Rates of carbonate cementation associated with sulphate reduction in DSDP/ODP sediments: implications for the formation of concretions

DSDP/ODP porewater profiles in organic carbon-bearing (<5% org. C) sediments commonly show decreases in Ca2+ concentrations and increases in alkalinity over depths where sulphate is being removed by microbial reduction. These Ca2+ depletion profiles represent the combined effect of diffusion, advection and reaction (addition by ion exchange and removal by precipitation mainly as CaCO3 and/or dolomite). A diagenetic model has been used to estimate the rate constant (k) for Ca2+ removal by precipitation during sulphate depletion over depths of 15-150 m, assuming first order kinetics. The rate constants for Ca2+ removal range from 10(-14) to 10(-11) s(-1) in 19 DSDP/ODP sediments, which span a range of bottom water temperatures (0-10 degreesC), lithologies (calcareous to clastic) and sedimentation rates (0.001-0.4 cm year(-1)). Values of k correlate with sedimentation rate (omega) such that log k=1.16 log omega-10.3, indicating that faster rates of Ca2+ removal occur at higher sedimentation rates where there are also higher degrees of saturation with respect to CaCO3 and dolomite. Depth-integrated masses of Ca2+ removed (<100 mumol cm(-2)) during sulphate depletion over these depth ranges are equivalent to a dispersed phase of approximately 1.5 wt.% CaCO3 or 3 wt.% dolomite in a compacted sediment. The complete occlusion of sediment porosity observed in concretions with isotopic signatures suggesting carbonate sourced from sulphate reduction therefore requires more time (a depositional hiatus), more rapid sulphate reduction (possibly by anaerobic methane oxidation) and/or the continued transport of isotopically light carbonate to the concretion site after sulphate reduction has ceased.