This certification campaign allows assignment of certified values for Ag, As, Cd, Cu, Fe, Hg, CH3Hg, Mn, Pb, Se and Zn with associated uncertainties following ISO guidelines. The certified values are derived from measurement results provided by the laboratories participating in the characterization study. Only validated methods were applied in the characterization of IAEA-476 CRM. As the certified values are combinations of SI traceable individual results, they are also traceable to the International System of Units.
14
15 APPENDIX I
RESULTS FROM THE LONG TERM STABILITY STUDY:
Figures 3-18 present individual mass fractions measured in unit kept 1 year at reference temperature (-20°C); at normal temperature (+20°C).
FIG. 3. Results of long term stability study for silver.
FIG. 4. Results of long term stability study for arsenic.
16
FIG. 5. Results of long term stability study for cadmium.
FIG. 6. Results of long term stability study for cobalt
FIG. 7. Results of long term stability study for chromium.
17 FIG. 8. Results of long term stability study for copper.
FIG. 9. Results of long term stability study for iron.
FIG. 10. Results of long term stability study for total mercury.
18
FIG. 11. Results of long term stability study for methyl mercury.
FIG. 12. Results of long term stability study for manganese.
FIG. 13. Results of long term stability study for nickel.
19 FIG. 14. Results of long term stability study for lead.
FIG. 15. Results of long term stability study for selenium.
FIG. 16. Results of long term stability study for strontium.
20
FIG. 17. Results of long term stability study for vanadium.
FIG. 18. Results of long term stability study for zinc.
21 APPENDIX II
RESULTS OF THE CHARACTERIZATION MEASUREMENTS
The reported by the participating results, their expended uncertainty, measurement techniques and CRMs used for quality assurance purposes are presented in Tables 8-23. Figures 19–34 provide graphical presentation of the individual results and their expanded uncertainties as well as the assigned value for the respective trace element and its expanded uncertainty (k=2), as a solid and dashed lines respectively.
TABLE 8. SILVER: RESULTS AS REPORTED BY PARTICIPANTS (mg kg-1) Laboratory
code Mean Expanded
uncertainty (U) CRM Method
6 0.055 0.027 DORM-2 ICP-MS
7 0.060 0.004 SRM 1566b NAA
9 0.065 0.001 Blank Spike ICP-MS
12 0.051 0.016 NIST1566b ICP-MS
IAEA 0.058 0.007 IAEA 407 ICP-MS
FIG. 19. Laboratory results for silver mass fraction (mg kg-1) in IAEA-476 .
22
TABLE 9. ARSENIC: RESULTS AS REPORTED BY PARTICIPANTS (mg kg-1) Laboratory
code Mean Expanded
uncertainty (U) CRM Method
3 22.2 1.6 NIST SRM-1547 NAA
5 21.2 1.7 IAEA 407 ET-AAS
6 21.7 3.3 DORM-2 ICP-MS
7 20.8 1.0 SRM 1566b NAA
8 20.8 1.2 IAEA407 ICP-MS
9 20.7 1.8 TORT-3 ICP-MS
11 19.9 1.0 NIST 1566b NAA
IAEA 21.4 3.0 IAEA 407 ICP-MS
FIG. 20. Laboratory results for arsenic mass fraction (mg kg-1) in IAEA-476.
23 TABLE 10. CADMIUM: RESULTS AS REPORTED BY PARTICIPANTS (mg kg-1)
Laboratory
code Mean Expanded
uncertainty (U) CRM Method
2 0.021 0.009 DORM 3 ICP-MS
5 0.027 0.002 IAEA 407 ET-AAS
6 0.030 0.009 DORM-2 ICP-MS
8 0.030 0.003 IAEA436 ICP-MS
9 0.029 0.001 TORT-3 ICP-MS
12 0.025 0.005 NIST1566b ICP-MS
IAEA 0.030 0.004 IAEA 407 ET-AAS
IAEA 0.032 0.004 IAEA 407 ICP-MS
IAEA 0.028 0.001 ID-ICP-MS
FIG. 21. Laboratory results for cadmium mass fraction (mg kg-1) in IAEA-476.
24
TABLE 11. COBALT: RESULTS AS REPORTED BY PARTICIPANTS (mg kg-1) Laboratory
code Mean Expanded
uncertainty (U) CRM Method
3 0.098 0.008 NIST SRM-1547 NAA
6 0.089 0.027 DORM-2 ICP-MS
7 0.101 0.006 SRM 1566b NAA
8 0.133 0.017 IAEA407 ICP-MS
9 0.096 0.008 TORT-3 ICP-MS
11 0.295 0.005 NIST 1566b NAA
12 0.076 0.018 NIST1566b ICP-MS
IAEA 0.147 0.024 IAEA 407 ICP-MS
FIG. 22. Laboratory results for cobalt mass fraction (mg kg-1) in IAEA-476.
