes 46, ,8 45,23 44,11 7,983 18, ,970 yes ,5 132,4 134,2 7,154 5, ,970 yes , ,8 7,89 5, ,144 yes 13, ,75 13,95 13,91 0,7707 5, ,793 yes 71, ,85 71,25 4,565 6, ,246 yes , ,5 31,44 10, ,507 yes , ,7 11, ,570 yes ,5 153,5 151,8 7,476 4, ,453 yes 8, ,615 9,03 8,957 1,015 11, ,832 yes ,5 681,5 682,6 24,96 3, ,681 yes , ,165 yes ,5 664,5 664,8 35,53 5, ,766 yes ,7 43,35 6, ,017 yes ,3 52,41 6, ,561 yes ,1 8,528 4, ,504 yes ,4 19,17 4, ,463 yes , ,6 5,244 4, ,179 yes ,9 5,161 4, ,447 yes ,5 467, ,75 5, ,691 yes 48, ,15 48,45 48,19 3,004 6, ,136 yes ,55 25,6 25,21 5,143 20, ,091 yes , ,2 6,365 5, ,944 yes ,4 7,009 6, ,389 yes 10,4 20 9,995 10,35 10,35 1,155 11, ,374 yes 66, ,2 66,78 66,28 3,867 5, ,457 yes ,9 19,45 15, ,339 yes 43, ,15 41,9 41,12 2,908 7, ,035 yes 42, ,75 42,75 43,47 5,069 11, ,221 yes 6, ,575 5,71 5,712 0,531 9, ,146 yes , ,7 12,69 5, ,361 yes ,7 31,97 4, ,390 yes ,3 153,9 7,502 4, ,658 yes ,3 152,9 9,046 5, ,214 yes 37, , ,57 5,083 13, Outlier test failed: C Cohcran, G1 Grubbs(1outlier algorithm), G2 Grubbs(2outliers algorithm), H Hampel, M manual SYKE Interlaboratory comparison test 3/2011

49 47 LIITE APPENDIX 7 / 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 24 Cd Cr Cu Fe Mn Ni Pb Zn Laboratory 25 Co Cr Fe Zn Laboratory 26 Ni Laboratory 27 As Cd Cu Hg Ni Pb Zn A1Hg T4Hg 0,789 yes ,45 35,4 34,21 4,308 12, ,841 yes ,9 65,75 65,08 4,367 6, ,141 H 46, ,8 45,23 44,11 7,983 18, ,045 yes ,8 7,89 5, ,787 yes ,5 31,44 10, ,184 yes ,5 153,5 151,8 7,476 4, ,584 yes ,5 682,6 24,96 3, ,056 yes , ,934 yes , ,7 43,35 6, ,590 yes , ,3 52,41 6, ,421 yes , ,1 8,528 4, ,615 yes , ,4 19,17 4, ,161 yes , ,9 5,161 4, ,519 yes , ,75 5, ,988 yes ,6 25,21 5,143 20, ,000 C ,4 7,009 6, ,630 yes ,9 19,45 15, ,815 yes ,7 12,69 5, ,618 yes , ,7 31,97 4, ,789 yes ,3 152,9 9,046 5, ,300 H 35, ,27 35,38 1,805 5, ,223 yes 53, ,5 52,4 53,41 3,604 6, ,090 H 45, ,5 45,4 45,73 2,523 5, ,388 yes ,8 7,89 5, ,788 yes ,5 682,6 24,96 3, ,334 yes ,7 43,35 6, ,466 yes ,7 12,69 5, ,066 yes ,5 153,3 152,9 9,046 5, ,273 yes , ,2 6,365 5, ,016 yes 85, ,45 83,74 5,423 6, ,199 yes ,54 6, ,268 yes 7, ,55 7,345 7,291 0, , ,151 yes 9, ,85 9,7 9,573 0,7089 7, ,495 yes 64, ,4 64,67 3,481 5, ,438 yes 5, ,285 5,197 0,4364 8, ,308 yes 71, ,5 71,85 71,25 4,565 6, ,411 yes , ,7 11, ,685 yes 8, ,3 9,03 8,957 1,015 11, ,244 yes 0, ,8 0,8145 0,8106 0, , ,628 yes 3, ,64 3,79 3,772 0,3658 9, ,206 yes 48, ,5 48,45 48,19 3,004 6, ,182 yes ,2 6,365 5, ,721 yes 10,4 20 9,65 10,35 10,35 1,155 11, ,362 yes 66, ,78 66,28 3,867 5, ,772 yes 43, ,9 41,12 2,908 7, ,298 yes 6, ,71 5,712 0,531 9, ,146 yes , ,7 12,69 5, ,584 yes ,5 154,3 153,9 7,502 4, ,483 yes 37, , ,57 5,083 13, Outlier test failed: C Cohcran, G1 Grubbs(1outlier algorithm), G2 Grubbs(2outliers algorithm), H Hampel, M manual SYKE Interlaboratory comparison test 3/2011

50 LIITE 7 / 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 0,938 yes ,9 47,52 6, yes ,7 6, ,922 yes , ,3 40,48 9, ,360 yes ,5 124,5 13,69 10, As 0,435 yes 85, ,1 83,45 83,74 5,423 6, yes 4,015 5,65 5,509 0, , ,347 yes ,4 15,82 8, H 7,38 25 <10 7,345 7,291 0, , B 0,556 yes 70, ,5 71,74 8,309 11, yes 13,9 15,4 15,2 2,881 18, yes 179, ,6 21,5 11, ,021 yes ,8 95,3 95,18 9,791 10, Cd 1,424 yes 9, ,7 9,7 9,573 0,7089 7, ,562 yes 33, ,9 33,1 33,82 1,974 5, ,267 yes ,3 65,75 65,08 4,367 6, ,083 yes 5, ,75 5,285 5,197 0,4364 8, Co 1,034 yes 35, ,95 35,27 35,38 1,805 5, ,777 yes 10, ,1 10,53 10,19 0,965 9, ,325 yes 53, ,7 52,4 53,41 3,604 6, ,100 yes 13, ,2 13,2 13,28 0,805 6, Cr 1,028 yes 45, ,35 45,4 45,73 2,523 5, ,268 yes 54, ,55 54,45 52,88 4,893 9, ,000 yes ,8 7,89 5, ,336 yes 13, ,55 13,95 13,91 0,7707 5, Cu 0,056 yes 71, ,2 71,85 71,25 4,565 6, ,273 yes ,5 322,5 317,6 16,5 5, ,175 yes ,5 151,8 7,476 4, ,907 yes 8, ,5 9,03 8,957 1,015 11, Fe 0,423 yes ,5 681,5 682,6 24,96 3, yes , ,295 yes ,7 43,35 6, ,025 yes , ,3 52,41 6, Hg A1Hg 1,402 yes 0, ,705 0,8145 0,8106 0, , L5M 1,350 yes 0, ,7665 0,5965 0,5919 0, , T4Hg 1,361 yes 3, ,43 3,79 3,772 0,3658 9, Mn 1,262 yes , ,1 8,528 4, ,278 yes ,5 431,2 17, ,161 yes , ,9 5,161 4, ,563 yes ,5 467, ,75 5, Mo 0,786 yes 47, ,25 45,5 45,75 1,61 3, ,512 yes 37, ,2 37,2 35,88 2,958 8, ,377 yes ,5 105,5 5,635 5, ,484 yes 28, ,85 29,2 29,15 1,396 4, Ni 0,041 yes 48, ,3 48,45 48,19 3,004 6, ,732 yes 28, ,55 28,7 28,71 2,54 8, ,944 yes ,4 7,009 6, ,865 yes 10, ,3 10,35 10,35 1,155 11, Pb 0,063 yes 66, ,78 66,28 3,867 5, ,191 yes ,5 124,3 14,77 11, ,305 yes 42, ,9 42,75 43,47 5,069 11, H 6, <10 5,71 5,712 0,531 9, Sb 0,393 yes 45, ,75 45,74 5,057 11, ,237 yes 18, ,05 18,2 18,92 2,045 10, ,326 yes 90, ,3 92,3 90,14 4,332 4, H 6,52 25 <10 6,63 6,702 1,204 17, Se 0,357 yes 65, ,15 64,1 64,55 4,599 7, yes 56,05 56,05 56,42 2,871 5, ,125 yes ,5 32,7 31,76 4,941 15, H 8,6 25 <20 8,305 8,663 1,002 11, Sn A2M 0,478 yes 25, ,6 25,65 25,08 3,346 13, L5M 0,321 yes 34, ,65 36,1 34,65 4,869 14, V 0,531 yes 58, ,85 58,05 58,53 2,215 3, yes 53,1 46,1 46,28 5,17 11, ,381 yes 96, ,05 95,6 96,58 4,505 4, H 10,8 20 <10 10,65 10,78 0,6983 6, Zn 0,437 yes , ,7 12,69 5, ,861 yes , ,18 6, Outlier test failed: C Cohcran, G1 Grubbs(1outlier algorithm), G2 Grubbs(2outliers algorithm), H Hampel, M manual SYKE Interlaboratory comparison test 3/2011

