Investigation of matrix effects for Pb isotope ratio measurements by multiple collector ICP-MS: verification and application of optimized analytical protocols
M. Rehkamper et K. Mezger, Investigation of matrix effects for Pb isotope ratio measurements by multiple collector ICP-MS: verification and application of optimized analytical protocols, J ANAL ATOM, 15(11), 2000, pp. 1451-1460
Previous studies have demonstrated the potential of multiple-collector indu
ctively coupled plasma mass spectrometry (MC-ICP-MS) for precise Pb isotopi
c measurements using admixed Tl for "external normalization" of instrumenta
l mass discrimination. The Micromass IsoProbe is a new, single-focusing MC-
ICP-MS instrument that does not employ an electrostatic sector for energy-f
ocusing. Instead, a hexapole collision cell is used to thermalize the ion b
eam. This study presents the first in-depth investigation of the applicatio
n of the IsoProbe to Pb isotope ratio measurements. With a Tl-based mass bi
as correction, multiple analyses of mixed Pb-Tl standard solutions typicall
y display reproducibilities (+/-2 sigma) of about 50 ppm for Pb-207:Pb-206,
100 ppm for Pb-208:Pb-206 and Pb-206:Pb-204, 150 ppm for Pb-207:Pb-204 and
175 ppm for Pb-208:Pb-204. Using an empirically optimized exponential law
normalization, the Pb isotope data show excellent agreement with reference
values obtained by thermal ionization mass spectrometry. The cross-calibrat
ion between NIST SRM 981 and 982 demonstrates that accurate results can be
obtained with this technique over a wide range of Pb isotopic compositions.
The Tl-corrected Pb data obtained on the IsoProbe, however, display correl
ations with the Pb:Tl ratio of the analyzed solutions. The addition of larg
e amounts of Tl to the samples is unfavorable for the accurate measurement
of the low-intensity Pb-204 ion beam. Analytical artifacts may also be gene
rated if high concentrations of concomitant elements are present in the sam
ple solutions. Matrix effects and instrumental memory, however, can be read
ily overcome by the adoption of appropriate analytical protocols and it is
demonstrated that sample measurements can achieve the same levels of precis
ion and accuracy as are routinely obtained for analyses of pure standard so
lutions.