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

Abstract

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 (³⁴ε_sr = 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.