25 TABLE 12. CHROMIUM: RESULTS AS REPORTED BY PARTICIPANTS (mg kg-1)
Laboratory
code Mean Expanded
uncertainty (U) CRM Method
2 3.16 0.14 DORM 3 ICP-MS
3 4.96 0.40 NIST SRM-1547 NAA
6 3.96 0.59 DORM-2 ICP-MS
7 5.01 0.26 SRM 1566b NAA
9 5.05 0.57 TORT-3 ICP-MS
11 3.30 0.20 NIST 2976 NAA
12 3.26 0.71 NIST1566b ICP-MS
13 2.69 0.54 IAEA-436 ICP-MS
FIG. 23. Laboratory results for chromium mass fraction (mg kg-1) in IAEA-476.
26
TABLE 13. COPPER: RESULTS AS REPORTED BY PARTICIPANTS (mg kg-1) Laboratory
code Mean Expanded
uncertainty (U) CRM Method
2 2.38 0.23 DORM 3 ICP-MS
5 2.62 0.28 IAEA 407 ET-AAS
6 2.32 0.35 DORM-2 ICP-MS
8 2.25 0.18 IAEA436 ICP-MS
9 2.30 0.71 TORT-3 ICP-MS
12 1.87 0.46 NIST1566b ICP-MS
13 2.49 0.50 IAEA-436 ICP-MS
IAEA 2.55 0.36 IAEA 407 ET-AAS
IAEA 2.72 0.33 IAEA 407 ICP-MS
IAEA 2.28 0.08 ID-ICP-MS
FIG. 24. Laboratory results for copper mass fraction (mg kg-1) in IAEA-476.
27 TABLE 14. IRON: RESULTS AS REPORTED BY PARTICIPANTS (mg kg-1)
Laboratory
code Mean Expanded
uncertainty (U) CRM Method
2 122 8 DORM 3 ICP-OES
3 151 12 NIST SRM-1547 NAA
6 143 21 DORM-2 ICP-MS
7 149 18 SRM 1566b NAA
9 139 11 TORT-3 ICP-MS
11 148 6 NIST 1566b NAA
12 125 28 NIST1566b ICP-MS
13 127 36 IAEA-436 ICP-OES
IAEA 149 21 IAEA 407 F-AAS
FIG. 25. Laboratory results for iron mass fraction (mg kg-1) in IAEA-476.
28
TABLE 15. TOTAL MERCURY: RESULTS AS REPORTED BY PARTICIPANTS (mg kg
-1)
Laboratory
code Mean Expanded
uncertainty (U) CRM Method
1 0.595 0.052 IAEA407 GC-ICPMS
1 0.605 0.016 IAEA407 ID-ICP-MS
3 0.572 0.044 DORM-4/BCR-463 CV-AAS
6 0.534 0.107 DORM-3 ICP-MS
8 0.527 0.038 IAEA407 ICP-MS
9 0.564 0.072 TORT-3 CV-AFS
10 0.600 0.102 DORM-4 Solid -AAS
11 0.637 0.076 DORM-4 CV-AAS
IAEA 0.568 0.024 ID-ICP-MS
IAEA 0.582 0.070 SRM 2703 Solid -AAS
FIG. 26. Laboratory results for total mercury mass fraction (mg kg-1) in IAEA-476.
29 TABLE 16. METHYL MERCURY: RESULTS AS REPORTED BY PARTICIPANTS (mg kg-1 as Hg)
Laboratory
code Mean Expanded
uncertainty (U) CRM Method
1 0.541 0.051 IAEA407 GC-ICPMS
3 0.537 0.026 BCR-463 CV-AFS
9 0.503 0.041 TORT-3 CV-AFS
10 0.562 0.073 DORM-4 CV-AFS
12 0.490 0.012 NRC DORM4 GC-AFS
IAEA 0.499 0.070 IAEA 407 GC-AFS
IAEA 0.530 0.024 ID-ICP-MS
FIG. 27. Laboratory results for methyl mercury mass fraction (mg kg-1as Hg) in IAEA-476.
