Validating the rhenium proxy for rock organic carbon oxidation using weathering profiles
Résumé
Chemical weathering over geological timescales acts as a source or sink of atmospheric carbon dioxide (CO2), while influencing long-term redox cycling and atmospheric oxygen (O2) at Earth's surface. There is a growing recognition that the oxidative weathering of rock organic carbon (OCpetro) can release more CO2 than is locally drawn down by silicate weathering, and may vary due to changes in erosion and climate. The element rhenium (Re) has emerged as a proxy to track the oxidative weathering of OCpetro, yet uncertainties in its application remain namely that we lack a systematic assessment of the comparative mobility of Re and OCpetro during sedimentary rock weathering. Here we measure Re and OCpetro loss across gradients in rock weathering at 12 global sites, spanning a range of initial OCpetro values from ~0.2 % to >10 %. At nine sites we use titanium to account for volume changes during weathering and assess Re and OCpetro loss alongside major elements that reflect silicate (Na, Mg), carbonate (Ca, Mg) and sulfide (S) weathering. Across the dataset, Re loss is correlated with OCpetro loss but not with loss of any other major element. Across the weathering profiles, the average molar ratio of OCpetro to Re loss was 0.84 ± 0.15, with 8 out of 9 sites having a ratio >0.74. At one site (Marcellus Shale), the average ratio was lower at 0.58 ± 0.11. The excess loss of Re matches expectations that, typically, between ~0 and 20 % of the Re liberated by sedimentary rock weathering derives from silicate or sulfide phases, while some OCpetro may be physically or chemically protected from weathering. Overall, our measurements provide validation for the Re proxy of OCpetro oxidation and allow future work to further improve our knowledge of regional and global-scale rates of this important source of CO2 in the geochemical carbon cycle.
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