Investigating sulfur partitioning between nominally volatile-free minerals and silicate melts

Abstract:

Despite the key role played by volatile species in magmatic systems, it is still challenging to quantify their concentrations in ancient melts. We suggested a quantitative approach for estimating S contents in basaltic melts (Callegaro et al., 2014), based on direct measurement of S on clinopyroxene and calculation of its concentration in the melt through an experimentally determined partition coefficient (KD). We further investigated the partitioning of sulfur between silicate melts and nominally volatile-free minerals (olivine, orthopyroxene, clinopyroxene, and plagioclase), as well as between melt and amphibole. Partitioning experiments were performed with basaltic, andesitic and dacitic bulk compositions, at hydrous and anhydrous conditions, and at high and low oxygen fugacities (fO₂), where sulfur in the melt is dominantly present as an S⁶⁺ or S^2- species, respectively (Wilke et al., 2011). Sulfur concentrations in melts were measured by electron microprobe and in crystals by synchrotron X-ray fluorescence. At low fO₂ the average crystal/liquid KDs for sulfur vary from 0.0004 (at a maximum) for olivine, to 0.003 (another maximum) for orthopyroxene, to 0.03 for clinopyroxene, and to 0.07 for plagioclase. The KDs correlate positively with the cation-oxygen bond lengths in the crystals. At high fO₂ the KDs drop to approximately one-third of those observed at low fO₂. These observations suggest that S^2- replaces oxygen in the crystal structure. Water has no measureable influence on the crystal/melt partitioning of sulfur. Clinopyroxene/melt KDs are correlated with the Mg/(Mg+Fe) ratio of the crystal, but appear insensitive to the ^IVAl in the structure. Plagioclase/melt S partitioning appears unaffected by anorthite content and iron concentration in the crystal. These new KDs allow the determination of sulfur concentration in the igneous melts co-existing with these crystals and provide insights into the volatile concentrations of ancient magmas and their possible impacts on the near-surface environment.

Callegaro S., Baker D.R., De Min A., Marzoli A., Geraki K., Betrand H., Viti C., Nestola F. (2014) Geology 42, 895–898.

Wilke M., Klimm K., Kohn S.C. (2011) Rev. Mineral. Geochem. 73, 41–78.