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SIMS analysis of oxygen isotopes: matrix effects in complex minerals and glasses

Eiler, John M. and Graham, Colin and Valley, John W. (1997) SIMS analysis of oxygen isotopes: matrix effects in complex minerals and glasses. Chemical Geology, 138 (3-4). pp. 221-244. ISSN 0009-2541. doi:10.1016/S0009-2541(97)00015-6.

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A large instrumental mass fractionation (IMF) occurs during the measurement of oxygen isotope ratios by secondary ion mass spectrometry and the magnitude of this fractionation can be dependent upon sample chemistry, resulting in so-called 'matrix effects'. We have made 373 measurements of the ^(18)O^−/^(16)O^− ratio (±0.5–1.1‰ internal precision, 1 s.d.) in 40 silicate and phosphate minerals and glasses for the purpose of characterizing this matrix effect. The magnitude of IMF decreases with increasing atomic mass of the sample, although this relationship is too poorly defined to be the basis of a precise empirical correction scheme. IMF is well correlated with simple measures of chemistry among related minerals and glasses (e.g. forsterite content in olivine; Na/(Na+K) in feldspathic glass), and with the atomic abundance of certain elements among several mineral groups (e.g. the sum: (Fe+Mn) in garnets, olivines and pyroxenes). Significant differences in IMF between minerals and glasses of the same chemical composition correlate with the mass of network modifying cations. Instrumental mass fractionation correlates strongly with sputter rate for albite and seven silicate glasses. Two mechanisms for producing matrix effects are proposed: (1) differences in the efficiency with which kinetic energy is transferred to the secondary oxygen atoms from the atoms in the near-surface region of the sample, and (2) simple variations in the fraction of sputtered oxygen atoms that are ionized, such that the observed instrumental fractionation diminishes as that fraction approaches 1. The correlation between sputter rate and instrumental mass fractionation in silicate glass and albite is well predicted by model (1). Our data suggest that a large range of silicate materials can be standardized using: (1) interpolation among chemically similar standards; (2) correlation of IMF with Fe+Mn content in materials rich in those elements; (3) model (1), particularly for materials that are compositionally related to standards One or more of these methods appear to be applicable to most silicate materials of interest and should permit accurate standardization of ion probe analyses without the stringent requirements that standards and unknowns be compositionally identical or compositionally similar members of the same solid solution series.

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Additional Information:© 1997 Elsevier Science B.V. Received 9 December 1996; accepted 4 February 1997. This work was supported by funding from the Department of Energy grant 93ER14389 JWV., National Science Foundation grants EAR9304372 JWV. and EAR9303975 S. Epstein and E. Stolper., and National Energy Research Council grant GR9/01806 (CMG). The invaluable contribution of John Craven to this study in instrument tuning and maintenance, ideas and suggestions, and helpful comments on the manuscript, is gratefully acknowledged. The ion microprobe laboratory is generously supported by NERC. We thank Mike Spicuzza for assistance in the stable isotope laboratory at the University of Wisconsin, and Ed Stolper for his encouragement and financial support of the first author’s contribution to this work. The manuscript benefited from thorough and insightful reviews by Ian Hutcheon, Kevin McKeegan and Richard Hervig. We thank Tom Tombrello and John Hartman for their insightful comments on this work, and Serge Nadau, George Rossman and Ian Cartwright for supplying some of the samples for this study.
Group:UNSPECIFIED, UNSPECIFIED, Division of Geological and Planetary Sciences
Funding AgencyGrant Number
Department of Energy (DOE)93ER14389
National Energy Research CouncilGR9/01806
Subject Keywords:Ion microprobe; Oxygen isotopes; Matrix effects; Standards
Issue or Number:3-4
Record Number:CaltechAUTHORS:20121023-130726712
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Official Citation:John M Eiler, Colin Graham, John W Valley, SIMS analysis of oxygen isotopes: matrix effects in complex minerals and glasses, Chemical Geology, Volume 138, Issues 3–4, 10 June 1997, Pages 221-244, ISSN 0009-2541, 10.1016/S0009-2541(97)00015-6. (
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:35038
Deposited By: Ruth Sustaita
Deposited On:23 Oct 2012 20:52
Last Modified:09 Nov 2021 23:12

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