Sedimentary sulfur isotopes and Neoarchean ocean oxygenation

Abrupt disappearance of mass-independent fractionation of sulfur isotopes (MIF-S) from the geologic record and an apparent ingrowth in seawater sulfate around 2.45 billion years ago (Ga) signal the first large-scale oxygenation of the atmosphere [the Great Oxygenation Event (GOE)]. Pre-GOE O2 production is evident from multiple other terrestrial and marine proxies, but oceanic O2 concentrations remain poorly constrained. Furthermore, current interpretations of S isotope records do not explain a concurrent expansion in the range of both MIF-S-diagnostic for low atmospheric O2-and δ34S beginning at 2.7 Ga. To address these unknowns, we developed a reaction-transport model to analyze the preservation patterns of sulfur isotopes in Archean sedimentary pyrites, one of the most robust and widely distributed proxies for early Earth biogeochemistry. Our modeling, paradoxically, reveals that micromolar levels of O2 in seawater enhance the preservation of large MIF-S signals, whereas concomitant ingrowth of sulfate expands the ranges in pyrite δ34S. The 2.7- to 2.45-Ga expansion in both Δ33S and δ34S ranges thus argues for a widespread and protracted oxygenation of seawater, at least in shallow marine environments. At the micromolar levels predicted, the surface oceans would support a strong flux of O2 to the atmosphere, where O2 sinks balanced these fluxes until the GOE. This microoxic seawater would have provided habitat for early aerobic microorganisms and supported a diversity of new O2-driven biogeochemical cycles in the Neoarchean.