Oxygen isotope evidence for sorption of molecular oxygen to pyrite surface sites and incorporation into sulfate in oxidation experiments

Pyrite oxidation experiments revealed two dependencies of the O-isotope composition of dissolved sulfates: O-isotope values decreased with longer duration of experiments and increasing grain size of pyrite. Both changes are interpreted as evidence for chemisorption of molecular O2 to pyrite surface sites. The sorption of molecular O2 is important at initial oxidation stages and more abundant in finer grained pyrite fractions and leads to its incorporation in the produced SO4. The calculated bulk contribution of atmospheric O2 in the dissolved SO4 reached up to 50% during initial oxidation stages (first 5 days, pH 2, fine-grained pyrite fraction) and decreased to less than 20% after about 100 days. Based on the direct incorporation of molecular O2 in the early-formed sulfates, chemisorption and electron transfer of molecular O2 on S sites of the pyrite surface are proposed, in addition to chemisorption on Fe sites. After about 10 days, the O of all newly-formed sulfates originates only from water, indicating direct interaction of hydroxyls from water with S at the anodic S pyrite surface site. Then, the role of molecular O2 is as proposed in previous studies: acting as electron acceptor only at the cathodic Fe pyrite surface site for oxidation of Fe(II) to Fe(III).