A new calcite reference material for in situ oxygen isotope analysis using secondary ion mass spectrometry: development and application constraints†

Abstract

The oxygen isotopic microanalysis of calcite is essential for obtaining high spatial resolution data linked to microstructures, a challenge for conventional techniques. This analysis, however, relies heavily on matrix-matched reference materials, of which only a few calcite standards are available. In this study, an inorganically precipitated calcite vein sample (WS-1) was evaluated through 225 SIMS oxygen isotope analyses and was found to have a homogeneous isotopic composition, with an external reproducibility ≤0.21‰ (1σ), suggesting its potential as a SIMS reference material. The precise δ¹⁸O_VPDB value, determined via traditional gas-source IRMS, was −16.52 ± 0.13‰ (1SD). Matrix effects were assessed using various carbonates, including abiotic aragonite (VS001/1-A), three abiotic calcites (NBS18, Cal-1, WS-1), and a high-Mg calcite (gorgonian coral). The results revealed negligible matrix effects between abiotic aragonite and calcites but significant differences between calcites and high-Mg calcite, likely due to Mg content or differences in biogenic crystal morphology and trace organic composition. This study demonstrates the utility of in situ oxygen isotopic microanalysis for calcite but emphasizes the need for caution when analyzing high-Mg calcitic skeletons.