Geochemical consequences of oxygen diffusion from the oceanic crust into overlying sediments and its significance for biogeochemical cycles based on sediments of the northeast Pacific

Exchange of dissolved substances at the sediment–water interface provides an important link between the short–term and long–term geochemical cycles in the ocean. A second, as yet poorly understood sediment–water exchange is supported by low–temperature circulation of seawater through the oceanic basement underneath the sediments. From the basement, upwards diffusing oxygen and other dissolved species modify the sediment whereas reaction products diffuse from the sediment down into the basement, where they are transported by the basement fluid and released to the ocean. Here, we investigate the impact of this “second” route with respect to transport, release and consumption of oxygen, nitrate, manganese, nickel, and cobalt on the basis of sediment cores retrieved from the Clarion Clipperton Zone (CCZ) in the equatorial Pacific Ocean. We show that in this abyssal ocean region characterised by low organic–carbon burial and sedimentation rates vast areas exist where the downward and upward directed diffusive fluxes of oxygen meet so that the sediments are oxic throughout. This is especially the case where sediments are thin or in the proximity of faults. Oxygen diffusing upward from the basaltic crust into the sediment contributes to the degradation of sedimentary organic matter. Where the oxygen profiles do not meet, they are separated by a suboxic sediment interval characterised by Mn2+ in the pore–water. Where the sediments are entirely oxic, nitrate produced in the upper sediment by nitrification is lost both by upward diffusion into the bottom water and by downward diffusion into the fluids circulating within the basement. Where pore–water manganese in the suboxic zones remains low, nitrate consumption is low and the sediment continues to deliver nitrate to the ocean bottom waters and basement fluid. We observe that at elevated pore–water manganese concentrations, nitrate consumption exceeds production and the basement becomes a nitrate source. Within the suboxic zone, not only manganese but also cobalt and nickel are released into the pore–water by reduction of oxides, diffuse towards the oxic/suboxic fronts above and below where they precipitate, effectively removing these metals from the suboxic zone and concentrating them at the oxic/suboxic redox boundaries. We show that not only diffusive fluxes in the top part of deep–sea sediments modify the geochemical composition over time, but also diffusive fluxes of dissolved constituents from the basement into the bottom layers of the sediment. Hence, paleoceanographic interpretation of sedimentary layers should carefully consider such deep secondary modifications in order to prevent misinterpretation as primary signatures