1. BAM IDepartment for Analytical Chemistry; Reference Materials Berlin, November 2006, 1 © H. Kipphardt, BAM I.1 Characterisation of High Purity Metals as Primary Standards for Element Determination Bundesanstalt für Materialforschung und –prüfung (BAM) H. Kipphardt, M. Czerwensky and R. Matschat

2. BAM IDepartment for Analytical Chemistry; Reference Materials Berlin, November 2006, 2 © H. Kipphardt, BAM I.1 High purity materials... … serve as primary standards for chemical measurements (mass or amount of substance of an identified substance)... used for calibration … to establish SI traceability SI Primary standard e.g. BAM-Y001 (copper) Primary calibration solution e.g. PTB-001 traceable commercial calibration solutions Measurement result in field laboratory e.g. copper in tap water

3. BAM IDepartment for Analytical Chemistry; Reference Materials Berlin, November 2006, 3 © H. Kipphardt, BAM I.1 (1) Commercial calibration solutions

4. BAM IDepartment for Analytical Chemistry; Reference Materials Berlin, November 2006, 4 © H. Kipphardt, BAM I.1 Dissolution of high purity metals

5. BAM IDepartment for Analytical Chemistry; Reference Materials Berlin, November 2006, 5 © H. Kipphardt, BAM I.1 Materials certified for purity...... hardly exist... usually incompletely characterised using semi-quantitative measurement techniques... no uncertainty statement

6. BAM IDepartment for Analytical Chemistry; Reference Materials Berlin, November 2006, 6 © H. Kipphardt, BAM I.1 Target: Primary standards...... of high metrological quality... small uncertainty according to GUM... serve as national standards for element analysis in Germany (with PTB)

7. BAM IDepartment for Analytical Chemistry; Reference Materials Berlin, November 2006, 7 © H. Kipphardt, BAM I.1 Primary standards of Type A...... intended for analyte calibration (i.e. element amount standard)... certified for the mass fraction of the matrix element in a ‘pure’ material... for use within the NMIs multiplication to the field via cooperation

8. BAM IDepartment for Analytical Chemistry; Reference Materials Berlin, November 2006, 8 © H. Kipphardt, BAM I.1 Primary standards of type A... w(E) known to better than 0.01 %... measurement of total impuritiy content (bulk and surface)... measurement of all impurity elements (including O, N...)... approach: 100 % -  Imp

9. BAM IDepartment for Analytical Chemistry; Reference Materials Berlin, November 2006, 9 © H. Kipphardt, BAM I.1 Certification approach ET and HG AAS ICP OES, (INAA) Gas and Non-metal analysis HR ICP MS LA-ICP MS FI-ICP MS validation additional information CGHE; PAA nuclear methods lowering detection limits combined uncertainty (GUM) certified value check of dissolution step continuous nebulization validation additional information consistency check

10. BAM IDepartment for Analytical Chemistry; Reference Materials Berlin, November 2006, 10 © H. Kipphardt, BAM I.1 BAM-Y001: overview of impurities w(Cu, BAM-Y001)= 0.999 968  0.000 010 with k=2

11. BAM IDepartment for Analytical Chemistry; Reference Materials Berlin, November 2006, 11 © H. Kipphardt, BAM I.1 Measurements using different methods HR ICP MS ET AAS ICP-OES HE/PAA HE/IR Photometrie INAA mass fraction in mg/kg 0,01 0,1 1 10 100 AgAsBiCCaCrFeNNiOPbSSbSeSiSn

12. BAM IDepartment for Analytical Chemistry; Reference Materials Berlin, November 2006, 12 © H. Kipphardt, BAM I.1 BAM-Y001 certification report

13. BAM IDepartment for Analytical Chemistry; Reference Materials Berlin, November 2006, 13 © H. Kipphardt, BAM I.1 BAM-Y001 Certificate

14. BAM IDepartment for Analytical Chemistry; Reference Materials Berlin, November 2006, 14 © H. Kipphardt, BAM I.1 Certified materials ElementValueUncertaintyUpper limit estimates BAM-Y001Cu0,999 9700,000 010- BAM-Y002Fe0,999 8620,000 044P BAM-Y003Si0,999 910,000 07H, F, Cl, Br, I BAM-Y004Pb0,999 920,000 06H, P, Si, F, Cl, Br, I BAM-Y005Sn0,999 910,000 06H, Si, F, Cl, Br, I BAM-Y006W0,999 810,000 10H, F, Cl, Br, I BAM-Y007Bi0,999 900,000 07H, K, Si, S, F, Cl, Br, I BAM-Y008Ga0,999 920,000 07H, Si, F, Cl, Br, I BAM-Y009NaCl0,999 840,000 09H, F, K, Si, S BAM-Y010KCl0,999 830,000 10H, F, Si, S, Mn, Fe, As

15. BAM IDepartment for Analytical Chemistry; Reference Materials Berlin, November 2006, 15 © H. Kipphardt, BAM I.1 Elements under investigation...

16. BAM IDepartment for Analytical Chemistry; Reference Materials Berlin, November 2006, 16 © H. Kipphardt, BAM I.1 Materials of type B... intended for matrix investigations (spectrometry)... certified for very low metallic impurities (typically 1-50  g/kg)

17. BAM IDepartment for Analytical Chemistry; Reference Materials Berlin, November 2006, 17 © H. Kipphardt, BAM I.1 BAM Cu type B: overview of impurities 500 mg/kg oxygen !

