High-precision measurement and standard calibration of triple oxygen isotopic compositions (δ18O, Δ′17O) of sulfate by F2 laser fluorination

Abstract

A new approach for measuring the triple oxygen isotope composition of sulfate minerals was developed using fluorine gas and an infrared laser to generate O2. A correction for the mass-dependent isotope effect observed during barite fluorination was rigorously calibrated. Analyte gas purification was performed via numerous cryofocus steps and the introduction of an in-line gas chromatograph. As with previous methods, our fluorination technique still requires pairing with independent δ18O measurements made by TC/EA conversion to carbon monoxide, but leads to higher yields than BrF5-based methods. We first calibrated our method against known silicate standards (UWG-2, SCO, NBS-28). Following from this, we report high-precision triple oxygen isotope ratios for international sulfate standards (IAEA-SO-5, IAEA-S O-6, NBS-127), and an internal laboratory standard, JMG. Replicate analyses of JMG yielded a Δ′17O value of −0.057 ± 0.004‰ (standard error), demonstrating per-meg level precision that approaches instrumental limits. We provide δ17O and δ18O values that can be translated into any preferred reference frame for comparison with gases, water, or rocks/minerals. Quantification of differences in triple oxygen isotope composition of the standard reference materials further enables application of this measure and approach on environmental and geological materials.