Estimating rates of authigenic carbonate precipitation in modern marine sediments

The formation of authigenic carbonate (AC) in marine sediments provides a plausible explanation for large, long-lasting marine δ13C excursions that does not require extreme swings in atmospheric O2 or CO2. AC precipitation during diagenesis is driven by alkalinity production during anaerobic organic matter oxidation and is coupled to sulfate reduction. To evaluate the extent to which this process contributes to global carbon cycling, we need to relate AC production to the geochemical and geomicrobiological processes and ocean chemical conditions that control it. We present a method to estimate modern rates of AC precipitation using an inversion approach based on the diffusion-advection-reaction equation and sediment pore fluid chemistry profiles as a function of depth. SEM images and semi-quantitative elemental map analyses provide further constraints. Our initial focus is on ODP sites 807 and 1082. We sum the diffusive, advective, and reactive terms that describe changes in pore fluid Ca and Mg concentrations due to precipitation of secondary carbonate. We calculate the advective and diffusive terms from the first and second derivatives of the Ca and Mg pore fluid concentrations using a spline fit to the data. Assuming steady-state behavior we derive net AC precipitation rates of up to 8 x 10-4 mmol m-2 y-1 for Site 807 and 0.6 mmol m-2 y-1 for Site 1082. Site 1082 sediments contain pyrite, which increases in amount down-section towards the estimated peak carbonate precipitation rate, consistent with sulfate-reduction-induced AC precipitation. However, the presence of gypsum and barite throughout the sediment column implies incomplete sulfate reduction and merits further investigation of the biogeochemical reactions controlling authigenesis. Further adjustments to our method could account for the small but non-negligible fraction of groundmass with a CaSO4 signature. Our estimates demonstrate that AC formation may represent a sizeable flux in the modern global carbon cycle, on order of 1013 g C y-1. Further, it is likely to have played an even more impactful role in the Paleozoic and Precambrian, when lower surface O2 concentrations created reducing conditions favoring increased carbon burial and alkalinity production during diagenesis.