30
TABLE 17. MANGANESE: RESULTS AS REPORTED BY PARTICIPANTS (mg kg-1) Laboratory
code Mean Expanded
uncertainty (U) CRM Method
2 17.6 1.0 DORM 3 ICP-MS
5 17.0 0.7 NIST 1566b F-AAS
6 16.7 1.7 DORM-2 ICP-MS
8 16.2 1.1 IAEA407 ICP-MS
9 17.5 4.1 TORT-3 ICP-MS
11 16.1 1.0 NIST 1566b NAA
12 15.6 3.4 NIST1566b ICP-MS
13 14.0 4.0 IAEA-436 ICP-MS
IAEA 18.3 3.3 IAEA 407 ET-AAS
IAEA 15.5 2.2 SRM 2976 F-AAS
FIG. 28. Laboratory results for manganese mass fraction (mg kg-1) in IAEA-476.
31 TABLE 18. NICKEL: RESULTS AS REPORTED BY PARTICIPANTS (mg kg-1)
Laboratory
code Mean Expanded
uncertainty (U) CRM Method
2 3.85 0.36 DORM 3 ICP-MS
6 4.56 0.68 DORM-2 ICP-MS
9 5.10 0.72 TORT-3 ICP-MS
12 3.72 0.89 NIST1566b ICP-MS
13 3.63 1.26 IAEA-436 ICP-MS
IAEA 4.9 0.1 ID-ICP-MS
FIG. 29. Laboratory results for nickel mass fraction (mg kg-1) in IAEA-476.
32
TABLE 19. LEAD: RESULTS AS REPORTED BY PARTICIPANTS (mg kg-1) Laboratory
code Mean Expanded
uncertainty (U) CRM Method
2 0.676 0.084 DORM 3 ICP-MS
5 0.533 0.037 NIST 1566b ET-AAS
6 0.660 0.132 DORM-2 ICP-MS
8 0.725 0.044 IAEA407 ICP-MS
9 0.704 0.043 TORT-3 ICP-MS
12 0.558 0.138 NIST1566b ICP-MS
13 0.621 0.156 IAEA-461 ICP-MS
IAEA 0.637 0.115 IAEA 407 ET-AAS
IAEA 0.669 0.080 IAEA 407 ICP-MS
IAEA 0.657 0.023 ID-ICP-MS
FIG. 30. Laboratory results for lead mass fraction (mg kg-1) in IAEA-476.
33 TABLE 20. SELENIUM: RESULTS AS REPORTED BY PARTICIPANTS (mg kg-1)
Laboratory
code Mean Expanded
uncertainty (U) CRM Method
2 2.15 0.20 DORM 3 ICP-MS
3 2.27 0.18 NIST SRM-1547 NAA
5 1.99 0.05 NIST 1566b Hyd-AAS
6 2.19 0.44 DORM-2 ICP-MS
7 2.20 0.12 SRM 1566b NAA
8 2.09 0.44 IAEA436 ICP-MS
9 2.05 0.07 TORT-3 ICP-MS
11 2.20 0.40 NIST 1566b NAA
12 1.97 0.42 NIST1566b ICP-MS
IAEA 2.12 0.30 IAEA 407 ICP-MS
FIG. 31. Laboratory results for selenium mass fraction (mg kg-1) in IAEA-476.
34
TABLE 21. STRONTIUM: RESULTS AS REPORTED BY PARTICIPANTS (mg kg-1) Laboratory
code Mean Expanded
uncertainty (U) CRM Method
2 147 17 ICP-OES
3 160 18 NIST SRM-1547 NAA
6 145 22 TORT-3 ICP-MS
7 154 8 SRM 1566b NAA
8 151 8 IAEA407 ICP-MS
9 151 11 TORT-3 ICP-MS
12 128 38 NIST1566b ICP-MS
13 128 38 IAEA-436 ICP-MS
IAEA 146 20 IAEA 407 F-AAS
IAEA 124 17 IAEA 407 ICP-MS
FIG. 32. Laboratory results for strontium mass fraction (mg kg-1) in IAEA-476.
35 TABLE 22. VANADIUM: RESULTS AS REPORTED BY PARTICIPANTS (mg kg-1)
Laboratory
code Mean Expanded
uncertainty (U) CRM Method
6 0.408 0.082 TORT-3 ICP-MS
9 0.280 0.035 TORT-3 ICP-MS
13 0.254 0.064 IAEA-461 ICP-MS
IAEA 0.430 0.060 IAEA 407 ICP-MS
FIG. 33. Laboratory results for vanadium mass fraction (mg kg-1) in IAEA-476.