51 49 LIITE APPENDIX 7 / 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 Laboratory Zn Laboratory Al As Cd Co Cr Cu Fe Mn Ni Pb Zn Laboratory Cr Fe Ni Zn ,184 yes ,3 152,9 9,046 5, ,617 yes 37, ,57 5,083 13, ,399 yes , ,9 47,52 6, ,913 yes ,3 40,48 9, ,760 H ,5 121,5 124,5 13,69 10, ,723 yes 85, ,45 83,74 5,423 6, ,953 yes , ,4 15,82 8, ,725 yes 9, ,7 9,573 0,7089 7, ,641 yes ,75 65,08 4,367 6, ,141 yes 5, ,285 5,197 0,4364 8, ,788 yes 35, ,27 35,38 1,805 5, ,398 yes 53, ,4 53,41 3,604 6, ,704 yes 13, ,2 13,28 0,805 6, ,663 yes 45, ,5 45,4 45,73 2,523 5, ,015 yes , ,8 7,89 5, ,055 yes 13, ,95 13,91 0,7707 5, ,308 yes 71, ,5 71,85 71,25 4,565 6, ,351 yes ,5 151,8 7,476 4, ,460 yes 8, ,5 9,03 8,957 1,015 11, ,657 yes ,5 681,5 682,6 24,96 3, ,255 yes ,7 43,35 6, ,216 yes ,3 52,41 6, ,075 yes , ,1 8,528 4, ,804 yes , ,9 5,161 4, ,592 yes ,5 467, ,75 5, ,144 H 48, ,45 48,19 3,004 6, ,425 H , ,4 7,009 6, ,584 yes 66, ,5 66,78 66,28 3,867 5, ,972 C 42, ,75 43,47 5,069 11, ,921 yes ,7 12,69 5, ,895 yes ,3 152,9 9,046 5, ,064 yes 37, ,57 5,083 13, ,020 yes 45, ,6 45,4 45,73 2,523 5, ,045 yes ,4 134,2 7,154 5, ,423 yes ,5 681,5 682,6 24,96 3, ,030 yes ,5 664,8 35,53 5, ,361 yes 48, ,75 48,45 48,19 3,004 6, ,182 yes ,2 6,365 5, ,146 yes , ,7 12,69 5, ,390 yes ,3 153,9 7,502 4, Outlier test failed: C Cohcran, G1 Grubbs(1outlier algorithm), G2 Grubbs(2outliers algorithm), H Hampel, M manual SYKE Interlaboratory comparison test 3/2011

52 LIITE 7 / 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 As 0,186 yes 85, ,7 83,45 83,74 5,423 6, ,140 yes ,4 15,82 8, Cd 1,177 yes 9, ,6 9,7 9,573 0,7089 7, ,390 yes ,9 65,75 65,08 4,367 6, Co 0,419 yes 35, ,55 35,27 35,38 1,805 5, ,724 yes 53, ,3 52,4 53,41 3,604 6, Cr 0,197 yes 45, ,25 45,4 45,73 2,523 5, ,522 yes , ,8 7,89 5, Cu 0,420 yes 71, ,9 71,85 71,25 4,565 6, ,000 yes ,5 151,8 7,476 4, Fe 0,165 yes ,6 681,5 682,6 24,96 3, ,377 yes , ,7 43,35 6, Hg A1Hg 0,713 yes 0, ,8785 0,8145 0,8106 0, , T4Hg 0,080 yes 3, ,843 3,79 3,772 0,3658 9, Mn 1,299 yes , ,1 8,528 4, Ni 0,588 yes 48, ,35 48,45 48,19 3,004 6, ,885 yes , ,4 7,009 6, Pb 1,171 yes 66, ,7 66,78 66,28 3,867 5, ,305 yes 42, ,9 42,75 43,47 5,069 11, Se 0,418 yes 65, ,35 64,1 64,55 4,599 7, ,362 yes ,45 32,7 31,76 4,941 15, V 0,103 yes 58, ,7 58,05 58,53 2,215 3, ,561 yes 96, ,25 95,6 96,58 4,505 4, Zn 0,052 yes , ,7 12,69 5, ,276 yes ,1 153,3 152,9 9,046 5, Laboratory 32 Al 0,665 yes , ,9 47,52 6, ,714 yes , ,789 yes ,5 394, ,87 6, ,200 yes ,5 124,5 13,69 10, As 0,691 yes 85, ,45 83,45 83,74 5,423 6, ,01 30 <4 3,98 3,887 1,027 26, ,945 yes , ,54 6, H 7,38 25 <10 7,345 7,291 0, , B 1,049 yes 70, ,75 72,5 71,74 8,309 11, ,696 yes 16, ,2 17,7 15,86 4,146 26, ,765 yes , ,5 11,85 6, ,974 yes ,25 95,3 95,18 9,791 10, Cd 0,055 yes 9, ,7 9,7 9,573 0,7089 7, ,171 yes ,75 35,4 34,21 4,308 12, ,588 yes 64, ,5 64,4 64,67 3,481 5, H 5,17 15 <6 5,285 5,197 0,4364 8, Cr 0,153 yes 45, ,05 45,4 45,73 2,523 5, ,843 yes 46, ,9 45,23 44,11 7,983 18, ,746 yes ,4 134,2 7,154 5, ,432 yes 13, ,45 13,95 13,91 0,7707 5, Cu 0,770 yes 71, ,65 71,85 71,25 4,565 6, ,131 yes ,5 31,44 10, ,685 yes , ,7 11, ,807 yes 8, ,3 9,03 8,957 1,015 11, Fe 0,102 yes ,5 681,5 682,6 24,96 3, ,881 H , ,015 yes ,5 664,5 664,8 35,53 5, ,283 yes ,3 52,41 6, Mn 0,654 yes ,1 8,528 4, ,599 yes ,4 19,17 4, ,204 yes , ,6 5,244 4, ,548 yes , ,75 5, Mo 0,722 C 47, ,4 45,5 45,75 1,61 3, ,990 yes 30, ,9 31,1 30,84 4,328 14, ,725 yes , ,5 3,982 3, ,852 H 28, ,55 29,2 29,15 1,396 4, Ni 0,515 yes 48, ,45 48,19 3,004 6, ,630 yes ,55 25,6 25,21 5,143 20, ,909 yes , ,2 6,365 5, ,077 H 10, ,6 10,35 10,35 1,155 11, Pb 0,042 yes 66, ,65 66,78 66,28 3,867 5, Outlier test failed: C Cohcran, G1 Grubbs(1outlier algorithm), G2 Grubbs(2outliers algorithm), H Hampel, M manual SYKE Interlaboratory comparison test 3/2011

