Understanding the isotopic composition of sedimentary sulfide: A multiple sulfur isotope diagenetic model for Aarhus Bay

Measurement of the multiple sulfur isotopes (32S/33S/34S) enables the calibration of microbial biosignatures and provides a unique diagnosis of S-based metabolic processes: sulfate reduction, disproportionation, and sulfide oxidation. All three metabolisms carry distinct geochemical consequences for S cycling in modern systems, and are particularly powerful for paleoenvironmental interpretations if their respective contributions can be separated. To hone those interpretations and to further develop a quantitative context for understanding early diagenetic sulfur cycling, we constructed a multiple S isotope reactive transport model for the sediments of a geochemically well-characterized system (Aarhus Bay, Denmark). The model reconciles pore water and solid phase concentration profiles of the major species associated with Fe/S/C cycling, and uses multiple S isotope systematics to predict the isotope profiles of the major S species, including pore water sulfate, free sulfide and solid phase pyrite. We note that very large fractionations associated with sulfate reduction (34εsr = 70‰) are required to reproduce the observed pore water profiles, and we reconcile these fractionations with low temperature theoretical predictions for isotope equilibrium fractionation. The minor sulfur isotope values (noted as Δ33S) of sulfate increase at shallow depths within the Aarhus Bay core, and decrease when sulfate drops below 10 mM. Values (Δ33S) for sulfide decrease nearly monotonically towards seawater sulfate values near the zone of sulfate depletion. Pyrite Δ33S values are nearly uniform downcore (0.170 ± 0.010‰) despite a ∼10‰ enrichment in surface versus deep pyrite δ34S values. Sulfate reduction is the most important process controlling S isotope pore water distributions, with modest contributions from oxidative S cycling. Further, microbial sulfate reduction demonstrates large fractionations typically not expected for shallow, organic rich (TOC ∼ 4%) continental margin systems.