Synthesis and Characterization of Metallic (Fe‐Ni, Fe‐Ni‐Si) Reference Materials for SIMS ³⁴S/³²S Measurements

Secondary ion mass spectrometry (SIMS) is often used to determine the sulfur contents and isotope ratios of metallic alloys in meteorites or high‐pressure experimental samples. However, SIMS analyses involve calibration and the determination of instrumental mass fractionation in reference materials with a matrix composition similar to that of the unknown samples. To provide metallic reference materials adapted to S measurements via SIMS, we synthesised a series of twenty‐eight alloys comprising four FeNi(±Si) compositions (Fe 95 Ni 5 , Fe 90 Ni 10 , Fe 80 Ni 20 , and Fe 80 Ni 15 Si 5 ) with S contents varying from 100 μg g −1 to 4 g/100g using the “melt spinning” method, which guarantees that the metal alloys are rapidly quenched at ~ 10 6 K s −1 . Sulfur contents were determined at the Service d'Analyse des Roches et Minéraux at the CRPG and absolute δ 34 S values were determined by multi‐collector ICP‐MS (MC‐ICP‐MS, ThermoScientific Neptune) and isotope ratio mass spectrometry (Thermoscientific Delta V). A δ 34 S value of 16.01 ± 0.31‰ was consistently obtained using the MC‐ICP‐MS, which was indistinguishable of the δ 34 S value of the FeS starting material (15.95 ± 0.08‰). It suggests that S did not undergo isotopic fractionation during the melting process. Of fifteen samples containing ≤ 5000 μg g −1 S, SIMS measurements with 15‐μm‐diameter spots were repeatable to within 10% relative (1 standard deviation, 1 s ) for S contents and 2‰ for δ 34 S values. However, samples containing > 5000 μg g −1 S showed FeNi–FeS immiscibility, leading to minor dispersion of the S mass fractions and δ 34 S values. No matrix effect was observed for Fe‐Ni, Si, or S contents in terms of the calibration curves and instrumental mass fractionation. We ultimately recommend eight samples as reliable reference materials for S isotopic measurements by SIMS, which we can share worldwide with other laboratories.