Isotopic Equilibration Between Sulfide and Organic Matter: Implications for Records of Sedimentary δ34S.

Abstract:

Records of the sulfur-isotopic composition of sedimentary pyrite have been used to constrain the evolutionary timing of major metabolic pathways, the size of the marine sulfate reservoir, and the redox balance of the planet. It remains a major challenge, however, to explain the enormous range of pyrite δ³⁴S values in the literature and their typical ~10‰ offset relative to sedimentary organic S. We investigate the development of pyrite and organic S records in Santa Barbara Basin, which has suboxic bottom water and high (≥4 wt%) organic matter burial. Concentration and δ³⁴S profiles of major sulfur species (sulfate, sulfide, elemental S, proto-kerogen, pyrite, and extractable organic matter) suggest the occurrence of S-isotope exchange between porewater sulfide and organic S, so we conducted laboratory experiments to test organic S exchangeability with ³⁴S-labelled sulfide–polysulfide solutions. We found that both extractable and proto-kerogen organic matter incorporated significant amounts of label within days, supporting the feasibility of equilibration between sulfide and organic matter in the environment. Unlike organic S, pyrite δ³⁴S values in Santa Barbara Basin sediments are up to 30‰ lower than those for porewater sulfide. We hypothesize that this strongly ³⁴S-depleted pyrite reflects the immediate products of bacterial sulfate reduction at organic-rich structures like microbial biofilms or aggregates and suggest that this δ34S difference between porewater sulfide and pyrite may be a more common than previously recognized. Pyrite δ³⁴S values are not necessarily reflective of porewater sulfide δ³⁴S, suggesting that this common assumption should be revisited. Sedimentary pyrite and organic S are potentially powerful and complementary archives of environmental information. To meaningfully interpret these records, it is essential that we take into account the complex processes affecting sedimentary pyrite and organic sulfur δ³⁴S in modern sediments.