Interlaboratory Proficiency Test NW 2/2014

Transkriptio

1 REPORTS OF FINNISH ENVIRONMENT INSTITUTE Interlaboratory Proficiency Test NW 2/2014 Alkalinity, ph, nutrients and conductivity in natural waters Mirja Leivuori, Kaija Korhonen-Ylönen, Teemu Näykki, Keijo Tervonen, Markku Ilmakunnas, Sari Lanteri and Riitta Koivikko Finnish Environment Institute

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3 Alkalinity, ph, nutrients and conductivity in natural waters Mirja Leivuori, Kaija Korhonen-Ylönen, Teemu Näykki, Keijo Tervonen, Markku Ilmakunnas, Sari Lanteri and Riitta Koivikko

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5 ALKUSANAT Suomen ympäristökeskus (SYKE) toimii ympäristönsuojelulain nojalla määrättynä ympäristöalan vertailulaboratoriona Suomessa. Yksi tärkeimmistä vertailulaboratorion tarjoamista palveluista on pätevyyskokeiden ja muiden vertailumittausten järjestäminen. SYKEn laboratoriotoiminnan testaus-, kalibrointi- ja tutkimustoiminta sekä vertailumittausten järjestäminen (Proftest SYKE) ovat FINAS akkreditoituja (SFS-EN ISO/IEC 17025, SFS-EN ISO/IEC 17043, Tämä pätevyyskoe on toteutettu SYKEn vertailulaboratorion toiminta-alueella ja se antaa ulkopuolisen laadunarvion laboratoriotulosten keskinäisestä vertailtavuudesta sekä laboratorioiden määritysten luotettavuudesta. Pätevyyskokeen onnistumisen edellytys on järjestäjän ja osallistujien välinen luottamuksellinen yhteistyö. Lämmin kiitos yhteistyöstä kaikille osallistujille! PREFACE Finnish Environment Institute (SYKE) is appointed National Reference in the environmental sector in Finland. The duties of the reference laboratory include providing interlaboratory proficiency tests and other comparisons for analytical laboratories and other producers of environmental information. The testing and the calibration laboratories as well as the proficiency testing provider (Proftest SYKE) of the SYKE laboratory center have been accredited by the Finnish Accreditation Services (EN ISO/IEC 17025, EN ISO/IEC 17043, This proficiency test has been carried out under the scope of the SYKE reference laboratory and it provides an external quality evaluation between laboratory results, and mutual comparability of analytical reliability. The success of the proficiency test requires confidential co-operation between the provider and participants. Thank you for your participation! Helsingissä 4 Kesäkuuta 2014 / Helsinki 4 June 2014 Laboratorionjohtaja / Director of 3 Proftest SYKE NW 14 / 02

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7 CONTENT 1 Introduction Organizing the proficiency test Responsibilities Participants Samples and delivery Homogeneity and stability studies Feedback from the proficiency test Processing the data Pretesting the data Assigned values Standard deviation for proficiency assessment and Results and conclusions Results Analytical methods Uncertainties of the results Evaluation of the results Summary Yhteenveto APPENDIX 1 : Participants in the proficiency test APPENDIX 2 : Preparation of the samples APPENDIX 3 : Homogeneity of the samples APPENDIX 4 : Stability of the samples APPENDIX 5 : Feedback from the proficiency test APPENDIX 6 : Evaluation of the assigned values and their uncertainties APPENDIX 7 : Terms in the results tables APPENDIX 8 : Results of each participant APPENDIX 9 : Results of participants and their uncertainties APPENDIX 10 : Summary of the s APPENDIX 11 : s in ascending order APPENDIX 12 : Influence of measurement methods to the results and results by methods.. 65 APPENDIX 13 : Estimation of the measurement uncertainties and examples of the reported values KUVAILULEHTI DOCUMENTATION PAGE PRESENTATIONBLAD Proftest SYKE NW 14 / 02 5

8 1 Introduction Proftest SYKE carried out the proficiency test (PT) for analysis of alkalinity, conductivity, N NH4, N NO3+NO2, N tot, P PO4, P tot, P PO4-dissolved, P tot-dissolved, and ph in natural waters in February A total of 38 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 proficiency test. The proficiency test was carried out in accordance with the international guidelines ISO/IEC [1], ISO [2] and IUPAC Technical report [3]. The Proftest SYKE has been accredited by the Finnish Accreditation Service as a proficiency testing provider (PT01, ISO/IEC 17043, This proficiency test has been carried out under the accreditation scope of the Proftest SYKE. 2 Organizing the proficiency test 2.1 Responsibilities Proftest SYKE, Finnish Environment Institute (SYKE), Centre, Hakuninmaantie 6, Helsinki, Finland Phone: , Fax The responsibilities in organizing the proficiency test were as follows: Mirja Leivuori coordinator Kaija Korhonen-Ylönen substitute of coordinator Keijo Tervonen technical assistance Markku Ilmakunnas technical assistance Sari Lanteri technical assistance Ritva Väisänen technical assistance Riitta Koivikko proficiency test trainee Teemu Näykki analytical expert (all the measurements) 2.2 Participants In total 38 laboratories participated in this proficiency test (Appendix 1). Altogether 87 % of the participating laboratories used accredited analytical methods at least for a part of the measurements. About 60 % of the Finnish participating laboratories provide data for use of the Finnish environmental authorities. For this proficiency test, the organizing laboratory (T03, has the codes 31 (SYKE, Helsinki) and 24 (SYKE, Oulu) in the result tables. 6 Proftest SYKE 14 / 02