53 51 LIITE APPENDIX 7 / 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 0,378 yes ,9 19,45 15, Laboratory 32 Pb 0,527 yes 43, ,8 41,9 41,12 2,908 7, H 6, <20 5,71 5,712 0,531 9, Sb 4,596 H 45, ,85 46,75 45,74 5,057 11, <6 7,435 7,047 5,834 82, ,170 yes 88, ,41 12,32 14, ,290 H 6, ,8 6,63 6,702 1,204 17, Se 4,628 H 65, ,1 64,1 64,55 4,599 7, yes 20,9 50,9 42,9 16,03 37, ,535 yes 36, ,25 36,45 36,18 4,631 12, H 8,6 25 <20 8,305 8,663 1,002 11, Sn A2M 2,008 yes 25, ,8 25,65 25,08 3,346 13, L5M H 34,7 35 <2 36,1 34,65 4,869 14, V 1,695 yes 58, ,35 58,05 58,53 2,215 3, ,132 yes 45, ,9 45,1 43,98 3,665 8, ,518 yes 95, ,9 95,35 95,33 4, ,278 yes 10, ,5 10,65 10,78 0,6983 6, Zn 1,223 yes ,7 12,69 5, ,095 yes ,7 31,97 4, ,974 yes ,5 154,3 153,9 7,502 4, ,389 yes 37, , ,57 5,083 13, Laboratory 33 Cu 4,930 H 71, ,85 71,25 4,565 6, ,789 yes ,5 151,8 7,476 4, Fe 0,409 yes ,5 682,6 24,96 3, ,463 yes , ,7 43,35 6, Zn 0,175 yes ,7 12,69 5, ,197 yes ,5 153,3 152,9 9,046 5, Laboratory 34 Al Cu Laboratory 35 Al As B Cd Co Cr Cu Fe Hg Mn Mo Ni A1Hg L5M T4Hg 6,695 H ,9 47,52 6, ,320 H 71, ,85 71,25 4,565 6, ,293 yes , ,9 47,52 6, ,725 yes , ,267 yes , ,87 6, ,939 yes 85, ,85 83,45 83,74 5,423 6, ,626 yes 4, ,032 3,98 3,887 1,027 26, ,816 yes , ,54 6, ,876 yes 70, ,95 72,5 71,74 8,309 11, ,748 yes 16, ,47 17,7 15,86 4,146 26, ,166 yes , ,5 11,85 6, ,260 yes 9, ,55 9,7 9,573 0,7089 7, ,080 yes ,27 35,4 34,21 4,308 12, ,650 yes 64, ,7 64,4 64,67 3,481 5, ,168 yes 35, ,5 35,27 35,38 1,805 5, ,254 yes 9, ,39 10,1 9,803 1,515 15, ,747 yes 52, , ,36 2,647 5, ,613 yes 45, ,3 45,4 45,73 2,523 5, ,334 yes 46, ,55 45,23 44,11 7,983 18, ,455 yes ,9 132,4 134,2 7,154 5, ,101 yes 71, ,9 71,85 71,25 4,565 6, ,883 yes , ,5 31,44 10, ,415 yes , ,7 11, ,114 yes ,9 681,5 682,6 24,96 3, ,675 C , ,681 yes ,7 664,5 664,8 35,53 5, ,433 yes 0, ,6205 0,8145 0,8106 0, , ,848 yes 0, ,712 0,5965 0,5919 0, , ,333 yes 3, ,865 3,79 3,772 0,3658 9, ,500 yes , ,1 8,528 4, ,372 yes , ,4 19,17 4, ,111 yes ,6 5,244 4, ,658 yes 47, ,55 45,5 45,75 1,61 3, ,451 yes 30, ,97 31,1 30,84 4,328 14, ,392 yes ,5 3,982 3, ,052 yes 48, ,25 48,45 48,19 3,004 6, Outlier test failed: C Cohcran, G1 Grubbs(1outlier algorithm), G2 Grubbs(2outliers algorithm), H Hampel, M manual SYKE Interlaboratory comparison test 3/2011

54 LIITE 7 / 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 1,012 yes ,9 25,6 25,21 5,143 20, Laboratory 35 Ni 0,545 yes ,2 6,365 5, Pb 0,641 yes 66, ,65 66,78 66,28 3,867 5, ,550 yes , ,9 19,45 15, ,936 yes 43, ,2 41,9 41,12 2,908 7, Sb 0,098 yes 45, ,35 46,75 45,74 5,057 11, yes 3,6 7,435 7,047 5,834 82, ,195 yes 88, , ,41 12,32 14, Se 0,275 yes 65, ,05 64,1 64,55 4,599 7, yes 27,48 50,9 42,9 16,03 37, ,166 yes 36, ,7 36,45 36,18 4,631 12, Sn A2M 0,191 yes 25, ,5 25,65 25,08 3,346 13, L5M 5,622 H 34,7 35 0,562 36,1 34,65 4,869 14, V 0,548 yes 58, ,8 58,05 58,53 2,215 3, ,591 yes 45, ,81 45,1 43,98 3,665 8, ,602 yes 95, ,9 95,35 95,33 4, Zn 0,049 yes , ,7 12,69 5, ,174 H , ,7 31,97 4, ,175 yes ,3 154,3 153,9 7,502 4, Laboratory 36 Al 0,475 yes , ,9 47,52 6, LT5 yes , ,296 yes ,4 394, ,87 6, ,820 H ,3 121,5 124,5 13,69 10, As 0,683 yes 85, ,5 83,45 83,74 5,423 6, LT5 yes 5,28 5,28 5,287 0, , ,840 yes , ,54 6, ,700 H 7, ,3 7,345 7,291 0, , B 1,448 yes 70, ,95 72,5 71,74 8,309 11, LT5 yes 57,72 40,38 40,46 19,93 49, ,064 yes , ,5 11,85 6, ,532 H ,6 95,3 95,18 9,791 10, Cd 1,629 yes 9, ,55 9,7 9,573 0,7089 7, LT5 yes 30,91 32,09 32,33 1,701 5, ,869 yes 64, ,56 64,4 64,67 3,481 5, ,400 H 5, ,15 5,285 5,197 0,4364 8, Co 0,391 yes 35, ,5 35,27 35,38 1,805 5, LT5 yes 10,15 10,9 10,95 0,9327 8, ,096 yes 52, , ,36 2,647 5, ,500 H 13, ,7 13,2 13,28 0,805 6, Cr 0,875 yes 45, ,7 45,4 45,73 2,523 5, LT5 yes 46,61 53,52 54,33 9,018 16, ,676 yes ,5 132,4 134,2 7,154 5, ,300 H 13, ,1 13,95 13,91 0,7707 5, Cu 0,056 yes 71, ,6 71,85 71,25 4,565 6, LT5 yes 305,4 313,1 313,7 9,769 3, ,589 yes , ,7 11, ,400 H 8, ,9 9,03 8,957 1,015 11, Fe 0,574 yes ,7 681,5 682,6 24,96 3, LT5 yes , ,190 yes ,4 664,5 664,8 35,53 5, ,280 yes ,3 52,41 6, Hg A1Hg H 0,82 20 <0,3 0,8145 0,8106 0, , L5M 5,516 H 0, ,0215 0,5965 0,5919 0, , T4Hg H 3,82 15 <0,3 3,79 3,772 0,3658 9, Mn 0,360 yes , ,1 8,528 4, LT5 yes 389,9 435,7 436,7 54,1 12, ,314 yes , ,6 5,244 4, ,260 H ,3 467, ,75 5, Mo 1,571 C 47, ,8 45,5 45,75 1,61 3, LT5 yes 25,09 32,6 32,89 9,026 27, ,151 yes , ,5 3,982 3, ,400 H 28, ,3 29,2 29,15 1,396 4, Ni 0,165 yes 48, ,3 48,45 48,19 3,004 6, LT5 yes 23,4 27,37 27,65 4,932 17, ,962 yes , ,2 6,365 5, ,580 H 10, ,8 10,35 10,35 1,155 11, Outlier test failed: C Cohcran, G1 Grubbs(1outlier algorithm), G2 Grubbs(2outliers algorithm), H Hampel, M manual SYKE Interlaboratory comparison test 3/2011

