Bundesanstalt für Materialforschung und prüfung BAM H Kipphardt

Bundesanstalt für Materialforschung und –prüfung (BAM) H. Kipphardt, M. Czerwensky and R. Matschat BAM I Department 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

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 Measurement result in field laboratory e. g. copper in tap water traceable commercial calibration solutions Primary calibration solution e. g. PTB-001 Primary standard © H. Kipphardt, BAM I. 1 e. g. BAM-Y 001 (copper) SI BAM I Department for Analytical Chemistry; Reference Materials Berlin, November 2006, 2

© H. Kipphardt, BAM I. 1 (1) Commercial calibration solutions BAM I Department for

© H. Kipphardt, BAM I. 1 Dissolution of high purity metals BAM I Department

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

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

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

Primary standards of type A. . . w(E) known to better than 0. 01 %. . . approach: 100 % - Imp. . . measurement of all impurity elements (including O, N. . . ) BAM I Department for Analytical Chemistry; Reference Materials © H. Kipphardt, BAM I. 1 . . . measurement of total impuritiy content (bulk and surface) Berlin, November 2006, 8

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

w(Cu, BAM-Y 001)= 0. 999 968 0. 000 010 with k=2 BAM I Department for Analytical Chemistry; Reference Materials Berlin, November 2006, 10 © H. Kipphardt, BAM I. 1 BAM-Y 001: overview of impurities

$Measurements using different methods mass fraction in mg/kg 100 HR ICP MS ET AAS$

Measurements using different methods mass fraction in mg/kg 100 HR ICP MS ET AAS ICP-OES HE/PAA HE/IR Photometrie INAA 10 1 0, 01 Ag As BAM I Bi C Ca Cr Fe Department for Analytical Chemistry; Reference Materials N Ni O Pb S Sb Se Si Sn Berlin, November 2006, 11 © H. Kipphardt, BAM I. 1 0, 1

© H. Kipphardt, BAM I. 1 BAM-Y 001 certification report BAM I Department for

© H. Kipphardt, BAM I. 1 BAM-Y 001 Certificate BAM I Department for Analytical

Certified materials Element Value Uncertainty Upper limit estimates BAM-Y 001 Cu 0, 999 970 0, 000 010 - BAM-Y 002 Fe 0, 999 862 0, 000 044 P BAM-Y 003 Si 0, 999 91 0, 000 07 H, F, Cl, Br, I BAM-Y 004 Pb 0, 999 92 0, 000 06 H, P, Si, F, Cl, Br, I BAM-Y 005 Sn 0, 999 91 0, 000 06 H, Si, F, Cl, Br, I BAM-Y 006 W 0, 999 81 0, 000 10 H, F, Cl, Br, I BAM-Y 007 Bi 0, 999 90 0, 000 07 H, K, Si, S, F, Cl, Br, I BAM-Y 008 Ga 0, 999 92 0, 000 07 H, Si, F, Cl, Br, I BAM-Y 009 Na. Cl 0, 999 84 0, 000 09 H, F, K, Si, S BAM-Y 010 KCl 0, 999 83 0, 000 10 H, F, Si, S, Mn, Fe, As BAM I Department for Analytical Chemistry; Reference Materials Berlin, November 2006, 14 © H. Kipphardt, BAM I. 1

© H. Kipphardt, BAM I. 1 Elements under investigation. . . BAM I Department

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

© H. Kipphardt, BAM I. 1 BAM Cu type B: overview of impurities 500

Conclusion 1 © H. Kipphardt, BAM I. 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 BAM I Department for Analytical Chemistry; Reference Materials Berlin, November 2006, 18

• 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 BAM I Department for Analytical Chemistry; Reference Materials Berlin, November 2006, 19 © H. Kipphardt, BAM I. 1 CCQM-P 62: Background

CCQM-P 62: methods used 1 2 3 4 5 6 10 BAM II ICPQMS ICP-SFMS (MR) ICP OES ICP-SFMS ET AAS ICP-QMS, INAA Al ICPQMS ICP-SFMS (MR) ICP OES ICP-SFMS ET AAS ICP-QMS Cu ICPQMS ICP-SFMS (MR) ICP OES ICP-SFMS (HR) ET AAS ICP-QMS Fe ICP OES ICPQMS ICP-SFMS (MR) ICP OES ICP-SFMS (MR) ET AAS INAA Pb ICPQMS ICP-SFMS, ET AAS ICP OES ICP-SFMS ET AAS ICP-QMS Zn ICPQMS ICP-SFMS ICP OES (MR), ET AAS ICP-SFMS ET AAS ICP-QMS, INAA BAM I Department for Analytical Chemistry; Reference Materials Berlin, November 2006, 20 © H. Kipphardt, BAM I. 1 Ag

CCQM-P 62: Additional IDMS experiments © H. Kipphardt, BAM I. 1 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-P 62 BAM I Department for Analytical Chemistry; Reference Materials Berlin, November 2006, 21

• 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] BAM I Department for Analytical Chemistry; Reference Materials Berlin, November 2006, 22 © H. Kipphardt, BAM I. 1 CCQM-P 62: overview of IDMS results

agreement < 30 % BAM I Department for Analytical Chemistry; Reference Materials Berlin, November 2006, 23 © H. Kipphardt, BAM I. 1 CCQM-P 62: results Pb

agreement 30 % BAM I Department for Analytical Chemistry; Reference Materials Berlin, November 2006, 24 © H. Kipphardt, BAM I. 1 CCQM-P 62: results Zn

well agreement, one exception BAM I Department for Analytical Chemistry; Reference Materials Berlin, November 2006, 25 © H. Kipphardt, BAM I. 1 CCQM-P 62: results Ag

problem: factor 5 BAM I Department for Analytical Chemistry; Reference Materials Berlin, November 2006, 26 © H. Kipphardt, BAM I. 1 CCQM-P 62: results Cu

problem: factor 10 BAM I Department for Analytical Chemistry; Reference Materials Berlin, November 2006, 27 © H. Kipphardt, BAM I. 1 CCQM-P 62: results Fe

problem: > factor 100 BAM I Department for Analytical Chemistry; Reference Materials Berlin, November 2006, 28 © H. Kipphardt, BAM I. 1 CCQM-P 62: results Al

problem: factor 8 BAM I Department for Analytical Chemistry; Reference Materials Berlin, November 2006, 29 © H. Kipphardt, BAM I. 1 CCQM-P 62: results total

CCQM-P 62: overview of results level / mg/kg observed spread / % max. contr. from homogen. / % 3 200 6 Al 2 3 orders of mag. 1 Cu 0. 7 factor 5 20 Fe 2. 7 factor 10 4 Pb 0. 3 30 15 Zn 1. 3 23 7 total 10 factor 8 BAM I Department for Analytical Chemistry; Reference Materials © H. Kipphardt, BAM I. 1 Ag Berlin, November 2006, 30

• 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 BAM I Department for Analytical Chemistry; Reference Materials Berlin, November 2006, 31 © H. Kipphardt, BAM I. 1 Conclusion 2: CCQM-P 62