9 2.3 Samples and delivery Three types of samples were delivered to the participants; synthetic, river and brackish water samples for analysis of alkalinity, conductivity, N NH4, N NO3+NO2, N tot, P PO4, P tot, P PO4-dissolved, P totdissolved, and ph. When preparing the samples, the purity of the used sample vessels was controlled. The randomly chosen sample vessels were filled with deionized water and the purity of the sample vessels was controlled after three days by analyzing P PO4, N NH4 or conductivity for phosphoric, nitrogen, and other compounds, respectively. According to the test results all used vessels fulfilled the purity requirements. The synthetic samples were mainly prepared from commercial reference material. The synthetic samples for ammonium nitrogen (N NH4 ), nitrate+nitrite nitrogen (N NO2+NO3 ), total nitrogen (N tot ) and phosphate phosphorus (P PO4 ) analysis were prepared from the NIST traceable certified reference material. Brackish water was collected on board R/V Aranda from the coastal area of the Gulf of Finland, in front of Espoo. The river water sample was collected from the River Karjaanjoki. The sample preparation is described in details in the Appendix 2. The samples were delivered on 18 February 2014 and mainly they arrived to the participants on the following day. 2 received the samples on 20 February The samples were requested to be analysed as follows: alkalinity ph, conductivity N NH4, N NO2+NO3, P PO4, P PO4-dissolved N tot, P tot, P tot-dissolved not later than The results were requested to be reported not later than 3 March Three laboratories delivered the results with delay, within two days. The preliminary results were delivered to the participants via on 10 March The correction for the preliminary results (N NO2+NO3, P PO4, P PO4-dissolved ) was delivered to the participants on 13 March 2014 due to missing results for one participant in the first preliminary results report. 2.4 Homogeneity and stability studies The homogeneity of the samples was tested by analyzing alkalinity, N NH4, N tot, P tot, P PO4-dissolved, P tot-dissolved, and ph. More detailed information of homogeneity studies is shown in Appendix 3. According to the homogeneity test results, all samples were considered homogenous. The stability of the samples was carried out by measuring ph, N NH4, and P PO4 from the samples stored at the room temperature for one day. The measurement values were checked against the results of the samples stored at 4 C. According to the test all samples were considered as stable. Along with the samples a water sample was delivered to the participants for the determination of the temperature when the samples were received. The temperature of few some samples had Proftest SYKE NW 14 / 02 7

10 been increased up to 11 C during transportation. The temperature of samples for laboratories 4, 7, 13, 19, 21, 22, 24, 33, 35 had increased up to 12.7 C, and the maximum temperature of 15.9 C was determined in the laboratory Feedback from the proficiency test The feedback from the proficiency test is shown in Appendix 5. The comments from the participants mainly dealt with their reporting errors with the samples. The comments from the provider are mainly focused to the lacking conversancy to the given information with the samples. Proftest SYKE is currently updating the results processing program and simultaneously the electronic interface will be improved. All the feedback is valuable and is exploited when improving the activities. 2.6 Processing the data Pretesting the data The normality of the data was tested by the Kolmogorov-Smirnov test. The outliers were rejected according to the Grubbs or Hampel test before calculating the mean. The results which differed more than 50 % or 5 times from the robust mean were rejected before the statistical robust results handling. More information about the statistical handling of the data is available from the Guide for participant [4] Assigned values The assigned values and their uncertainties are presented in Appendix 6. The NIST traceable calculated concentrations were used as the assigned values for measurements of N NO2+NO3, N tot, P PO4 and P tot in the synthetic samples. For the calculated assigned values the expanded measurement uncertainty (k=2) was estimated using standard uncertainties associated with individual operations involved in the preparation of the sample. The main individual source of the uncertainty was the uncertainty of the concentration in the stock solution. For the other samples and measurements the robust means of the results reported by the participants were used as the assigned value. The uncertainty of the assigned value was calculated using the robust standard deviation of the reported results [2, 4]. For the calculated assigned values, the expanded measurement uncertainty was estimated using standard uncertainties associated with individual operations involved in the preparation of the sample. The uncertainty of the calculated assigned values was less than 1 %. When using the robust mean of the participant results as the assigned value, the uncertainties of the assigned values varied between 0.3 % and 4.9 % (Appendix 6). 8 Proftest SYKE 14 / 02