55 53 LIITE APPENDIX 7 / 25 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 9,894 H 66, ,75 66,78 66,28 3,867 5, Laboratory 36 Pb LT5 yes 111,9 120,4 121,5 11,29 9, ,696 yes 43, ,72 41,9 41,12 2,908 7, ,384 yes 6, ,5 5,71 5,712 0,531 9, Sb 0,044 yes 45, ,75 45,74 5,057 11, LT5 yes 4,07 11,79 12,01 9,176 76, ,314 yes 88, , ,41 12,32 14, ,420 H 6, ,55 6,63 6,702 1,204 17, Se 0,928 yes 65, ,95 64,1 64,55 4,599 7, LT5 yes 34,15 50,25 50,63 19,03 37, ,995 yes 36, ,9 36,45 36,18 4,631 12, ,420 H 8, ,305 8,663 1,002 11, Sn A2M H 25,1 25 <20 25,65 25,08 3,346 13, L5M H 34,7 35 <0,02 36,1 34,65 4,869 14, V 0,428 yes 58, ,15 58,05 58,53 2,215 3, LT5 yes 38,58 45,77 45,94 8,505 18, ,732 yes 95, ,97 95,35 95,33 4, ,320 H 10, ,15 10,65 10,78 0,6983 6, Zn 0,233 yes ,7 12,69 5, LT5 yes 638,7 694,3 695,1 65,48 9, ,730 yes ,3 153,9 7,502 4, ,510 H 37, , ,57 5,083 13, Laboratory 37 Al As Cd Co Cu Fe Hg Mn Ni Pb Zn A1Hg L5M T4Hg 2,899 H ,9 47,52 6, ,927 yes , ,172 H , ,87 6, ,160 H ,3 40,48 9, ,720 H ,5 124,5 13,69 10, ,381 yes 85, ,45 83,74 5,423 6, ,596 yes 4, ,05 3,98 3,887 1,027 26, ,762 yes ,4 15,82 8, ,388 yes 7, ,1 7,345 7,291 0, , ,657 yes 9, ,26 9,7 9,573 0,7089 7, ,171 H ,4 34,21 4,308 12, ,595 yes ,1 65,75 65,08 4,367 6, ,335 yes 5, ,04 5,285 5,197 0,4364 8, ,670 yes 35, ,27 35,38 1,805 5, ,407 yes 9, ,2 10,1 9,803 1,515 15, ,400 yes 53, ,8 52,4 53,41 3,604 6, ,401 yes 13, ,9 13,2 13,28 0,805 6, ,793 yes 71, ,85 71,25 4,565 6, ,262 yes ,5 31,44 10, ,274 yes ,7 11, ,789 yes ,5 151,8 7,476 4, ,000 H 8, ,03 8,957 1,015 11, ,080 yes ,5 682,6 24,96 3, ,563 yes , ,120 yes ,5 664,8 35,53 5, ,736 yes , ,7 43,35 6, ,266 yes ,3 52,41 6, ,238 yes 0, ,8395 0,8145 0,8106 0, , ,917 yes 0, ,5205 0,5965 0,5919 0, , ,222 yes 3, ,17 3,79 3,772 0,3658 9, ,336 yes ,1 8,528 4, ,520 yes , ,4 19,17 4, ,204 yes , ,6 5,244 4, ,446 yes , ,9 5,161 4, ,880 yes ,5 467, ,75 5, ,031 yes 48, ,5 48,45 48,19 3,004 6, ,333 yes ,65 25,6 25,21 5,143 20, ,180 yes ,4 7,009 6, ,442 yes 10,4 20 8,9 10,35 10,35 1,155 11, ,608 yes 66, ,5 66,78 66,28 3,867 5, ,000 yes ,9 19,45 15, ,052 yes 42, ,6 42,75 43,47 5,069 11, ,006 yes 6, ,6 5,71 5,712 0,531 9, ,689 yes ,7 12,69 5, Outlier test failed: C Cohcran, G1 Grubbs(1outlier algorithm), G2 Grubbs(2outliers algorithm), H Hampel, M manual SYKE Interlaboratory comparison test 3/2011

56 LIITE 7 / 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 1,056 yes , ,7 31,97 4, Laboratory 37 Zn 3,506 H ,3 153,9 7,502 4, ,526 yes ,3 152,9 9,046 5, ,174 yes 37, ,57 5,083 13, Laboratory 38 As 0,651 yes 85, ,09 83,45 83,74 5,423 6, yes 6,75 5,65 5,509 0, , ,726 yes , ,54 6, ,981 yes 7, ,285 7,345 7,291 0, , Cd 0,746 yes 9, ,29 9,7 9,573 0,7089 7, ,947 yes 33, ,1 33,82 1,974 5, ,299 yes 64, ,79 64,4 64,67 3,481 5, ,012 yes 5, ,95 5,285 5,197 0,4364 8, Co 0,399 yes 35, ,09 35,27 35,38 1,805 5, ,325 yes 10, ,64 10,53 10,19 0,965 9, ,538 yes 52, , ,36 2,647 5, ,361 yes 13, ,66 13,2 13,28 0,805 6, Cr 0,295 yes 45, ,03 45,4 45,73 2,523 5, ,508 yes 54, ,85 54,45 52,88 4,893 9, ,231 yes ,4 132,4 134,2 7,154 5, ,484 yes 13, ,4 13,95 13,91 0,7707 5, Cu 0,305 yes 71, ,31 71,85 71,25 4,565 6, ,016 yes ,6 322,5 317,6 16,5 5, ,169 yes , ,7 11, H 8,91 20 <9,3 9,03 8,957 1,015 11, Mn 0,659 yes , ,1 8,528 4, ,562 yes ,8 427,5 431,2 17, ,120 yes , ,6 5,244 4, ,153 yes ,3 467, ,75 5, Mo 0,505 yes 47, ,91 45,5 45,75 1,61 3, ,157 yes , ,5 3,982 3, ,323 yes 28, ,6 29,2 29,15 1,396 4, Ni 0,144 yes 48, ,8 48,45 48,19 3,004 6, ,297 yes 28, ,98 28,7 28,71 2,54 8, ,782 yes , ,2 6,365 5, ,534 yes 10, ,96 10,35 10,35 1,155 11, Pb 0,127 yes 66, ,37 66,78 66,28 3,867 5, ,560 yes ,8 126,5 124,3 14,77 11, ,334 yes 43, ,17 41,9 41,12 2,908 7, H 6, <10,4 5,71 5,712 0,531 9, Sb 1,448 yes 45, ,43 46,75 45,74 5,057 11, ,594 yes 18, ,98 18,2 18,92 2,045 10, H 88,1 25 <1, ,41 12,32 14, ,074 yes 6, ,395 6,63 6,702 1,204 17, Se 0,348 yes 65, ,11 64,1 64,55 4,599 7, ,764 yes 36, ,86 36,45 36,18 4,631 12, ,628 yes 8,6 25 9,275 8,305 8,663 1,002 11, Zn 0,189 yes , ,7 12,69 5, ,358 yes ,8 704, ,18 6, ,013 yes ,1 154,3 153,9 7,502 4, H 37,3 20 <61, ,57 5,083 13, Laboratory 39 Hg A1Hg 0,207 yes 0, ,837 0,8145 0,8106 0, , L5M 0,871 yes 0, ,5255 0,5965 0,5919 0, , T4Hg 0,084 yes 3, ,844 3,79 3,772 0,3658 9, Laboratory 40 Pb 0,000 yes 66, ,79 66,78 66,28 3,867 5, ,000 yes 43, ,52 41,9 41,12 2,908 7, ,000 yes 6, ,137 5,71 5,712 0,531 9, Outlier test failed: C Cohcran, G1 Grubbs(1outlier algorithm), G2 Grubbs(2outliers algorithm), H Hampel, M manual SYKE Interlaboratory comparison test 3/2011

