Trace-element budgets in the Ohio/Sunbury shales of Kentucky: Constraints on ocean circulation and primary productivity in the Devonian–Mississippian Appalachian Basin

The hydrography of the Appalachian Basin in late Devonian–early Mississippian time is modeled based on the geochemistry of black shales and constrained by others' paleogeographic reconstructions. The model supports a robust exchange of basin bottom water with the open ocean, with residence times of less than forty years during deposition of the Cleveland Shale Member of the Ohio Shale. This is counter to previous interpretations of these carbon-rich units having accumulated under a stratified and stagnant water column, i.e., with a strongly restricted bottom bottom-water circulation. A robust circulation of bottom waters is further consistent with the palaeoclimatology, whereby eastern trade-winds drove upwelling and arid conditions limited terrestrial inputs of siliciclastic sediment, fresh waters, and riverine nutrients. The model suggests that primary productivity was high (~2 g C m−2 d−1), although no higher than in select locations in the ocean today. The flux of organic carbon settling through the water column and its deposition on the sea floor was similar to fluxes found in modern marine environments. Calculations based on the average accumulation rate of the marine fraction of Ni suggest the flux of organic carbon settling out of the water column was approximately 9% of primary productivity, versus an accumulation rate (burial) of organic carbon of 0.5% of primary productivity. Trace-element ratios of V:Mo and Cr:Mo in the marine sediment fraction indicate that bottom waters shifted from predominantly anoxic (sulfate reducing) during deposition of the Huron Shale Member of the Ohio Shale to predominantly suboxic (nitrate reducing) during deposition of the Cleveland Shale Member and the Sunbury Shale, but with anoxic conditions occurring intermittently throughout this period.