Influence of glass composition on secondary ion mass spectrometry instrumental mass fractionation for Si and Ca isotopic analyses

Rationale In situ secondary ion mass spectrometry (SIMS) analysis requires the use of standards to unravel the instrumental mass fractionation (IMF) induced by the analytical procedures. Part of this IMF might be caused by the nature of the sample and the differences in composition and structure between the sample and the standards. This “matrix effect” has been tentatively corrected for by using standards with chemical compositions equivalent to the samples, or by the empirical use of chemical parameters. However, these corrections can only be applied to a narrow compositional range and fail to take proper account of the matrix effect when a wider chemical field is tested. Methods We synthesized a series of glasses whose compositions span a very large part of the NCMAS (Na2O‐CaO‐MgO‐Al2O3‐SiO2) system. Si and Ca isotopic analyses were performed on two ion microprobes (Cameca IMS‐1270 and IMS‐1280). Results The matrix effect observed may reach 20‰ between extreme compositions and cannot be accounted for by the previously used “chemical” parameters (e.g. SiO2, SiO2/(SiO2 + Al2O3)) nor by the NBO/T parameter. It therefore appears necessary to consider not only the structure of the glasses, but also the nature of the different atoms. Consequently, we assessed the use of another concept, the optical basicity, based on the electronegativities of the constitutive elements of glass. Conclusions We show that this parameter significantly improves the efficiency of the matrix‐effect correction and that it can be applied across the entire NCMAS compositional range studied here. Furthermore, the use of optical basicity reduces the number of glass standards required for a reliable isotopic study, and it can also be used to probe the structure of the glass. Copyright © 2016 John Wiley & Sons, Ltd.