Molybdenum isotope fractionation in glacial diamictites tracks the onset of oxidative weathering of the continental crust

Molybdenum isotopes in twenty-four composites of glacial diamictites spanning depositional ages of 2900 to 300 Ma show a systematic shift to lighter compositions and a decrease in Mo concentration over time. The diamictites fall into three age groups relative to the Great Oxidation Event (GOE): pre-GOE (2.43 – 2.90 Ga), syn-GOE (2.20 – 2.39 Ga), and post-GOE (0.33 – 0.75 Ga). Pre-GOE composites have an average δ⁹⁸Mo_NIST3134 of +0.03‰ (± 0.18‰), syn-GOE composites average −0.29‰ (± 0.60‰), and post-GOE composites average −0.45‰ (± 0.51‰). These groups are statistically different at p=0.05. We use the pre-GOE data to estimate the average Archean upper continental crust (UCC) δ⁹⁸Mo signature as +0.03 ± 0.18‰ (2σ), which falls within the range of previous estimates of modern igneous rocks. As the diamictites represent a mixture of igneous and weathered crust, the shift to lighter Mo values over time likely reflects Mo isotope fractionation during oxidative weathering and increased retention of light Mo isotopes in weathered regolith and soils. We hypothesize that this fractionation is due to the mobilization of oxidized Mo following the GOE, and subsequent adsorption of light Mo onto Fe-Mn oxides and/or organic matter in weathered regolith. We conclude that Mo isotopes in continental weathering products record the rise of atmospheric oxygen and onset of oxidative weathering. As the regolith formed under oxidative conditions is isotopically lighter than average continental igneous rocks, mass balance dictates that Mo isotope fractionation during oxidative weathering should result in isotopically heavy groundwater and river water, which is observed in modern systems.