The oxidation state of sulfur in synthetic and natural glasses determined by X-ray absorption spectroscopy

Abstract

Sulfur K-edge X-ray absorption near edge structure (XANES) spectra were recorded for experimental glasses of various compositions prepared at different oxygen fugacities ( fO 2) in one-atmosphere gas-mixing experiments at 1400 °C. This sample preparation method only results in measurable S concentrations under either relatively reduced (log fO 2 < −9) or oxidised (log fO 2 > −2) conditions. The XANES spectra of the reduced samples are characterised by an absorption edge crest at 2476.4 eV, typical of S 2−. In addition, spectra of Fe-bearing compositions exhibit a pronounced absorption edge shoulder. Spectra for all the Fe-free samples are essentially identical, as are the spectra for the Fe-bearing compositions, despite significant compositional variability within each group. The presence of a sulfide phase, such as might exsolve on cooling, can be inferred from a pre-edge feature at 2470.5 eV. The XANES spectra of the oxidised samples are characterised by an intense transition at 2482.1 eV, typical of the sulfate anion SO 4 2−. Sulfite (SO 3 2−) has negligible solubility in silicate melts at low pressures. The previous identification of sulfite species in natural glass samples is attributed to an artefact of the analysis (photoreduction of S 6+). S 4+ does, however, occur unambiguously with S 6+ in Fe-free and Fe-poor compositions prepared in equilibrium with CaSO 4 at 4–16 kbar, and when buffered with Re/ReO 2 at 10 kbar. Solubility of S 4+ thus requires partial pressures of SO 2 considerably in excess of 1 bar. A number of experiments were undertaken in an attempt to access intermediate fO 2s more applicable to terrestrial volcanism. Although these were largely unsuccessful, S 2− and S 6+ were found to coexist in some samples that were not in equilibrium with the imposed fO 2. The XANES spectra of natural olivine-hosted melt inclusions and submarine glasses representative of basalts at, or close to, sulfide saturation show mainly dissolved S 2−, but with minor sulfate, and additionally a peak at 2469.5 eV, which, although presumably due to immiscible sulfide, is 1 eV lower than that typical of FeS. These sulfate and sulfide-related peaks disappear with homogenisation of the inclusions by heating to 1200 °C followed by rapid quenching, suggesting that both these features are a result of cooling under natural conditions. The presence of small amounts of sulfate in otherwise reduced basaltic magmas may be explained by the electron exchange reaction: S 2− + 8Fe 3+ = S 6+ + 8Fe 2+, which is expected to proceed strongly to the right with decreasing temperature. This reaction would explain why S 2− and S 6+ are frequently found together despite the very limited fO 2 range over which they are thermodynamically predicted to coexist. The S XANES spectra of water-rich, highly oxidised, basaltic inclusions hosted in olivine from Etna and Stromboli confirm that nearly all S is dissolved as sulfate, explaining their relatively high S contents.