Sulphur isotopic fractionation between sulphate and sulphide in hydrothermal ore deposits: disequilibrium vs equilibrium processes

Correlative fractionation relationships of sulphur isotope data for coexisting sulphate and sulphide pairs from hydrothermal ore deposits on δ³⁸S versus Δ³⁴S diagrams are deciphered theoretically. Taking into account dissolved H₂S and SO₄^2- in hydrothermal fluids during precipitation of both sulphate and sulphide minerals, a 4-species closed system is suggested for describing the conservation of mass among all sulphur-bearing species on the δ-Δ diagrams. The covariation in the δ³⁴S values of both sulphate and sulphide is ascribed to isotopic exchange between oxidized and reduced sulphur species during mineral precipitation. The isotopic exchange could be a thermodynamic process due to simple cooling of high temperature fluids, which results in an equilibrium fractionation, or a kinetic process due to mixing of two sulphur reservoirs, which leads to a disequilibrium fractionation. The δ³⁴S value of total sulphur in a hydrothermal system could change due to the precipitation of minerals, or due to the escape of H₂S and/or SO₄^2-. Sulphur isotope data for anhydrite and pyrite pairs from the Luohe porphyrite iron deposit in the Yangtze River Valley is used to illustrate the mixing responsible for the disequilibrium fractionation.