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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 (Fe95Ni5, Fe90Ni10, Fe80Ni20, and Fe80Ni15Si5) 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 ~ 106 K s−1. Sulfur contents were determined at the Service d'Analyse des Roches et Minéraux at the CRPG and absolute δ34S values were determined by multi‐collector ICP‐MS (MC‐ICP‐MS, ThermoScientific Neptune) and isotope ratio mass spectrometry (Thermoscientific Delta V). A δ34S value of 16.01 ± 0.31‰ was consistently obtained using the MC‐ICP‐MS, which was indistinguishable of the δ34S 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, 1s) for S contents and 2‰ for δ34S values. However, samples containing > 5000 μg g−1 S showed FeNi–FeS immiscibility, leading to minor dispersion of the S mass fractions and δ34S 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. [ABSTRACT FROM AUTHOR]

Effects of H2O on the solution behavior of fluorine and chlorine in peralkaline sodium aluminosilicate glasses quenched from melts at high temperature (1400 °C) and pressure (1.5 GPa) were studied by combining solubility measurements and Raman spectroscopy. With increasing H2O content from 0 to ~10 wt%, the fluorine solubility increases from 3.3 to 4.4 mol% in Al-free glasses and from 6.3 to 9.3 mol% in Al-rich glasses (10 mol% Al2O3). In contrast, in the same H2O concentration range the chlorine solubility decreases from 5.7 to 3.4 mol% in Al-free glasses and from 3.6 to 1.7 mol% in Al-rich glasses. In Al-free glasses, interaction between H2O and the silicate to depolymerize the network is Q4 + H2O ↔ Q²(H) and Q³ + H2O ↔ Q²(H). The effect of water on silicate melt structure is different in halogen-bearing melts because in hydrous melt systems both F and Cl can act to depolymerize the melt further. For fluorine, this is accomplished via formation of Si-F, Al-F, and Na-F bonding in addition to Si-OH, whereas in chlorine-bearing hydrous melts, there is no interaction between Si4+ and Cl-. The halogen solubility in the magmatic liquid influences mineral/melt partition coefficients of chlorine and fluorine and implies partition coefficients different from unity. Moreover because of the contrasting effects of H2O on fluorine and chlorine solubility, the Cl/F ratio in magmas formed in water-rich environments such as subduction zones can be a sensitive indicator of H2O content during arc magmas genesis. Transport properties of melts, such as diffusion and viscosity, also vary differently in halogen-bearing hydrous melts compared with halogen-free systems. Moreover, those effects on melt properties are the strongest in F-bearing systems. [ABSTRACT FROM AUTHOR]

The effect of pressure and temperature on the structure of silicate melts coexisting with silica-saturated aqueous electrolyte fluids enriched in fluorine or chlorine in the Na2O-Al2O3-SiO2-H2O system has been described. In situ measurements were conducted with the samples at desired temperatures and pressures in a hydrothermal diamond-anvil cell (HDAC) by using microRaman and FTIR spectroscopy techniques. The data were acquired at temperatures and pressures up to 800 °C and 1264 MPa, respectively. In silicate melts, the intensity of the infrared bands assigned to the stretch vibration of OH-groups is smaller than those of coexisting molecular H2O when F and Cl are present in the melt structure. This difference reflects the interaction of F or Cl with H2O in the melts. With decreasing pressure and temperature (P-T) conditions, SiF complexes are favored in the melt over that in coexisting fluid, perhaps because of decreasing silicate concentration in fluids with decreasing temperature and pressure. In these melts, the solubility of Cl, likely in the form of NaCl, increases with decreasing P-T conditions, whereas the abundance of such complexes in coexisting fluids decreases in favor of HCl. Our experimental data were employed to model the ascent of a fluid-saturated magma from the upper mantle to the shallow crust. This modeling offers insights into F and Cl partitioning between and the speciation of F and Cl in melts and magmatic fluids. We suggest that the formation of stable SiF and NaCl complexes and their increasing solubilities in silicate melts during magma ascent may explain the late volcanic degassing of F and Cl compared with the degassing behavior of other volatile species. [ABSTRACT FROM AUTHOR]