Triple oxygen isotope insight into terrestrial pyrite oxidation.

Abstract

The mass-independent minor oxygen isotope compositions (Δ'¹⁷O) of atmospheric O₂ and [Formula: see text] are primarily regulated by their relative partial pressures, [Formula: see text]/[Formula: see text] Pyrite oxidation during chemical weathering on land consumes [Formula: see text] and generates sulfate that is carried to the ocean by rivers. The Δ'¹⁷O values of marine sulfate deposits have thus been proposed to quantitatively track ancient atmospheric conditions. This proxy assumes direct [Formula: see text] incorporation into terrestrial pyrite oxidation-derived sulfate, but a mechanistic understanding of pyrite oxidation-including oxygen sources-in weathering environments remains elusive. To address this issue, we present sulfate source estimates and Δ'¹⁷O measurements from modern rivers transecting the Annapurna Himalaya, Nepal. Sulfate in high-elevation headwaters is quantitatively sourced by pyrite oxidation, but resulting Δ'¹⁷O values imply no direct tropospheric [Formula: see text] incorporation. Rather, our results necessitate incorporation of oxygen atoms from alternative, ¹⁷O-enriched sources such as reactive oxygen species. Sulfate Δ'¹⁷O decreases significantly when moving into warm, low-elevation tributaries draining the same bedrock lithology. We interpret this to reflect overprinting of the pyrite oxidation-derived Δ'¹⁷O anomaly by microbial sulfate reduction and reoxidation, consistent with previously described major sulfur and oxygen isotope relationships. The geologic application of sulfate Δ'¹⁷O as a proxy for past [Formula: see text]/[Formula: see text] should consider both 1) alternative oxygen sources during pyrite oxidation and 2) secondary overprinting by microbial recycling.