ALBERT

Description: We emphasize the importance of marine silicate weathering (MSiW) reactions in anoxic sediment as fundamental in generating alkalinity and cations needed for carbonate precipitation and preservation along continental margins. We use a model that couples thermodynamics with aqueous geochemistry to show that the CO2 released during methanogenesis results in a drop in pH to 6.0; unless these protons are buffered by MSiW, carbonate minerals will dissolve. We present data from two regions: the India passive margin and the active subduction zone off Japan, where ash and/or rivers supply the reactive silicate phase, as reflected in strontium isotope data. Offshore India and Korea, alteration of continent-derived silicates results in pore water enriched in radiogenic 87Sr, with 87Sr/86Sr ratios as high as 0.7095 and 0.7104, respectively. Off Japan, strontium in pore water influenced by ash alteration is depleted in 87Sr, with 87Sr/86Sr as low as 0.7065. Carbonate minerals formed by alkalinity and cations generated through MSiW carry these strontium isotopic signals, and are typically dolomite, siderite, and Fe-rich calcite. These contrast with the aragonite and high-magnesium calcite that form during anaerobic oxidation of methane and incorporate the coeval seawater 87Sr/86Sr signal. We show that MSiW is necessary for authigenic carbonate formation and preservation along continental margins, which remove carbon from Earth's surface at rates previously estimated to be at least 1012 mol yr−1. In addition, these authigenic carbonates are of relevance to studies of the deep biosphere, fluid flow, seismogenesis, slope stability, and reservoir characteristics.

Description: Highlights • Release of dissolved Sr2+ with low 87Sr/86Sr, as well as Ca2+ and Ba2+ suggests ongoing volcanic ash alteration. • A concurrent increase in Fe2+ and a depletion of CH4 with a decrease in C of CH4 and DIC suggest Fe-AOM. • We for the first time document the potential linkage between ash alteration and methane oxidation via Fe-AOM. • The rate of Fe-AOM is estimated to be ∼0.4 μmol cm−2 yr−1, equivalent to ∼12% of total CH4 removal. Abstract We present geochemical data collected from volcanic ash-bearing sediments on the upper slope of the northern Hikurangi margin during the RV SONNE SO247 expedition in 2016. Gravity coring and seafloor drilling with the MARUM-MeBo200 allowed for collection of sediments down to 105 meters below seafloor (mbsf). Release of dissolved Sr2+ with isotopic composition enriched in 86Sr (87Sr/86Sr minimum = 0.708461 at 83.5 mbsf) is indicative of ash alteration. This reaction releases other cations in the 30-70 mbsf depth interval as reflected by maxima in pore-water Ca2+ and Ba2+ concentrations. In addition, we posit that Fe(III) in volcanogenic glass serves as an electron acceptor for methane oxidation, a reaction that releases Fe2+ measured in the pore fluids to a maximum concentration of 184 μM. Several lines of evidence support our proposed coupling of ash alteration with Fe-mediated anaerobic oxidation of methane (Fe-AOM) beneath the sulfate-methane transition (SMT), which lies at ∼7 mbsf at this site. In the ∼30-70 mbsf interval, we observe a concurrent increase in Fe2+ and a depletion of CH4 with a well-defined decrease in C-CH4 values indicative of microbial fractionation of carbon. The negative excursions in C values of both DIC and CH4 are similar to that observed by sulfate-driven AOM at low SO concentrations, and can only be explained by the microbially-mediated carbon isotope equilibration between CH4 and DIC. Mass balance considerations reveal that the iron cycled through the coupled ash alteration and AOM reactions is consumed as authigenic Fe-bearing minerals. This iron sink term derived from the mass balance is consistent with the amount of iron present as carbonate minerals, as estimated from sequential extraction analyses. Using a numerical modeling approach we estimate the rate of Fe-AOM to be on the order of 0.4 μmol cm−2 yr−1, which accounts for ∼12% of total CH4 removal in the sediments. Although not without uncertainties, the results presented reveal that Fe-AOM in ash-bearing sediments is significantly lower than the sulfate-driven CH4 consumption, which at this site is 3.0 μmol cm−2 yr−1. We highlight that Fe(III) in ash can potentially serve as an electron acceptor for methane oxidation in sulfate-depleted settings. This is relevant to our understanding of C-Fe cycling in the methanic zone that typically underlies the SMT and could be important in supporting the deep biosphere.