Experimental determination of the rate and equilibrium fractionation factors of sulfur isotope exchange between sulfate and sulfide in slightly acid solutions at 300°C and 1000 bars

A sulfur isotope fractionation of 20.0 ± 0.2‰ was measured between aqueous sulfide and sulfate at 300°C and 1000 bars using gold-cell hydrothermal solution equipment. The value is 2‰ smaller than previously published values. Rates of exchange were determined as a function of pH and total sulfur content. Initial mean ³⁴S concentration was changed to approach equilibrium from two directions. Half-times ranged from 3.4 to 8.2 days, with shorter times obtained for more acid and more concentrated solutions.The sulfate-sulfide isotope temperature scale based on theory should be revised according to this new fractionation factor. The rate data permit assessment of the extent to which equilibrium may be attained in some natural systems. For example, the lack of agreement between temperatures based on sulfide mineral pairs and sulfide-sulfate mineral pairs from Kuroko ore deposits of Japan might imply that the residence time of sulfate and sulfide in Kuroko solutions was not longer than 1000 years, if the present kinetic data are correct. Geothermal systems such as the Wairakei system of New Zealand may reach sulfur isotope equilibrium between sulfate and sulfide in 300 years at 300°C, but would be increasingly removed from equilibrium at lower temperatures if residence times were 300 years or less.