57 55 LIITE APPENDIX 8 / 1 LIITE 8. SUMMARY OF THE z SCORES APPENDIX 8. Analyte Sample\Lab Al S. S S S. S S S S. S S S.. S S U S S. S.. S u... S S.... S... q S. S. S LO LT S Q. S S. S. S. S.. S S. S S. S S. S S.... S.. S. S Q. S S S. S S U S. S. S.. S S. S S. S As S. q S S. S S S S. S S S. S S S. S S. S. S S S... S Q.... S... S.. S. q LO LT S S. S Q. S. S S S. S Q S. S S. S S. S S.... S.. u. S S S. S S Q. S S S.. S. S. S S S.. S. S B S. S u.. S S. S. Q.... S S. S S.... S S... S q.. S.. LO LT Q.. S S. S. S. S.. S S. S S S. S S.. S S. S. Q.... S S. S S.. Cd 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 LO5.... S.... S S... S.. LT 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 u. S S S S. S S S. q S S. S S S S Co S. S S S. S S. S. S. S. S S S. S S. q. q S S... S S.... S... S S. S. S LO5.... S.... S S... S.. LT S S. S Q U S. S. S. S S S. S S. S S. S S.... U.. S. S S U. S S S. S S U S. S. S. S S S. S S. S Cr 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 LO5.... q.... S S... S.. LT 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 S. S S S S. S S S. S S S. S S S S Cu S. S S S. S S U S. S S S. u S Q U S S S S. S S S. S. S S.... S... q S. S. S LO5.... S.... S S... S.. LT S S. S S U 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 Fe S. S S S. S S S S. S S S.. S S S S S. S.. S u... q S.... S... S S. S. S LO LT S S. S S S S. q 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 Hg A1Hg.. S... S S S S u S S S S. S S S. S.. L5M.. S. S... q S u S. S.. S S S. S.. T4Hg.. S..... S S S S S S U. S S S. S.. Mn 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 LO5.... S.... S S... S.. LT 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. q S S. S S. S Mo S. S S.. S S. S. S. S.. S S. S S... S. S... S..... S... S.. S.. LO5.. S. S.... S S... S.. LT SYKE Interlaboratory comparison test 3/

58 LIITE APPENDIX 8 / 2 56 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.. Ni S. S S S. S S S S. S S S. S S S. S S S S. q S S. q. S S.... S... q S. S. S LO5.... S.... S S... S.. LT S S. S Q 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 S. S S S. S S q S Pb S. S S S. S S S S. S S S. q S S. S S Q S. S S S. S. S S.... S... S S. S. Q LO5.... S.... S S... S.. LT 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 u. S S S.. S. S. S S S.. S S S Sb S. S S u.. S. S. Q. S. q S S. S S LO5.. S S S.... Q S... S.. LT S q.. 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.. Se q. S S... S. S. S. S.. S S. S S LO LT S... S. S. S. S.. S S. S S.. S. S S q. S S. S S... S... S. S.. S S. Q S.. Sn A2M S. S S... S. S. S.... S S.. S.. L5M.. S.... u. S. S S.. V S. S S S. S S. S. S. S.. S S. S S... S S S... S..... S... S.. S.. LO LT 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.. Zn 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. S. S LO5.... S.... S S... S.. LT 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 % Accredited yes 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. u S S Q S.. Q. q LO LT S.. S S U S S U S u.. S... U U As... S S S. S S.. S S S S S. S LO LT S.... S.. S S. S S Q. S..... S S U S S.. 89 B.... S... S.. S S S.. S LO LT S.. S q S... S... U Cd... S S S. S S.. S S S S S S.. S. U LO5.... S S SYKE Interlaboratory comparison test 3/

59 57 LIITE APPENDIX 8 / 3 Analyte Sample\Lab LT S.... S.. S S. S.. 95 S... S S. S..... S S S Q U S Q.. 79 Co. u.. S S. S... S S S S S. S LO5.... S S LT S S. S S.. S S. S..... S S S U S S.. 86 Cr. u.. S S U S S.. S S. S.. 89 u q.. S LO5.... S S.. 83 LT S. S.. S S. S.. 95 S q.. S Q. S S S.. S... U. S.. 91 Cu... S S S. S S U u q S S S.. 77 S S.. S. S LO5.... S S LT S.... S.. S S S S.. 91 S... S S. S. S... S S Q S.. S... U u Fe S S.. S S S S S S. S S S S u.. S. S LO LT S. S.. S S S S S.. S S. S. S... S S... S S.. S... q S Hg A1Hg... S S.. S... q. S. S. 90 L5M.... S S u S. S. 81 T4Hg... S S.. S... u. S. S. 89 Mn S... S S. S S.. S S q S.. 96 S S.. S. S LO5.... S S LT S.. S S S S.. 95 S... S S S S... S S.. S... u S S.. 92 Mo.... S... S.. S S. S S.. S LO5.... S LT S.. S S. S S S... u... U. S.. 88 Ni... S S u S S S.. S S S S.. 96 S S.. S. S LO5.... S S LT S S.. S. S.. S S. S.. 91 S... S u. S..... S S S... U... U S S.. 83 Pb... S S S. S S.. S u Q S. S 86 S S.. S. S LO5.... S S LT S.... S.. S q. S. S S S. S..... U S S S.. S 95 Sb.... S... U.. S S. S LO5.... S S.. 88 LT Q.. S S S U... U. S.. 79 Se.... S.. S U.. S S. S LO LT SYKE Interlaboratory comparison test 3/ %

60 LIITE APPENDIX 8 / 4 58 Analyte Sample\Lab Q.. S S. S S.. S U. S.. 83 Sn A2M.... S... q.. S L5M.... S u V.... S.. S S.. S S S.. S LO LT S.. S S S.. S S... U Zn S S. S S S S S S S. S S S S S S.. u. S LO5.... S S LT S.. S. S.. S q u S.. 91 S S.. S Q. S. S... S S S Q.. S... U u % Accredited yes yes yes yes yes yes yes % %* percentage of satisfactory results Totally satisfactory, % In all: 90 In accredited: 92 In nonaccredited: 85 SYKE Interlaboratory comparison test 3/2011

61 ANALYTICAL METHODS 59 APPENDIX 9.1/1 Hg/Pretreatment/Measurement: Lab 1) Sample Oxidant/ Equipment and temperature in Measurement reducing digestion 3 A1Hg No digestion ICPMS T4Hg HNO 3 Autoclave 30min. 121 C L5M HNO 3 Closed vessels MWO 40 min. 170 C 10 A1Hg, T4Hg HNO 3 Microwave oven (CEM, Mars5) 175 C CVAAS L5M HNO 3 /HCl Microwave oven (CEM, Mars5) 175 C 13 A1Hg, T4Hg KBr/KBrO 3 Room temperature CV/AFS 14 A1Hg, T4Hg KBr/KBrO 3 CV/AFS L5M Milestone DMA C Oxidation with O 2 + AAS 15 A1Hg, T4Hg KBr Hydride/FIAS 17 A1Hg, T4Hg HNO 3 Autoclave 120 C ICPMS L5M Oxygen combustion Leco/AMA Oxidation with O 2 + AAS 19 A1Hg, T4Hg KMnO 4 /HNO 3 / Water bath 95 C 2h CVAAS K 2 S 2 O 8 L5M KMnO 4 /HNO 3 / Water bath 95 C 2h K 2 S 2 O 8 27 A1Hg, T4Hg KBr CV/AFS 28 A1Hg, T4Hg KMnO 4 CVAAS L5M KMnO 4 Microwave oven 175 C 31 A1Hg, T4Hg KMnO 4, HNO 3 Water bath 95 C FIMSAAS 39 A1Hg, T4Hg Bromation Amalgamation CV/AFS L5M Dry substance determination in 105 C Oxidation with O 2 + AAS 1) Laboratories 5, 7, 8, 9, 11, 12, 18, 21, 35, 36 and 37 didn't report the pretreatment method.

