First-principles calculations of sulphur isotope fractionation in MX2 minerals, with M = Fe, Co, Ni and X2 = AsS, SbS

Iron, Co and Ni are first row transition metals and are all able to combine with S, As, and Sb to form disulphides, sulpharsenides and sulphantimonides, respectively, all of which exhibit substitutions of metal and metalloid elements in their structures. As an important tracer in the geochemistry of ore deposits, S isotope fractionation in sulphides can be used to analyse the ore-forming process and the source of ore-forming elements. However, there have been few studies of S isotope fractionation in sulpharsenides and sulphantimonides. Studying the isotope fractionation of the various members of this structural group can provide systematic information regarding S isotope fractionation in transition metal disulphides, sulpharsenides and sulphantimonides. In this paper, the S isotope fractionation parameters for Fe, Co and Ni sulpharsenides and sulphantimonides were calculated using first-principles methods based on density functional theory in the temperature range of 0–1000 °C. Our calculations show that the order of heavy S isotope enrichment is arsenopyrite > cobaltite > gudmundite > costibite > gersdorffite > ullmannite. For sulphides with the same anion pair, the main factor affecting S isotope fractionation is the metal-sulphur bond strength. For most of the sulphides studied in this paper, S isotope fractionation arising from substitution of metalloid elements is much smaller than that of metal elements.