36
TABLE 23. ZINC: RESULTS AS REPORTED BY PARTICIPANTS (mg kg-1) Laboratory
code Mean Expanded
uncertainty (U) CRM Method
2 51.6 2.2 DORM 3 ICP-OES
3 55.0 4.0 NIST SRM-1547 NAA
5 53.1 2.1 IAEA 407 F-AAS
6 56.4 8.5 DORM-2 ICP-MS
7 55.3 2.7 SRM 1566b NAA
8 51.8 3.2 IAEA436 ICP-MS
9 50.2 2.4 TORT-3 ICP-MS
11 62.0 2.0 NIST 1566b NAA
13 52.0 10.0 IAEA-436 ICP-MS
IAEA 52.1 7.3 IAEA 407 F-AAS
IAEA 53.0 7.4 IAEA 407 ICP-MS
IAEA 51.9 2.0 ID-ICP-MS
FIG. 34. Laboratory results for zinc mass fraction (mg kg-1) in IAEA-476.
37 REFERENCES
[1] INTERNATIONAL ORGANIZATION FOR STANDARDIZATION, ISO/IEC 17025:2017. General requirements for the competence of testing and calibration laboratories, Geneva, (2017).
[2] INTERNATIONAL ORGANIZATION FOR STANDARDIZATION, ISO Guide 17034:2016, General requirements for the competence of reference material producers, ISO, Geneva (2016).
[3] INTERNATIONAL ORGANIZATION FOR STANDARDIZATION, ISO Guide 35:2006, Reference Materials – General and Statistical Principles for Certification, ISO, Geneva (2006).
[4] LINSINGER T., PAUWELS J., VAN DER VEEN A., SCHIMMEL H., LAMBERTY A., Homogeneity and stability of reference materials, Accredit. Qual. Assur. 6 1 (2001) 20–25.
[5] INTERNATIONAL ORGANIZATION FOR STANDARDIZATION, Statistical methods for use in proficiency testing by interlaboratory comparisons, ISO 13528:2005 (E), ISO, Geneva (2005).
[6] JOINT COMMITTEE FOR GUIDES IN METROLOGY (JGCM), Evaluation of measurement data – Guide to the expression of uncertainty in measurement, JGCM 100:
2008 (GUM with miNor corrections), (2008).
[7] VESPER, A., EMONS, H., GNEZDA, M., JAIN, C., MILLER, G., REJ, R., SCHUMANN, G., TATE, J., THIENPONT, L., VAKS, E., Characterization and qualification of commutable reference materials for laboratory medicine; Approved Guideline, CLSI document EP30-A, Clinical and Laboratory Standards Institute, Wayne, PA (2010).
39 LIST OF PARTICIPANTS
BRAZIL
Favaro, D. IPEN-CNEN /SP
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Franco, H. ALS Environmental (Vancouver)
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440 Desalaberry Ave
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Environmental Chemistry Research Hakuninmaantie 6
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Fisicaro, P. Laboratoire National Essais
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Oster, C. Laboratoire National Essais
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40
GERMANY
Manthey-Karl, M. MAX RUBNER-INSTITUT
Institut für Sicherheit und Qualität bei Milch und Fisch
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INTERNATIONAL ATOMIC ENERGY AGENCY
Horsky, M. IAEA Laboratories Seibersdorf
Reaktorstrasse 1
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Azemard, S. International Atomic Energy Agency
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Vassileva, E. International Atomic Energy Agency
4 quai Antoine 1er 98000 MONACO
PERU
Bedregal, P. Instituto PeruaNo de Energía Nuclear
Laboratorio de Técnicas Analíticas (TEAN)
Av. Canadá 1470 SAN BORJA LIMA 41
RUSSINA FEDERATION
Glushchenkova, G.F. CJSC "Water Research and Control Center"
CJSC "WRCC"
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SLOVENIA
Jacimovic, R. Jozef Stefan Institute
Dept. of Environmental Sciences Jamova cesta 39
1000 LJUBLJANA
41 UNITED KINGDOM
Fisher, A. School of Geography, Earth and
Environmental Science University of Plymouth Drake Circus
PLYMOUTH, DEVON PL4 8AA UNITED STATES OF AMERICA
Mc Farland, F. Brooks Applied Labs
18804 North Creek Pkwy, Suit #100 Bothell
WASHINGTON 98011
43 CONTRIBUTORS TO DRAFTING AND REVIEW
The following persons, contributes to the draft and review of this report
Azemard, S. International Atomic Energy Agency
Vasileva-Veleva, E. International Atomic Energy Agency
The following persons, contributes to the review of this report
Arend, V. International Atomic Energy Agency
Barilaro-Hamonic, L. International Atomic Energy Agency
Horski, M International Atomic Energy Agency
Sander, S. International Atomic Energy Agency
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IAEA/AQ/57
IAEA Analytical Quality in Nuclear Applications Series No. 57
Certification of Trace Elements and Methylmercury Mass Fractions in Fish Homogenate IAEA-476
INTERNATIONAL ATOMIC ENERGY AGENCY VIENNA
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