Sims Oxygen Isotope Matrix Effects In Silicate Glasses: Quantifying The Role Of Chemical Composition

Instrumental mass fractionation (IMF) associated with Secondary Ion Mass Spectrometry (SIMS) measurements of oxygen isotope compositions in silicate glasses was studied using a set of 27 synthesized glasses spanning a compositionally broad range of six major oxides: SiO2, TiO2, Al2O3, total FeO (FeOt), MgO and CaO. The impact of chemical composition on the IMF values was investigated using a Cameca 1280-HR during a single SIMS analytical session operated under constant instrumental conditions. The data measured were compared with the 818O values obtained by laser fluorination gas source mass-spectrometry (LF). The offset between the 818O(LF) and 818O(SIMS) was found to reach up to 5%o. Our data document that SIMS oxygen isotope matrix effects in silicate glasses strongly depend on the chemical composition of silicate glasses, here the cation-oxygen bond strength was found to have a strong influence on the IMF value. We tested a variety of models based on single oxide contents and various composition-dependent parameters, but none were fully satisfactory for predicting IMF. Neither mean atomic mass nor NBO/T (the ratio of non-bridging oxygens per tetrahedrally coordinated cation) show a strong correlation with the IMF values (R2 of 0.45 and 0.46, respectively). Among the single oxides, only the model based on the SiO2 content is useful for prediction of the IMF in silicate glasses, but this model has a large standard error (1a = +/- 0.90%o) and was also found to break down for glasses with high Na and K contents. We propose an empirical model based on the correlation of six major element oxides that shows a strong correlation with IMF (R2 = 0.98, 1a = +/- 0.40%o). This model describes the experimental data with uncertainties that are roughly a factor of two better than the correction methods proposed in earlier studies. We also investigated using the correlation between IMF and isotope I-18O index, which describes the correlation between atomic bond strength and relative oxygen isotope enrichment in silicate substances (R2 = 0.87). Although our efforts provide refinements to the SIMS determination of 818O in natural silicate glasses, truly accurate IMF corrections will need further refinements related to the impact of alkali elements.