18. BAM IDepartment for Analytical Chemistry; Reference Materials Berlin, November 2006, 18 © H. Kipphardt, BAM I.1 Conclusion 1 primary standards seem to be necessary, - also for analytical chemistry their realisation has been successfully demonstrated realisation requires a variety of methods and staying power

19. BAM IDepartment for Analytical Chemistry; Reference Materials Berlin, November 2006, 19 © H. Kipphardt, BAM I.1 CCQM-P62: Background Purity of Nickel with respect to six metallic analytes Quantity of interest: w(Ag)+w(Al)+w(Cu)+w(Fe)+w(Pb)+w(Zn) and interim results; expected range: 0.1 – 5.0 mg/kg Participants: 5 + BAM I, BAM II for homogeneity and IDMS NRC, for IDMS BAM Status: completed

20. BAM IDepartment for Analytical Chemistry; Reference Materials Berlin, November 2006, 20 © H. Kipphardt, BAM I.1 CCQM-P62: methods used 12345610 BAM IBAM II AgICP- QMS ICP-SFMS (MR) ICP OESICP-SFMSET AASICP-QMS, INAA AlICP- QMS ICP-SFMS (MR) ICP OESICP-SFMSET AASICP-QMS CuICP- QMS ICP-SFMS (MR) ICP OESICP-SFMS (HR) ET AASICP-QMS FeICP OES ICP- QMS ICP-SFMS (MR) ICP OESICP-SFMS (MR) ET AASINAA PbICP- QMS ICP-SFMS, ET AAS ICP OESICP-SFMSET AASICP-QMS ZnICP- QMS ICP-SFMS (MR), ET AAS ICP OESICP-SFMSET AASICP-QMS, INAA

21. BAM IDepartment for Analytical Chemistry; Reference Materials Berlin, November 2006, 21 © H. Kipphardt, BAM I.1 CCQM-P62: Additional IDMS experiments Because of the inconsistent results in the pilot study, additionally IDMS was applied as ‘reference’: IDMS for Al is impossible NRC: Ag, Pb, Zn BAM: Pb, Zn, Cu, Fe IDMS is not used to calculate mean of CCQM-P62

22. BAM IDepartment for Analytical Chemistry; Reference Materials Berlin, November 2006, 22 © H. Kipphardt, BAM I.1 CCQM-P62: overview of IDMS results Good consistency of results for Pb and Zn. Some experimental problems with Fe measurements. w(Ag+Cu+Fe+Pb+Zn) = (3,09 ± 0,12) mg/kg [without Al]

23. BAM IDepartment for Analytical Chemistry; Reference Materials Berlin, November 2006, 23 © H. Kipphardt, BAM I.1 CCQM-P62: results Pb agreement < 30 %

24. BAM IDepartment for Analytical Chemistry; Reference Materials Berlin, November 2006, 24 © H. Kipphardt, BAM I.1 CCQM-P62: results Zn agreement 30 %

25. BAM IDepartment for Analytical Chemistry; Reference Materials Berlin, November 2006, 25 © H. Kipphardt, BAM I.1 CCQM-P62: results Ag well agreement, one exception

26. BAM IDepartment for Analytical Chemistry; Reference Materials Berlin, November 2006, 26 © H. Kipphardt, BAM I.1 CCQM-P62: results Cu problem: factor 5

27. BAM IDepartment for Analytical Chemistry; Reference Materials Berlin, November 2006, 27 © H. Kipphardt, BAM I.1 CCQM-P62: results Fe problem: factor 10

28. BAM IDepartment for Analytical Chemistry; Reference Materials Berlin, November 2006, 28 © H. Kipphardt, BAM I.1 CCQM-P62: results Al problem: > factor 100

29. BAM IDepartment for Analytical Chemistry; Reference Materials Berlin, November 2006, 29 © H. Kipphardt, BAM I.1 CCQM-P62: results total problem: factor 8

30. BAM IDepartment for Analytical Chemistry; Reference Materials Berlin, November 2006, 30 © H. Kipphardt, BAM I.1 CCQM-P62: overview of results level / mg/kgobserved spread / % max. contr. from homogen. / % Ag32006 Al23 orders of mag.1 Cu0.7factor 520 Fe2.7factor 104 Pb0.33015 Zn1.3237 total10factor 8

31. BAM IDepartment for Analytical Chemistry; Reference Materials Berlin, November 2006, 31 © H. Kipphardt, BAM I.1 Conclusion 2: CCQM-P62 number of participants low => limited interest (or ability) concluded discrepancies by a factor of 8 for the value of the target quantity, not covered by the corresponding uncertainties discrepancies based on discrepancies for individual impurities Results for a ‘rather simple task’ => worldwide the characterisation of high purity materials is not to be comparable. few clusters of laboratories can be detected 3 laboratories report rather low values IDMS confirms the lower values for Pb, Zn, Ag, Cu, Fe GDMS shows very low value for Al => may be for some labs the blank is not fully under control

32. BAM IDepartment for Analytical Chemistry; Reference Materials Berlin, November 2006, 32 © H. Kipphardt, BAM I.1 END