Organic haze, glaciations and multiple sulfur isotopes in the Mid-Archean Era

We use sulfur (S) isotope signatures within ancient sediments and a photochemical model of sulfur dioxide (SO2) photolysis to interpret the evolution of the atmosphere over the first half of Earth's history. A decrease in mass-independent sulfur isotope fractionation has been reported in Archean rocks deposited between ~ 2.7 Ga and ~ 3.2 Ga, and is reinforced by new S isotope data that we report here. This pattern has been interpreted by some as evidence that atmospheric oxygen (O2) was elevated during this time. In this paper, we argue against that conclusion, and show that it is inconsistent with other geochemical data. In its place, we propose a new model that can explain the sulfur isotope record that can also avoid conflicts with independent constraints on O2 and account for concurrent glacial deposits. Specifically, we suggest that prior to the rise of O2 excursions in the sulfur isotope record were modulated by the thickness of an organic haze. This haze would have blocked the lower atmosphere from the UV fluxes responsible for the anomalous sulfur photochemistry and would have caused an anti-greenhouse effect that triggered the glaciations. We used a photochemical model to verify that a haze could have affected the isotopic signal in this manner, and to examine how changes in atmospheric methane (CH4) and carbon dioxide (CO2) concentrations could have controlled haze thickness. Finally, we combined the resulting relationships with climate models and sulfur isotope and glacial records to deduce a new evolutionary sequence for Archean climate, surface chemistry, and biology.