Solubility and speciation of sulfur in silicate melts: The Conjugated Toop-Samis-Flood-Grjotheim (CTSFG) model

Abstract

A Conjugated Toop-Samis-Flood-Grjotheim (CTSFG) model is developed by combining the framework of the Toop-Samis polymeric approach with the Flood-Grjotheim theoretical treatment of silicate melts and slags. Electrically equivalent ion fractions are computed over the appropriate matrixes (anionic and cationic) in a Temkin notation for fused salts, and are used to weigh the contribution of the various disproportionation reactions of type: M2/pO(melt)+ 1/2S(gas)+M2/pS(melt)+1/2O2(gas) M2/po(melt)+1/2S2(gas)+3/2O2(gas)-M2/pSO4(melt)v being the charge of the generic Mp-1 cation. The extension of the anionic matrix is calculated in the framework of a previously developed polymeric model (Ottonello et al., 2001), based on a parameterization of Lux-Flood acid-base properties of melt components. Model activities follow the Raoultian behavior implicit in the Temkin notation, without the needs of introducing adjustable parameters. The CTSFG model is based on a large amount of data available in literature and exhibits a satisfactory heuristic capability, with virtually no compositional limits, as long as the structural role given to each oxide holds. The model may be employed to compute gas-melt equilibria involving sulfur and allows computing sulfide and sulfate contents of silicate melts whenever the fugacity of a gaseous sulfur species and oxygen are known. Alternatively, the model calculates the oxidation state of the system (i.e., oxygen fugacity), whenever an analytical determination of either sulfide/sulfate or ferrous/ferric ratios in the melt is provided. Calculated sulfide and sulfate capacities allow the estimates of sulfur abundance in various melts of geological interest, both under anhydrous and hydrous conditions or, alternatively, of fS2, given fO2 and the bulk sulfur content. In this case, fSO2 and fH2S may be eventually computed along the water-sulfur-melt boundary provided fH2O is known.