Incomplete sulfide oxidation under sub-oxic conditions: Rates and aqueous sulfur speciation

Abstract

The oxidative dissolution of sulfide minerals consumes oxygen and can generate redox gradients in mine wastes that affect the mobility of redox-sensitive solutes. However, the controls of oxygen depletion on sulfide reactivity and sulfur mobilization remain poorly constrained, complicating the long-term assessment of drainage quality dynamics. We investigated pyrite and Fe-rich sphalerite weathering using aqueous S speciation and quantitative mineralogical analyses under controlled, ambient versus sub-oxic, conditions at 6 < pH < 9. Titration assays revealed that oxidation rates for pyrite (up to 10−10 mol m−2 s−1) were higher than for sphalerite (up to 10−11 mol m−2 s−1) and, for both minerals, decreased by two orders-of-magnitude under sub-oxic (<50 ppm O2) conditions. Precipitation of secondary S-bearing minerals was restricted to elemental S, with no sulfate- or thiosulfate-salts detectable >0.01 wt%. Sulfate was the dominant aqueous S species produced in all experiments, but significant amounts of thiosulfate, tetrathionate, and sulfite were also found. These dissolved intermediate S species were abundant under both sub-oxic and oxic conditions, and broadly in line with known sulfide oxidation mechanisms, even though the weathering of pyrite produced several factors less incompletely oxidized S than that of sphalerite, under otherwise comparable conditions. This work shows that a range of intermediate S species may be produced even in low-reactivity conditions and may help optimize the management of such mine waste materials.