11 2.6.3 Standard deviation for proficiency assessment and The target value for the standard deviation for proficiency assessment was estimated on the basis of the concentration, the results of homogeneity and stability tests, the uncertainty of the assigned value, and the long-term variation in the former proficiency tests. The target value for the total standard deviation for the ph was set to 0.2 ph units and to 5-15 % for the other measurements. When using the robust mean as the assigned value, the reliability 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 is the standard deviation for proficiency assessment (total deviation divided by 2) [3]. When testing the reliability of the assigned value the criterion was mainly fulfilled and the assigned values were considered reliable. The reliability of the target value of the standard deviation and the corresponding was estimated by comparing the deviation for proficiency assessment (s p ) with the robust standard deviation of the reported results (s rob ) [3]. The criterion s rob / s p < 1.2 was mainly fulfilled. In the following cases, the criterion for the reliability of the assigned value and for the reliability of the target value for the deviation was not met and, therefore, the evaluation of the performance is weakened in this proficiency test: Sample N3A, A1A B2P Measurement Alkalinity-2 (few participants, n=8) Ptot, Ptot-diss 3 Results and conclusions 3.1 Results The results and the performance of each laboratory are presented in Appendix 8 and the summary of the results in Table 1. The reported results with their expanded uncertainties (k=2) are presented in Appendix 9. The summary of the s is shown in Appendix 10 and z scores in the ascending order in Appendix 11. The robust standard deviations of the results varied from 0.7 to 13.5 % (Table 1).The robust standard deviation was lower than 5 % for 48 % of the results and lower than 10 % for 93 % of the results (Table 1). The robust standard deviation of results was 11.2 % and 13.5 % in the synthetic samples for P tot and N NH4 measurements, respectively. The robust standard deviations were approximately in the same range as in the previous similar proficiency test Proftest SYKE 1/2012 [5], where the deviations varied from 0.6 % to 31.7 %. For N NH4, P PO4, P PO4-dissolved and P tot-dissolved in river water the robust standard deviation was lower than in the previous similar proficiency test [5]. Proftest SYKE NW 14 / 02 9

12 Table 1. The summary of the results in the proficiency test 2/2014. Analyte Sample Unit Assigned value Mean Rob. mean Median SD rob SD rob % 2*sp % n Acc z % Alkalinity-1 A1A mmol/l N3A mmol/l Alkalinity-2 A1A mmol/l N3A mmol/l Conductivity A1J ms/m B2H ms/m N3H ms/m N-NH4 A1N µg/l B2N µg/l N3N µg/l N-NO2+NO3 A1N µg/l B2N µg/l N3N µg/l Ntot A1N µg/l B2N µg/l N3N µg/l ph A1H B2H N3H P-PO4 A1P µg/l B2P µg/l N3P µg/l P-PO4-diss B2P µg/l N3P µg/l Ptot A1P µg/l B2P µg/l N3P µg/l Ptot-diss B2P µg/l N3P µg/l Rob. mean: the robust mean, SD rob: the robust standard deviation, SD rob %: the robust standard deviation as percent, 2*s p %: the total standard deviation for proficiency assessment at the 95 % confidence interval, Acc z %: the results (%), where ïzï 2, n: the number of the participants. 3.2 Analytical methods The participants were allowed to use different analytical methods for the measurements in the PT. The used analytical methods and results of the participants grouped by methods are shown in more detail in Appendix 12. The statistical comparison of the analytical methods was done for the data where the number of the results was 5. Alkalinity Alkalinity was measured using titration with two or more end points (Alkalinity-1) by 19 laboratories. Only 5 laboratories reported alkalinity results based on one end point titration (Alkalinity-2). Systematically, the Alkalinity-1 results were lower than Alkalinity-2 results (Appendix 12). This is caused by the difference in the titration end point calculation. The 10 Proftest SYKE 14 / 02

13 standard deviation for the Alkalinity-1 measurements was 3 times lower than for the Alkalinity-2 measurements (Table 1). Conductivity Conductivity was measured mostly (19 laboratories) based on the standard method EN (Appendix 12). Ammonium nitrogen, N NH4 Most participants (55 %) determined ammonium nitrogen using the standard method SFS 3032 (manual indophenol blue spectrophotometric method) and 24 % of the participants used the corresponding automatic standard method EN ISO Depending on the sample, two to four participants used the spectrophotometric salicylate method modified for Aquachem technique and 1 2 participants used some other method (Appendix 12). In the statistical comparison between the methods the following statistically significant differences were observed: Sample /Analyte Method Conclusion N3N / NNH4 SFS 3032 SFS-EN ISO The difference between means was significant and SFS-EN ISO method gives significantly higher concentrations (Appendix 12). Nitrate + nitrite nitrogen, N NO2+NO3 Nitrate+nitrite nitrogen was determined using several methods. In average ca. 73 % of the participants used the standard method EN ISO The standard method 3030, the standard method EN ISO and the sulfanilamide spectrophotometric method after hydrazine reduction modified for Aquachem technique were used by 1 to 3 participants depending on the sample. Other method was used by 2 participants. In the statistical comparison between the methods no statistically significant differences were observed. Total nitrogen, N tot Most participants (over 65 %) determined total nitrogen according to the standard method EN ISO Depending of the sample from 5 to 7 laboratories used other methods. In the statistical method comparison no significant differences were observed between the methods. ph Approximately 52 % of the participants measured ph using universal electrode and 33 % of the participants used an electrode for low ionic waters. A specific electrode was used by one or two participants. In the statistical method comparison no significant differences were observed between the electrodes. Proftest SYKE NW 14 / 02 11