62 APPENDIX 9.1/2 ANALYTICAL METHODS 60 Metals/Pretreatment the waste water sample T4M no digestion digestion with acid Metals/Pretreatment the sludge L5M digestion with HNO 3 LO5 digestion with HNO 3 + HCl LT5 digestion with HNO 3 + HF Metals/ Measurement from the water and the sludge samples Analyte Code Method Al, B, Cd, Co, 1 FAAS Cr, Cu, Fe, Mn, 2 GAAS Mo, Ni, Pb, Se, 3 ICPOES Sn, V, Zn 4 ICPMS 5 Hydride generation 6 Other method, please specify As 2 GAAS 3 ICPOES 4 ICPMS 5 Hydride generation 6 Other method, please specify Hg/ Measurement from the water and the sludge samples Analyte Code Method Hg 1 CVAAS 2 ICPOES 3 Hydride/FIAS 4 Oxidation with O 2 + AAS (e.g. Lecoanalyser) 5 CVAFS 6 Other method, please specify

63 61 APPENDIX 9.2 SIGNIFICANT DIFFERENCES IN THE RESULTS REPORTED USING DIFFERENT SAMPLE DIGESTION 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 Al X Mn X Sb X Digestion Samples and LO5 Analyte Sample/Method 2) X (mg kg 1 ) sd n Significant difference Cr X LO Mo X LO Sb X LO Se X LO where X: th e 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 LO5 digestion with HNO 3 + HCl (aqua regia)

64 APPENDIX 9.3 SIGNIFICANT DIFFERENCES IN THE RESULTS REPORTED USING DIFFERENT MEASUREMENT METHODS 62 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 1. FAAS X: meth 13, ICPOES ICPMS As 2. GAAS X: meth 23, ICPOES ICPMS B 3. ICPOES X: meth ICPMS Cd 2. GAAS X: meth ICPMS Cr 1. FAAS X: meth 13, ICPOES ICPMS GAAS X: meth ICPMS Cu 1. FAAS X: meth 13, ICPOES ICPMS GAAS X: meth ICPMS Fe 1. FAAS X: meth ICPOES Mn 1. FAAS X: meth 13, ICPOES ICPMS FAAS X: meth ICPOES FAAS X: meth ICPOES Mo 3. ICPOES X: meth ICPMS ICPOES X: meth ICPMS Ni 2. GAAS X: meth 24, ICPOES ICPMS Se 3. ICPOES X: meth ICPMS ICPOES X: meth ICPMS Zn 1. FAAS X: meth 13, ICPOES ICPMS FAAS X: meth 13, 14, ICPOES ICPMS where: X: the mean value sd: the standard deviation n: the number of the result

65 63 APPENDIX 9.4 RESULTS GROUPED ACCORDING TO THE METHODS Method code see the Appendix 9.1

66 LIITE APPENDIX 9.4 / 1 64 LIITE 9.4. APPENDIX 9.4. Al Meth 1 Meth 2 Meth 3 Meth 4 Meth 6 Al Meth 1 Meth 2 Meth 3 Meth 4 Al LO Meth 3 Meth 4 SYKE Interlaboratory comparison test 3/2011

67 65 LIITE APPENDIX 9.4 / 2 Al Meth 1 Meth 2 Meth 3 Meth 4 Al Meth 1 Meth 2 Meth 3 Meth 4 Al Meth 1 Meth 2 Meth 3 Meth 4 SYKE Interlaboratory comparison test 3/2011

68 LIITE APPENDIX 9.4 / 3 66 As Meth 2 Meth 3 Meth 4 Meth 5 As 7 6,5 6 5,5 5 4,5 4 3,5 3 2,5 2 1,5 Meth 2 Meth 3 Meth 4 Meth 5 As LO5 9 8,5 8 7,5 7 6,5 6 5,5 5 4,5 4 3,5 3 Meth 3 Meth 4 SYKE Interlaboratory comparison test 3/2011

69 67 LIITE APPENDIX 9.4 / 4 As Meth 2 Meth 3 Meth 4 As Meth 2 Meth 3 Meth 4 Meth 5 As Meth 2 Meth 3 Meth 4 Meth 5 SYKE Interlaboratory comparison test 3/2011

70 LIITE APPENDIX 9.4 / 5 68 B Meth 3 Meth 4 B Meth 3 Meth 4 B LO Meth 3 Meth 4 SYKE Interlaboratory comparison test 3/2011

71 69 LIITE APPENDIX 9.4 / 6 B Meth 3 Meth 4 B Meth 3 Meth 4 B Meth 3 Meth 4 SYKE Interlaboratory comparison test 3/2011

72 LIITE APPENDIX 9.4 / 7 70 Cd 13 12, , ,5 10 9,5 9 8,5 8 7,5 7 6,5 Meth 2 Meth 3 Meth 4 Cd Meth 1 Meth 2 Meth 3 Meth 4 Cd LO Meth 3 Meth 4 SYKE Interlaboratory comparison test 3/2011

73 71 LIITE APPENDIX 9.4 / 8 Cd Meth 2 Meth 3 Meth 4 Cd Meth 1 Meth 2 Meth 3 Meth 4 Cd 7 6,5 6 5,5 5 4,5 4 3,5 Meth 2 Meth 3 Meth 4 SYKE Interlaboratory comparison test 3/2011

74 LIITE APPENDIX 9.4 / 9 72 Co Meth 1 Meth 2 Meth 3 Meth 4 Co Meth 1 Meth 2 Meth 3 Meth 4 Co LO Meth 3 Meth 4 SYKE Interlaboratory comparison test 3/2011

75 73 LIITE APPENDIX 9.4 / 10 Co Meth 1 Meth 2 Meth 3 Meth 4 Co Meth 1 Meth 2 Meth 3 Meth 4 Co Meth 1 Meth 2 Meth 3 Meth 4 SYKE Interlaboratory comparison test 3/2011

76 LIITE APPENDIX 9.4 / Cr Meth 1 Meth 2 Meth 3 Meth 4 Cr Meth 1 Meth 2 Meth 3 Meth 4 Cr LO Meth 3 Meth 4 SYKE Interlaboratory comparison test 3/2011

77 75 LIITE APPENDIX 9.4 / 12 Cr Meth 2 Meth 3 Meth 4 Cr Meth 1 Meth 2 Meth 3 Meth 4 Cr Meth 2 Meth 3 Meth 4 SYKE Interlaboratory comparison test 3/2011

78 LIITE APPENDIX 9.4 / Cu Meth 1 Meth 2 Meth 3 Meth 4 Meth 6 Cu Meth 1 Meth 3 Meth 4 Cu LO Meth 3 Meth 4 SYKE Interlaboratory comparison test 3/2011

79 77 LIITE APPENDIX 9.4 / 14 Cu Meth 1 Meth 2 Meth 3 Meth 4 Cu Meth 1 Meth 2 Meth 3 Meth 4 Cu Meth 1 Meth 2 Meth 3 Meth 4 SYKE Interlaboratory comparison test 3/2011

80 LIITE APPENDIX 9.4 / Fe Meth 1 Meth 3 Meth 4 Fe Meth 1 Meth 3 Meth 4 Fe LO Meth 3 Meth 4 SYKE Interlaboratory comparison test 3/2011

