A heavy molybdenum reservoir in Neoarchean seawater tracks extensive iron oxidation
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Progressively heavier molybdenum isotope compositions (δ 98 Mo) in Neoarchean marine sediments have been interpreted as evidence for widespread surface oxygenation prior to the Great Oxidation Event. Here, we assess whether the deposition of banded iron formations (BIFs) — iron-rich sedimentary rocks formed predominantly in the Neoarchean — can account for this isotopic signal through processes operating under pervasively anoxic conditions. BIF samples analyzed here possess a wide range of δ 98 Mo values, which are attributed to the combined effects of Mo adsorption onto primary ferric iron (Fe) oxyhydroxides and subsequent diagenetic incorporation into Fe-Mo-sulfides. Given the isotopic fractionation associated with Mo adsorption, we estimate that Neoarchean seawater δ 98 Mo ranged from 1.5‰ and 1.6‰, and was more stable than previously suggested. If Mo in Neoarchean rivers had an average isotopic composition like today, a mass balance model predicts that only a modest manganese oxide sink is required to generate these heavy δ 98 Mo values. Instead, the dominant control may have been the removal of isotopically light Mo via adsorption to abundant ferric oxyhydroxide particles setting through a ferruginous water column. These findings imply that the Neoarchean Mo isotope record may track extensive photosynthetic iron oxidation rather than pervasive oxygen accumulation in the surface ocean.