Description: Serpentinized peridotite and gabbronorite represent the host rocks to the active, ultramafic-hosted Logatchev hydrothermal field at the Mid-Atlantic Ridge. We use trace element, δ18O and 87Sr/86Sr data from bulk rock samples and mineral separates in order to constrain the controls on the geochemical budget within the Logatchev hydrothermal system. The trace element data of serpentinized peridotite show strong compositional variations indicating a range of processes. Some peridotites experienced geochemical modifications associated with melt-rock interaction processes prior to serpentinization, which resulted in positive correlations of increasing high field strength element (HFSE) concentrations and light rare earth element (LREE) contents. Other serpentinites and lizardite mineral separates are enriched in LREE, lacking a correlation with HFSE due to interaction with high-temperature, black-smoker type fluids. The enrichment of serpentinites and lizardite separates in trace elements, as well as locally developed negative Ce-anomalies, indicate that interaction with low-T ambient seawater is another important process in the Logatchev hydrothermal system. Hence, mixing of high-T hydrothermal fluids during serpentinization and/or re-equilibration of O-isotope signatures during subsequent low-T alteration is required to explain the trace element and δ18O temperature constraints. Highly radiogenic 87Sr/86Sr signatures of serpentinite and lizardite separates provide additional evidence for interaction with seawater-derived fluids. Sparse talc alteration at the Logatchev site are most likely caused by Si-metasomatism of serpentinite associated with the emplacement of shallow gabbro intrusion(s) generating localized hydrothermal circulation. In summary the geochemistry of serpentinites from the Logatchev site document subsurface processes and the evolution of a seafloor ultramafic hydrothermal system.

Description: 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.