81 79 LIITE APPENDIX 9.4 / 16 Fe Meth 1 Meth 3 Meth 4 Fe Meth 1 Meth 3 Meth 4 Fe Meth 1 Meth 3 Meth 4 SYKE Interlaboratory comparison test 3/2011

82 LIITE APPENDIX 9.4 / Hg A1Hg 1,2 1,1 1 0,9 0,8 0,7 0,6 0,5 Meth 1 Meth 2 Meth 3 Meth 4 Meth 5 Meth 6 Hg L5M 1,1 1 0,9 0,8 0,7 0,6 0,5 0,4 0,3 0,2 0,1 Meth 1 Meth 2 Meth 3 Meth 4 Meth 5 Meth 6 Hg T4Hg 5,2 5 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 1 Meth 2 Meth 3 Meth 4 Meth 5 Meth 6 SYKE Interlaboratory comparison test 3/2011

83 81 LIITE APPENDIX 9.4 / 18 Mn Meth 1 Meth 3 Meth 4 Mn Meth 1 Meth 3 Meth 4 Mn LO Meth 3 Meth 4 SYKE Interlaboratory comparison test 3/2011

84 LIITE APPENDIX 9.4 / Mn Meth 1 Meth 3 Meth 4 Mn Meth 1 Meth 3 Meth 4 Mn Meth 1 Meth 3 Meth 4 SYKE Interlaboratory comparison test 3/2011

85 83 LIITE APPENDIX 9.4 / 20 Mo Meth 3 Meth 4 Mo Meth 3 Meth 4 Mo LO Meth 3 Meth 4 SYKE Interlaboratory comparison test 3/2011

86 LIITE APPENDIX 9.4 / Mo Meth 3 Meth 4 Mo Meth 3 Meth 4 Mo Meth 3 Meth 4 SYKE Interlaboratory comparison test 3/2011

87 85 LIITE APPENDIX 9.4 / 22 Ni Meth 2 Meth 3 Meth 4 Ni Meth 1 Meth 2 Meth 3 Meth 4 Ni LO Meth 3 Meth 4 SYKE Interlaboratory comparison test 3/2011

88 LIITE APPENDIX 9.4 / Ni LT Meth 3 Meth 4 Ni Meth 2 Meth 3 Meth 4 Ni Meth 1 Meth 2 Meth 3 Meth 4 SYKE Interlaboratory comparison test 3/2011

89 87 LIITE APPENDIX 9.4 / 24 Ni Meth 2 Meth 3 Meth 4 Pb Meth 2 Meth 3 Meth 4 Meth 6 Pb Meth 1 Meth 2 Meth 3 Meth 4 SYKE Interlaboratory comparison test 3/2011

90 LIITE APPENDIX 9.4 / Pb LO Meth 3 Meth 4 Pb Meth 2 Meth 3 Meth 4 Meth 6 Pb Meth 2 Meth 3 Meth 4 SYKE Interlaboratory comparison test 3/2011

91 89 LIITE APPENDIX 9.4 / 26 Pb 8 7,5 7 6,5 6 5,5 5 4,5 4 Meth 2 Meth 3 Meth 4 Meth 6 Sb Meth 2 Meth 3 Meth 4 Sb Meth 3 Meth 4 SYKE Interlaboratory comparison test 3/2011

92 LIITE APPENDIX 9.4 / Sb LO Meth 3 Meth 4 Sb Meth 2 Meth 3 Meth 4 Sb Meth 3 Meth 4 SYKE Interlaboratory comparison test 3/2011

93 91 LIITE APPENDIX 9.4 / 28 Sb Meth 2 Meth 3 Meth 4 Se Meth 2 Meth 3 Meth 4 Meth 6 Se Meth 3 Meth 4 SYKE Interlaboratory comparison test 3/2011

94 LIITE APPENDIX 9.4 / Se LO Meth 3 Meth 4 Se Meth 3 Meth 4 Se Meth 2 Meth 3 Meth 4 Meth 6 SYKE Interlaboratory comparison test 3/2011

95 93 LIITE APPENDIX 9.4 / 30 Se Meth 3 Meth 4 Meth 6 Sn A2M Meth 3 Meth 4 Sn L5M Meth 3 Meth 4 SYKE Interlaboratory comparison test 3/2011

96 LIITE APPENDIX 9.4 / V Meth 2 Meth 3 Meth 4 V Meth 3 Meth 4 V LO Meth 3 Meth 4 SYKE Interlaboratory comparison test 3/2011

97 95 LIITE APPENDIX 9.4 / 32 V Meth 3 Meth 4 V Meth 2 Meth 3 Meth 4 V Meth 3 Meth 4 SYKE Interlaboratory comparison test 3/2011

98 LIITE APPENDIX 9.4 / Zn Meth 1 Meth 2 Meth 3 Meth 4 Zn Meth 1 Meth 3 Meth 4 Zn LO Meth 3 Meth 4 SYKE Interlaboratory comparison test 3/2011

99 97 LIITE APPENDIX 9.4 / 34 Zn Meth 1 Meth 2 Meth 3 Meth 4 Zn Meth 1 Meth 3 Meth 4 Zn Meth 1 Meth 3 Meth 4 SYKE Interlaboratory comparison test 3/2011

100 APPENDIX 10 EXAMPLES OF MEASUREMENT UNCERTAINTIES REPORTED BY THE LABORATORIES 98 For evaluation of the measurement uncertainty the participants have been 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 537 1) 4. using the data obtained in the analysis of CRM (besides IQC data). see e.g.nordtest TR 537 1) 5. using the IQC data and the results obtained in proficiency tests. see e.g. NORDTEST TR 537 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)

101 99 LIITE APPENDIX 10 / 1 LIITE 10. APPENDIX 10. Al 25 Uncertainty, % Meth2 Meth3 Meth4 Meth5 Meth6 Al Uncertainty, % Meth2 Meth3 Meth4 Meth5 Meth7 Al Uncertainty, % 25 Meth2 Meth3 Meth4 Meth5 Meth6 Meth SYKE Interlaboratory comparison test 3/2011

102 LIITE APPENDIX 10 / As 30 Uncertainty, % Meth2 Meth3 Meth4 Meth5 Meth6 As Uncertainty, % Meth2 Meth3 Meth4 Meth5 Meth6 Meth7 B Uncertainty, % Meth2 Meth3 Meth4 Meth5 Meth SYKE Interlaboratory comparison test 3/2011

103 101 LIITE APPENDIX 10 / 3 B Uncertainty, % Meth2 Meth3 Meth4 Meth5 Meth6 Meth7 Cd Uncertainty, % Meth2 Meth3 Meth4 Meth5 Meth6 Cd 25 Meth2 Meth3 Meth4 Uncertainty, % Meth5 Meth SYKE Interlaboratory comparison test 3/2011

104 LIITE APPENDIX 10 / Co Uncertainty, % Meth2 Meth3 Meth4 Meth5 Meth6 Meth7 Cr Uncertainty, % Meth2 Meth3 Meth4 Meth5 Meth6 Cr Uncertainty, % Meth2 Meth3 Meth4 Meth5 Meth6 Meth SYKE Interlaboratory comparison test 3/2011

105 103 LIITE APPENDIX 10 / 5 Cu Uncertainty, % Meth2 Meth3 Meth4 Meth5 Meth6 Cu Uncertainty, % Meth2 Meth3 Meth4 Meth5 Meth7 Fe 25 Meth2 Meth3 Meth4 Meth5 Uncertainty, % Meth6 Meth SYKE Interlaboratory comparison test 3/2011

106 LIITE APPENDIX 10 / Hg L5M Uncertainty, % Meth2 Meth3 Meth4 Meth5 Meth6 Hg T4Hg 25 Uncertainty, % Meth2 Meth3 Meth4 Meth5 Meth6 Mn 25 Meth2 Meth3 Meth4 Meth5 Uncertainty, % Meth6 Meth SYKE Interlaboratory comparison test 3/2011