14 Phosphate phosphorus, P PO4 Approximately 40 % of the participants determined phosphate phosphorus using the standard method EN ISO (Automatic (CFA, FIA) ammonium molybdate method). Nearly as common method (34 %) was the withdrawn Finnish standard method The ammonium molybdate spectrophotometric method modified for Aquachem technique was used by 20 % of the laboratories. Only one laboratory used the standard method EN ISO 6878 (manual spectrophotometric method). In the statistical comparison between the methods the following statistically significant differences were observed: Sample /Analyte Method Conclusion B2P / PPO4 Ammonium molybdate method, Aquachem application Withdrawn SFS 3025 Manual ammoniummolybdate method. The differences between means and standard deviations were significant and Aquachem application gives significantly lower concentrations (Appendix 12). Total phosphorus, P tot Approximately 45 % of the participants determined total phosphorus using the standard method EN ISO The withdrawn standard method SFS 3026 was used by 24 % of the participants. The manual standard method EN ISO 6878 was used by 1 or 2 participants depending on the sample. Ammonium molybdate method modified for Aquachem technique was used by 6 participants. In the statistical comparison between the methods the following statistically significant differences were observed: Sample /Analyte Method Conclusion B2P / Ptot N3P / Ptot Withdrawn SFS 3026 Manual ammoniummolybdate method Ammonium molybdate method, Aquachem application Automatic (CFA, FIA) ammonium molybdate method Withdrawn SFS 3026 Manual ammoniummolybdate method Automatic (CFA, FIA) ammonium molybdate method The results gained with the withdrawn SFS 3026 method were significantly higher than those with the ammonium molybdate methods. However, some of the variation between the results is explained by the measurement uncertainties (Appendix 12). It is recommended that the withdrawn SFS 3026 method should be updated. The results gained with the withdrawn SFS 3026 method were significantly higher than those with the automatic ammonium molybdate method. The variation between the results is explained by the measurement uncertainties, thus the difference is not clearly significant (Appendix 12). Dissolved phosphorus compounds, P PO4-dissolved, P tot-dissolved The share of used analytical methods for dissolved phosphorus compounds were almost similar than for the non-filtered samples. In the present PT no details of the used filter type were questioned, otherwise some of the differences between the used methods could be explained with the used type of filters. 12 Proftest SYKE 14 / 02

15 In statistical comparison between the methods the following statistically significant differences were observed: Sample /Analyte Method Conclusion B2P / PPO4-diss Ammonium molybdate method, Aquachem application Withdrawn SFS 3025 Manual ammoniummolybdate method Automatic (CFA, FIA) ammonium molybdate method 3.3 Uncertainties of the results The results gained with the ammonium molybdate method (Aquachem application) were significantly lower than those with the automatic ammonium molybdate method or the results gained with the withdrawn SFS 3026 method (Appendix 12). The variation between the results is explained with the measurement uncertainties and the number of results is low, thus the difference is not clearly significant (Appendix 12). About 76 % of the participants reported the expanded uncertainties (k=2) with their results for at least some of their results (Table 3, Appendix 13). The range of the reported uncertainties varied between the measurements and the sample types. Several approaches were used for estimating of measurement uncertainty (Appendix 13). The most used approach was based on the internal quality data (Meth 4 and Meth 6). At maximum five laboratories used MUkit measurement uncertainty software for the estimation of their uncertainties. The free software is available in the webpage: Generally, the used approach for estimating measurement uncertainty did not make definite impact on the uncertainty estimates. In Finland has published the national quality recommendations for data entered into water quality registers, in order to promote the enhancement of environmental measurements quality standards and traceability [6]. In these instructions have recommendations for measurement uncertainties for tested analytes in natural waters from 5 % to 15 %. In this proficiency test some of participants had their measurement uncertainties within these limits, while some did not achieve them. Nevertheless, harmonization of the uncertainties estimation should be continued. Table 3. The range of the expanded measurement uncertainties (k=2, U%) reported with the results by the participants and recommendation for natural waters [6]. Analyte / Water type Synthetic, U% Brackish, U% River, U% Recommendation, U% [6] Alkalinity Alkalinity Conductivity N-NH N-NO2+NO Ntot ph ph unit P-PO P-PO4-diss Ptot Ptot-diss Proftest SYKE NW 14 / 02 13

16 4 Evaluation of the results The evaluation of the participants was based on s, which were calculated using the assigned and the estimated target values for the total deviation (Appendix 7). The s were interpreted as follows: Criteria Performance z 2 Satisfactory 2 < z < 3 Questionable z ³ 3 Unsatisfactory In total, 86 % of the results were satisfactory when total deviation of 5 15 % and 0.2 ph units from the assigned values were accepted. The summary of the performance evaluation and comparison to the previous performance is presented in Table 3. All samples passed the stability test and, thus, no estimation was needed for the effect of increased temperature during the sample transportation. Table 3. Summary of the performance evaluation in the proficiency test 2/2014. Analyte 2 s p, % Satisfactory results, % Assessment Alkalinity Good performance. Only two results were unsatisfactory (Appendix 11). In the PT SYKE 1/2012 the performance was satisfactory for 98 % of the results [5]. Alkalinity The evaluation for the samples A1A and N3A is only approximate due to the low number of the participants. The performance of the synthetic sample measurement was weak and, thus, the total performance was weak. In the PT SYKE 1/2012 the performance was satisfactory for 91 % of the results [5]. Conductivity 5 88 Both in the PT SYKE 1/2012 and PT SYKE 2/2013 the performance was satisfactory for 85 % of the results [5, 7]. N-NH In the PT SYKE 2/ % of the results and in the PT SYKE 1/ % of the results were satisfactory [5, 7]. N-NO 2+NO In the PT SYKE 2/ % of the results and in the PT SYKE 1/ % of the results were satisfactory [5, 7]. N tot Good performance. In the PT SYKE 2/ % of the results and in the PT SYKE 1/ % of the results were satisfactory [5, 7]. ph Good performance. In the PT SYKE 2/2013 the performance was satisfactory for 92 % and in the PT SYKE 1/2012 for 94 % of the results [5, 7]. P-PO In the PT SYKE 2/ % of the results and in the PT SYKE 1/ % of the results were satisfactory [5, 7]. P-PO 4-diss In the PT SYKE 1/ % of the results were satisfactory [5]. P tot The evaluation for the sample B2P is only approximate due to high variability in the results. In the PT SYKE 2/ % of the results and in the PT SYKE 1/ % of the results were satisfactory [5, 7]. P tot-diss The evaluation for the sample B2P is only approximate due to high variability in the results. In the PT SYKE 1/ % of the results were satisfactory [5]. 14 Proftest SYKE 14 / 02