107 105 LIITE APPENDIX 10 / 7 Mo Uncertainty, % Meth2 Meth3 Meth4 Meth5 Meth6 Mo Uncertainty, % Meth2 Meth3 Meth4 Meth5 Meth6 Ni Meth1 Meth2 Uncertainty, % Meth3 Meth4 Meth5 Meth SYKE Interlaboratory comparison test 3/2011

108 LIITE APPENDIX 10 / Pb Uncertainty, % Meth2 Meth3 Meth4 Meth5 Meth6 Pb Uncertainty, % Meth2 Meth3 Meth4 Meth5 Meth6 Meth7 Sb Uncertainty, % Meth2 Meth3 Meth4 Meth5 Meth6 Meth SYKE Interlaboratory comparison test 3/2011

109 107 LIITE APPENDIX 10 / 9 Se Uncertainty, % Meth2 Meth3 Meth4 Meth5 Sn A2M Uncertainty, % Meth3 Meth4 Meth5 Meth6 V 25 Meth2 Meth3 Meth4 Uncertainty, % Meth5 Meth SYKE Interlaboratory comparison test 3/2011

110 LIITE APPENDIX 10 / Zn Uncertainty, % Meth2 Meth3 Meth4 Meth5 Meth6 Zn Uncertainty, % 25 Meth2 Meth3 Meth4 Meth5 Meth6 Meth SYKE Interlaboratory comparison test 3/2011

111 Documentation page 109 Publisher Finnish Environment Institute (SYKE) Date January 2012 Author(s) Mirja Leivuori, Kaija Korhonen, Timo SaraAho, Teemu Näykki, Keijo Tervonen, Sari Lanteri and Markku Ilmakunnas Title of publication Proficiency test SYKE 3/2011 Metals in water and sludge Parts of publication/ other project publications Abstract The publication is available only in the internet Proftest SYKE carried out the proficiency test for analysis of metals in waters and soil in April August The measured analytes were: Al, As, B, Cd, Co, Cr, Cu, Fe, Hg, Mn, Mo, Ni, Pb, Sb, Se, Sn, V and Zn. In total 3 9 la boratories p articipated in the pr oficiency test. Th e sam ple types were: artificial and natural water, municipal and industrial waste water and sludge. Basically, the calculated concentrations or the robust mean of the results reported by the participant were u sed as th e assigned values for measurands. Th e eva luation of th e p erformance o f t he 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, 90 % of the total data in this proficiency test were satisfactory when the deviations of % from th e assigned values wer e accepted. Keywords Publication series and number Theme of publication water analysis, metals, Al, As, B, Cd, Co, Cr, Cu, Fe, Hg, Mn, Mo, Ni, Pb, Sb, Se, Sn, V, Zn, water, sludge, environmental laboratories, proficiency test, interlaboratory comparisons Reports of Finnish Environment Institute 22/2012 Project name and number, if any Financier/ commissioner Project organization ISSN ISBN (online) (PDF) No. of pages Language 111 English Restrictions Public Price For sale at/ distributor Financier of publication Printing place and year Helsinki 2012 Other information Finnish Environment Institute, Customer service [email protected] Phone Fax Finnish Environment Institute, P.O. Box 140, FI00251 Helsinki, Finland

112 Kuvailulehti Julkaisija Suomen ympäristökeskus (SYKE) Julkaisuaika Tammikuu Tekijä(t) Mirja Leivuori, Kaija Korhonen, Timo SaraAho, Teemu Näykki, Keijo Tervonen, Sari Lanteri ja Markku Ilmakunnas Julkaisun nimi SYKE Proficiency Test 3/2011 Metals in waters and sludge Julkaisun osat/ muut saman projektin tuottamat julkaisut Tiivistelmä Julkaisu on saatavana vain internetistä. Suomen ympäristökeskuksen laboratorio järjesti pätevyyskokeen ympäristönäytteitä analysoiville laboratorioille kesällä Pätevyyskokeessa mää ritettiin synteettisestä näytteestä, ko lmesta erityyppisestä vesinäytteestä sekä lietenäytteestä seuraavat metallit: Al, As, B, Cd, Co, Cr, Cu, Fe, Hg, Mn, Mo, Ni, Pb, Sb, Se, Sn, V ja Zn. Pätevyyskokeeseen osallistui y hteensä 39 laboratoriota, joista yksi r aportoi ka hdella e ri menetelmällä a nalysoidut tu lokset. L aboratorioiden pätevyyden arviointi te htiin z arvon avulla. Mittaussuureen vertailuarvona käytettiin pääsääntöisesti laskennallista pitoisuutta tai osallistujien ilmoittamien tulosten robustia keskiarvoa. Koko tulosaineistossa h yväksyttäviä tuloksia oli 90 %, kun vertailuarvosta s allittiin % :n poikkeama. Asiasanat Julkaisusarjan nimi ja numero Julkaisun teema vesianalyysi, metallit, liete, Al, As, B, Cd, Co, Cr, Cu, Fe, Hg, Mn, Mo, Ni, Pb, Sb, Se, Sn, V, Zn, vesi ja ympäristölaboratoriot, pätevyyskoe, laboratorioiden välinen vertailumittaus Reports of Finnish Environment Institute 22/2012 Projektihankkeen nimi ja projektinumero Rahoittaja/ toimeksiantaja Projektiryhmään kuuluvat organisaatiot ISSN ISBN (verkkoj.) (PDF) Sivuja Kieli 111 Englanti Luottamuksellisuus Julkinen Hinta Julkaisun myynti/ jakaja Julkaisun kustantaja Painopaikka ja aika Helsinki 2012 Muut tiedot Suomen ympäristökeskus, asiakaspalvelu Sähköpostiosoite: [email protected] puh faksi Suomen ympäristökeskus, PL 140, Helsinki

113 Presentationsblad 111 Utgivare Finlands Miljöcentral (SYKE) Datum Januari 2012 Författare Mirja Leivuori, Kaija Korhonen, Timo SaraAho, Teemu Näykki, Keijo Tervonen, Sari Lanteri och Markku Ilmakunnas Publikationens titel Provningsjämförelse 3/2011 Metaller i vatten och slam Publikationens delar/ andra publikationer inom samma projekt Sammandrag Publikationen finns tillgänglig på internet Under AprilAugusti 2011 genomförde F inlands Miljöcentral en provningsjämförelse, som omfattade bestämningen av Al, As, B, Cd, Co, Cr, Cu, Fe, Hg, Mn, Mo, Ni, Pb, Sb, Se, Sn, V och Zn i vatten och slammet. Tillsammans 39 laboratorier deltog i jämförelsen. Som referensvärde a v an alytens k oncentration an vändes m est det teoretiska värdet eller robust medelvärdet a v del tagarnas r esultat. Resultaten värderades m ed h jälp a v z värden. I jämförelsen var 90 % a v alla resultaten tillfredsställande, när total deviation på % f rån r eferensvärdet accepterades. Nyckelord Publikationsserie och nummer Publikationens tema vattenanalyser, metaller, Al, As, B, Cd, Co, Cr, Cu, Fe, Hg, Mn, Mo, Ni, Pb, Sb, Se, Sn, V, Zn slam, provningsjämförelse, vatten och miljölaboratorier Reports of Finnish Environment Institute 22/2012 Projektets namn och nummer Finansiär/ uppdragsgivare Organisationer i projektgruppen ISSN ISBN (online) (PDF) Sidantal Språk 111 Engelska Offentlighet Offentlig Pris Beställningar/ distribution Förläggare Tryckeri/ tryckningsort och år Finlands miljöcentral, informationstjänsten [email protected] Tfn Fax Finlands Miljöcentral, PB 140, Helsingfors Helsingfors 2012 Övriga uppgifter

114 SYKE PROFICIENCY TEST 3/2011 ISBN (PDF) ISSN (online) SYKE FINNISH ENVIRONMENT INSTITUTE