17 5 Summary The Proftest SYKE carried out the proficiency test (PT) for analysis of alkalinity, conductivity, N NH4, N NO3+NO2, N tot, P PO4, P tot, P PO4-diss, P tot-diss, and ph in natural waters in February One synthetic sample, one river water sample and one brackish water sample were distributed. In total, 38 laboratories participated in this PT. Either the theoretical concentration or the robust mean of the results reported by the participants was chosen to be the assigned value for the measurand. The uncertainty for the assigned value was estimated at the 95 % confidence interval and it was generally lower than 1 % for the calculated assigned values and for assigned values based on the robust mean it was between %. The evaluation of the performance was based on the s, which was calculated using the standard deviation for proficiency assessment at 95 % confidence level. In this proficiency test 86 % of the data was regarded to be satisfactory when the result was accepted to deviate from the assigned value 0.2 ph unit in the ph determinations and 5 to 15 % in the other determinations. 6 Yhteenveto Proftest SYKE järjesti luonnonvesiä analysoiville laboratorioille pätevyyskokeen helmikuussa Pätevyyskokeessa määritettiin alkaliniteetti, ravinteet ja sähkönjohtavuus synteettisistä näytteistä, jokivedestä ja rannikkovedestä. Pätevyyskokeeseen osallistui yhteensä 38 laboratoriota. Mittaussuureen vertailuarvona käytettiin laskennallista pitoisuutta tai osallistujien tulosten robustia keskiarvoa. Vertailuarvolle laskettiin mittausepävarmuus 95 % luottamusvälillä. Vertailuarvon laajennettu epävarmuus oli alle 1 % laskennallista pitoisuutta vertailuarvona käytettäessä ja muilla välillä %. Pätevyyden arviointi tehtiin z-arvon avulla ja tulosten sallittiin poiketa vertailuarvosta phmäärityksessä 0.2 ph-yksikköä ja muissa määrityksissä 5 15 %. Koko aineistossa hyväksyttäviä tuloksia oli 86 %. Proftest SYKE NW 14 / 02 15

18 REFERENCES 1. SFS-EN ISO 17043, Conformity assessment General requirements for Proficiency Testing. 2. ISO 13528, Statistical methods for use in proficiency testing by interlaboratory comparisons. 3. Thompson, M., Ellison, S. L. R., Wood, R., The International Harmonized Protocol for the Proficiency Testing of Analytical Chemistry laboratories (IUPAC Technical report). Pure Appl. Chem. 78: , 4. Proftest SYKE Guide for laboratories: Running proficiency test ( 1E2CE936D48C%7D/39886). 5. Korhonen-Ylönen, K., Leivuori, M., Näykki, T., Järvinen, O., Tervonen, K., Lanteri, S., Ilmakunnas, M. and Väisänen, R. Laboratorioiden välinen pätevyyskoe 1/2012: Alkaliniteetti, ph, ravinteet ja sähkönjohtavuus luonnonvesistä. Suomen ympäristökeskuksen raportteja 15/ Näykki, T., Kyröläinen, H., Witick, A., Mäkinen, I. Pehkonen, R., Väisänen, T., Sainio, P. ja Luotola M Laatusuositukset ympäristöhallinnon vedenlaaturekistereihin vietävälle tiedolle: vesistä tehtävien analyyttien määritysrajat, mittausepävarmuudet sekä säilytysajata ja tavat. (Quality recommendations for data entered into the environmental administration s water quality registers: Quantification limits, measurement uncertainties, strorage times and methods associated with analytes determined from waters). Ympäristöhallinnon ohjeita 4/2013. (Environmental administration Guidelines 4/2013). 45 s. ( 7. Korhonen-Ylönen, K., Näykki, T., Leivuori, M., Tervonen, K., Lanteri, S. and Ilmakunnas, M. Proficiency test SYKE 2/2013. Chlorophyll a, colour, conductivity, nutrients, ph and turbidity in natural waters. Reports of Finnish Environment Institute 20/ Proftest SYKE 14 / 02

19 APPENDIX 1 (1/1) APPENDIX 1: Participants in the proficiency test Estonia Finland Russia Sweden Estonian Marine Institute, Tartu University Marine Ecology Lab of Marine Systems Institute Tallinn University of Technology, Thermal Engineering Department Ahma Ympäristö Oy, Ilmajoki Ahma Ympäristö Oy, Rovaniemi Almalab Eurofins Viljavuuspalvelu, Mikkeli Haapaveden kaupungin ympäristölaboratorio HSY Käyttölaboratorio, Helsinki HY, Tvärminnen eläintieteellinen asema, Hanko Jyväskylän yliopisto, Ympäristöntutkimuskeskus KCL Kymen Laboratorio Oy Kokemäenjoen vesistön vesiensuojeluyhdistys ry Lounais-Suomen vesi- ja ympäristötukimus Oy Maintpartner Oy, Laboratorio- ja ympäristöpalvelut Metropolilab Oy Metsäntutkimuslaitos, Rovaniemi Metsäntutkimuslaitos/Keskuslaboratorio MTT, Laboratorio Nab Labs Oy, Oulu Neste Oil Oyj, Tutkimus ja kehitys/vesilaboratorio Novalab Oy Ramboll Finland Oy, Ramboll Analytics, Lahti Saimaan Vesi- ja Ympäristötutkimus Oy, Lappeenranta Savo-Karjalan Ympäristötutkimus Oy, Joensuu Savo-Karjalan Ympäristötutkimus Oy, Kuopio SGS Inspection Services Oy SYKE of Hakuninmaa, Helsinki SYKE of Joensuu SYKE of Oulun SYKE/Marine Research Centre Tampereen Vesi/Viemärilaitoksen laboratorio Vaasan kaupungin ympäristölaboratorio Yara Suomi Oy, Uusikaupunki Ålands miljö- och hälsoskyddsmyndighet, Laboratoriet Hydromet, Saint Petersburg, Russia Russian State Hydrometeorological University ITM, Stockholm University Proftest SYKE NW 14 / 02 17

20 APPENDIX 2 (1/1) APPENDIX 2: Preparation of the samples Analyte/Sample A1J B2H N3H g25 Initial concentration. ms/m Addition ms/m KCl Assigned value. ms/m A1H B2H N3H ph Initial concentration. ph unit Na2HPO4/ Addition. mmol/l KH2PO4 ph unit Assigned value. ph unit A1A N3A Alkalinity-1 Initial concentration. mmol/l Alkalinity-2 Na2CO3 - - Addition. mmol/l 0.17 Assigned value. mmol/l 0.337/ /0.397 A1P B2P N3P PPO4 Initial concentration. µg/l Addition. µg/l KH2PO Assigned value. µg/l A1P B2P N3P Ptot Initial concentration. µg/l Addition. µg/l KH2PO Assigned value. µg/l B2P N3P PPO4diss Initial concentration. µg/l Addition. µg/l Assigned value. µg/l Ptotdiss Initial concentration. µg/l Addition. µg/l Assigned value. µg/l A1N B2N N3N NNO2+NO3 Initial concentration. µg/l Addition. µg/l NaNO Assigned value. µg/l A1N B2N N3N NNH4 Initial concentration. µg/l < 1 2 Addition. µg/l NH4Cl Assigned value. µg/l A1N B2N N3N Ntot Initial concentration. µg/l NaNO3 90 Addition. µg/l NH4Cl 19 Na2EDTA Assigned value. µg/l Proftest SYKE 14 / 02

21 APPENDIX 3 (1/1) APPENDIX 3: Homogeneity of the samples Homogeneity of the brackish and river water samples was tested by analysing the concentration of the analyte from 8 subsamples. Criteria for homogeneity: s a /s p <0.5 and s bb 2 <c, where s p % = standard deviation for proficiency assessment s a = analytical deviation, standard deviation of the results within sub samples s bb = between-sample deviation, standard deviation of the results between sub samples c = F1 x s all 2 + F2 x s a 2, where s all 2 = (0.3 x s p ) 2 F1 = 2.01 and F2 = 1.25, when the number of sub samples is 8 Analyte/Sample Analyte/Sample µg/l or mmol/l sp,% sp sa sa/sp sa/sp<0,5? sbb sbb 2 c sbb 2 <c? Alkalinity/N3A Yes Yes NNH4/B2N Yes Yes NNH4/N3N Yes Yes Ntot/B2N Yes Yes Ntot/N3N Yes Yes Ptot/B2P No 1) Yes Ptot/N3P Yes Yes 1) The analytical deviation explained the un-filling of the criteria. Based on the other measurements the sample B2 could be regarded as homogeneous. Conclusion: Based on the test the samples could be regarded homogenous. Homogeneity of the ph samples was tested by measuring ph value from 10 subsamples. Criteria for homogeinity: s bb < 0.5 s p Analyte/Sample Analyte/Sample sp 0,5 sp Standard deviation (sbb) sbb < 0,05? ph/ B2H Yes ph/ N3H Yes Conclusion: The criteria for homogeneity fulfilled. The samples could be regarded as homogenous. Proftest SYKE NW 14 / 02 19

22 APPENDIX 4 (1/1) APPENDIX 4: Stability of the samples The samples were delivered 18 February 2014 and they arrived to the participants mainly on the following day. The samples were requested to be analysed as follows: Alkalinity, ph, condictivity, N NH4, N NO3+NO2, P PO4, P PO4-dissolved 20 February 2014 N tot, P tot, P tot-dissolved before 28 February 2014 Stability of ph-, N NH4 - and P PO4 -samples was tested by analyzing the samples stored at the temperatures 4 and 25 ºC. Criteria for stability: D < 0.3 s p, where D = the difference of results measured from the samples stored at the temperatures 4 C and 25 C s p = standard deviation for proficiency assessment ph Sample Results Sample Results Sample Results Date (25 ºC) (4 ºC) Date (25 ºC) (4 ºC) Date (25 ºC) (4 ºC) A1H B2H N3H D sp D <0.3 sp YES D < 0.3 sp YES D < 0.3 sp YES N NH4 Sample Results, µg/l Sample Results, µg/l Sample Results, µg/l Date (25 ºC) (4 ºC) Date (25 ºC) (4 ºC) Date (25 ºC) (4 ºC) A1N B2N N3N D sp D <0.3 sp NO D < 0.3 sp YES D < 0.3 sp YES P PO4 Sample Results, µg/l Sample Results, µg/l Sample Results, µg/l Date (25 ºC) (4 ºC) Date (25 ºC) (4 ºC) Date (25 ºC) (4 ºC) A1P B2P N3P D sp D <0.3 sp YES D < 0.3 sp YES D < 0.3 sp NO Conclusion: According to the test, the concentration of N NH4 in the sample A1N and P PO4 in the sample N3P might change, if the temperature in the sample increased during the distribution. However, the difference is smaller than the analytical error. Thus the measurements and samples could be regarded stable enough for the proficiency test. 20 Proftest SYKE 14 / 02

23 APPENDIX 5 (1/1) APPENDIX 5: Feedback from the proficiency test Laboratoratory Comments on technical excecution Action / Proftest 2 Sample N3N had leaked a bit. The provider will be more carefully in preparation of samples. 26 Part of the results was missing from the preliminary report. Due to the unexpected technical malfunction some of the results were not included in the data treatment. The provider corrected this and updated preliminary report was delivered to all participants. Comments to the results Action / Proftest 10 The participant had reported the result of N NO2+NO3 erroneously in the sample N3N. The right result was 464 µg/l. 18, 28, 25 In the preliminary results the unit of nitrogen compounds was mg/l when it should be µg/l. The result of N NO2+NO3 was an outlier in the statistical treatment, and thus it did not affect the performance evaluation. If the result had been reported correctly, it would have been satisfactory. The participant can re-calculate s according to the guide for participating laboratories in Proftest proficiency testing schemes ( proftest/ en > Running proficiency test). This error did not influence the performance evaluation of the participants. The error was corrected in the final report. The provider will be more carefully in the future. FEEDBACK TO THE PARTICIPANTS Comments 14 The laboratory reported the measurement uncertainty for ph in ph units, not as percent as required. The provider did not correct this. In the data evaluation program measurement uncertainty is handled as percent, so the participant should follow the instructions from the provider. 30 The laboratory reported two or three replicate results, though no replicates were requsted. The provider used average value in the evaluation. Proftest SYKE NW 14 / 02 21

24 APPENDIX 6 (1/1) APPENDIX 6: Evaluation of the assigned values and their uncertainties Analyte Sample Unit Assigned value Uncertainty, % Evaluation method of assigned value u/sp Alkalinity-1 A1A mmol/l 0,337 1,4 Robust mean 0,19 N3A mmol/l 0,375 1,6 Robust mean 0,21 Alkalinity-2 A1A mmol/l 0,370 5,4 Mean 0,72 N3A mmol/l 0,397 4,4 Mean 0,59 Conductivity A1J ms/m 6,53 1,2 Robust mean 0,24 B2H ms/m ,2 Robust mean 0,24 N3H ms/m 8,98 1,1 Robust mean 0,22 N-NH4 A1N µg/l 19,4 0,3 Calculated value 0,02 B2N µg/l 73,3 3,7 Robust mean 0,25 N3N µg/l 75,0 3,5 Robust mean 0,23 N-NO2+NO3 A1N µg/l 90,5 1) 0,6 Calculated value 0,06 B2N µg/l 154 1,8 Robust mean 0,18 N3N µg/l 469 2,9 Robust mean 0,29 Ntot A1N µg/l 208 1) 0,3 Calculated value 0,02 B2N µg/l 452 3,3 Robust mean 0,22 N3N µg/l 815 2,6 Robust mean 0,26 ph A1H 5,53 0,3 Robust mean 0,08 B2H 7,97 0,6 Robust mean 0,24 N3H 7,42 0,7 Robust mean 0,26 P-PO4 A1P µg/l 9,33 1) 0,3 Calculated value 0,03 B2P µg/l 21,6 1,8 Robust mean 0,18 N3P µg/l 41,6 1,7 Robust mean 0,17 P-PO4-diss B2P µg/l 21,1 3,3 Robust mean 0,33 N3P µg/l 41,0 2,0 Robust mean 0,20 Ptot A1P µg/l 9,33 1) 0,3 Calculated value 0,03 B2P µg/l 26,6 3,9 Robust mean 0,39 N3P µg/l 48,6 2,5 Robust mean 0,25 Ptot-diss B2P µg/l 25,2 4,9 Robust mean 0,49 N3P µg/l 46,1 2,6 Robust mean 0,26 1) NIST traceable assigned value. Criterion for reliability of the assigned value u/s p < 0.3, where: s p = target value of the standard deviation for proficiency assessment u = standard uncertainty of the assigned value 22 Proftest SYKE 14 / 02

25 APPENDIX 7 (1/1) APPENDIX 7: Terms in the results tables Results of each participant Analyte The tested parameter Sample The code of the sample z value Calculated as follows: z = (x i - X)/s p, where x i = the result of the individual laboratory X = the reference value (the assigned value) s p = the target value of the standard deviation for proficiency assessment Assigned value The reference value 2* s p % The target value of total standard deviation for proficiency assessment (s p ) at the 95 % confidence level 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, % n (stat) Number of results in statistical processing Summary on the s S satisfactory ( -2 z 2) Q questionable ( 2< z < 3), positive error, the result deviates more than 2 s p from the assigned value q questionable ( -3 < z < -2), negative error, the result deviates more than 2 s p from the assigned value U unsatisfactory (z 3), positive error, the result deviates more than 3 s p from the assigned value u unsatisfactory (z -3), negative error, the result deviates more than 3 s p from the assigned value Robust analysis The items of data are sorted into increasing order, x 1, x 2, x i,,x p. Initial values for x * and s * are calculated as: x* = median of x i (i = 1, 2,...,p) s* = 1,483 median of x i * x (i = 1, 2,...,p) The mean x* and s* are updated as follows: Calculate φ = 1.5 s*. A new value is then calculated for each result x i (i = 1, 2 p): { x* - φ, if x i < x* - φ x i * = { x* + φ, if x i > x* + φ, { x i otherwise The new values of x * and s * are calculated from: * * x = å xi / p * * * 2 s = å( xi - x ) /( 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 [2]. Proftest SYKE NW 14 / 02 23

26 APPENDIX 8 (1/19) APPENDIX 8: Results of each participant 1 Alkalinity-2 mmol/l A1A mmol/l N3A Conductivity ms/m A1J ms/m B2H ms/m N3H N-NH4 µg/l A1N µg/l B2N µg/l N3N N-NO2+NO3 µg/l A1N µg/l B2N µg/l N3N Ntot µg/l A1N µg/l B2N µg/l N3N ph A1H B2H N3H P-PO4 µg/l A1P µg/l B2P µg/l N3P Ptot µg/l A1P µg/l B2P µg/l N3P Alkalinity-2 mmol/l A1A mmol/l N3A Conductivity ms/m A1J ms/m B2H ms/m N3H N-NH4 µg/l A1N µg/l B2N µg/l N3N N-NO2+NO3 µg/l A1N µg/l B2N µg/l N3N Ntot µg/l A1N µg/l B2N µg/l N3N ph A1H B2H N3H Proftest SYKE 14 / 02

27 APPENDIX 8 (2/19) 2 P-PO4 µg/l A1P µg/l B2P µg/l N3P Ptot µg/l A1P µg/l B2P µg/l N3P Alkalinity-1 mmol/l A1A mmol/l N3A Conductivity ms/m A1J ms/m B2H ms/m N3H N-NH4 µg/l A1N µg/l B2N µg/l N3N N-NO2+NO3 µg/l A1N µg/l B2N µg/l N3N Ntot µg/l A1N µg/l B2N µg/l N3N ph A1H B2H N3H P-PO4 µg/l A1P µg/l B2P µg/l N3P P-PO4-diss µg/l B2P µg/l N3P Ptot µg/l A1P µg/l B2P µg/l N3P Ptot-diss µg/l B2P µg/l N3P Alkalinity-1 mmol/l N3A Conductivity ms/m B2H ms/m N3H N-NH4 µg/l B2N µg/l N3N N-NO2+NO3 µg/l B2N < µg/l N3N Ntot µg/l B2N < µg/l N3N < Proftest SYKE NW 14 / 02 25

28 APPENDIX 8 (3/19) 4 ph B2H N3H P-PO4 µg/l B2P µg/l N3P P-PO4-diss µg/l B2P µg/l N3P Ptot µg/l B2P < µg/l N3P < Ptot-diss µg/l B2P < µg/l N3P < N-NH4 µg/l B2N N-NO2+NO3 µg/l B2N Ntot µg/l B2N ph B2H P-PO4 µg/l B2P P-PO4-diss µg/l B2P Ptot µg/l B2P Ptot-diss µg/l B2P Alkalinity-1 mmol/l A1A mmol/l N3A Conductivity ms/m A1J ms/m B2H ms/m N3H N-NH4 µg/l A1N µg/l B2N µg/l N3N N-NO2+NO3 µg/l A1N µg/l B2N µg/l N3N Ntot µg/l A1N µg/l B2N µg/l N3N ph A1H B2H N3H P-PO4 µg/l A1P µg/l B2P µg/l N3P P-PO4-diss µg/l B2P µg/l N3P Proftest SYKE 14 / 02

29 APPENDIX 8 (4/19) 6 Ptot µg/l A1P µg/l B2P µg/l N3P Ptot-diss µg/l B2P µg/l N3P Alkalinity-1 mmol/l A1A mmol/l N3A Conductivity ms/m A1J ms/m B2H ms/m N3H N-NH4 µg/l A1N µg/l B2N µg/l N3N N-NO2+NO3 µg/l A1N µg/l B2N µg/l N3N Ntot µg/l A1N µg/l B2N µg/l N3N ph A1H B2H N3H P-PO4 µg/l A1P µg/l B2P µg/l N3P P-PO4-diss µg/l B2P µg/l N3P Ptot µg/l A1P µg/l B2P µg/l N3P Ptot-diss µg/l B2P µg/l N3P Alkalinity-1 mmol/l A1A mmol/l N3A Conductivity ms/m A1J ms/m N3H N-NH4 µg/l A1N µg/l N3N N-NO2+NO3 µg/l A1N µg/l N3N ph A1H N3H Proftest SYKE NW 14 / 02 27