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.

Description: Numerous studies have provided compelling evidence that the Pacific Ocean has experienced substantial glacial/interglacial changes in bottom-water oxygenation associated with enhanced carbon dioxide storage in the glacial deep ocean. Under postulated low glacial bottom-water oxygen concentrations (O), redox zonation, biogeochemical processes and element fluxes in the sediments must have been distinctively different during the last glacial period (LGP) compared to current well-oxygenated conditions. In this study, we have investigated six sites situated in various European contract areas for the exploration of polymetallic nodules within the Clarion-Clipperton Zone (CCZ) in the NE Pacific and one site located in a protected Area of Particular Environmental Interest (APEI3) north of the CCZ. We found bulk sediment Mn maxima of up to 1 wt% in the upper oxic 10 cm of the sediments at all sites except for the APEI3 site. The application of a combined leaching protocol for the extraction of sedimentary Mn and Fe minerals revealed that mobilizable Mn(IV) represents the dominant Mn(oxyhydr)oxide phase with more than 70% of bulk solid-phase Mn. Steady state transport-reaction modeling showed that at postulated glacial O of 35 μM, the oxic zone in the sediments was much more compressed than today where upward diffusing pore-water Mn2+ was oxidized and precipitated as authigenic Mn(IV) at the oxic-suboxic redox boundary in the upper 5 cm of the sediments. Transient transport-reaction modeling demonstrated that with increasing O during the last glacial termination to current levels of ∼ 150 μM, (1) the oxic-suboxic redox boundary migrated deeper into the sediments and (2) the authigenic Mn(IV) peak was continuously mixed into subsequently deposited sediments by bioturbation causing the observed mobilizable Mn(IV) enrichment in the surface sediments. Such a distinct mobilizable Mn(IV) maximum was not found in the surface sediments of the APEI3 site, which indicates that the oxic zone was not as condensed during the LGP at this site due to two- to threefold lower organic carbon burial rates. Leaching data for sedimentary Fe minerals suggest that Fe(III) has not been diagenetically redistributed during the LGP at any of the investigated sites. Our results demonstrate that the basin-wide deoxygenation in the NE Pacific during the LGP was associated with (1) a much more compressed oxic zone at sites with carbon burial fluxes higher than 1.5 mg Corg m−2 d−1, (2) the authigenic formation of a sub-surface mobilizable Mn(IV) maximum in the upper 5 cm of the sediments and (3) a possibly intensified suboxic-diagenetic growth of polymetallic nodules. As our study provides evidence that authigenic Mn(IV) precipitated in the surface sediments under postulated low glacial O, it contributes to resolving a long-standing controversy concerning the origin of widely observed Mn-rich layers in glacial/deglacial deep-sea sediments.

Description: The dataset includes solid-phase geochemistry data of sediment cores from Site C0023 (Hole A) that was recovered during International Ocean Discovery Program (IODP) Expedition 370 in the Nankai Trough offshore Japan in the Pacific Ocean (Drilling vessel Chikyu). Site C0023 was established on 17 September 2016. Coring terminated on 3 November 2016. Stable carbon isotopes of total organic carbon measurement occurred on an EA-IRMS system after complete decalcification of homogenized sediment samples with 10% HCl. The δ13C-TOC values are expressed relative to VPDB (Vienna Pee Dee Belemnite).

Description: The dataset includes rock magnetic end-member unmixing data of sediment cores from Site C0023 (Hole A) that was recovered during International Ocean Discovery Program (IODP) Expedition 370 in the Nankai Trough offshore Japan in the Pacific Ocean (Drilling vessel Chikyu). Site C0023 was established on 17 September 2016. Coring terminated on 3 November 2016. End-member modelling of isothermal remanent magnetization (IRM) acquisition curves were performed to characterize the iron mineralogy. IRM acquisition curves were measured using a Princeton Measurements Corporation Vibrating Sample Magnetometer (VSM). IRM was imparted stepwise (non-linearly) up to a maximum field of 1 T with an averaging time of 200 ms. Unmixing of IRM acquisition curves were performed using the web application MAX UnMix by Maxbauer et al. (2016). Mean coervity (Bh) is given in log10 B mT and dispersion parameter (DP) in log. EC is the extrapolated contribution to the total IRM.

Description: The dataset includes solid-phase geochemistry data of sediment cores from Site C0023 (Hole A) that was recovered during International Ocean Discovery Program (IODP) Expedition 370 in the Nankai Trough offshore Japan in the Pacific Ocean (Drilling vessel Chikyu). Site C0023 was established on 17 September 2016. Coring terminated on 3 November 2016. Algal lipid biomarker analysis was performed after Sturt et al. (2004) and HPLC-MS analyses after Becker et al. (2015). Biomarker concentrations are reported as the integrated peak area of the sum of all detected diols normalized to kg extracted sediment (PA/kg).

Description: During the PS118 research cruise with the German research vessel RV POLARSTERN (Feb 2019- April 2019), sediments were collected with a multicorer from 7 stations along a 400 mile transect from the eastern shelf of the Antarctic Peninsula to the West of the South Orkney Islands. A total of 69 high-resolution O2 profiles were measured in 23 cores in the upper sediment layer using optical microsensors (Optodes, Pyroscience) in order to determine oxygen penetration depths and diffusive oxygen uptake (DOU). Pore-water samples were taken at depth resolutions of 1 cm from 0-10 cm and below 10 cm with a resolution of 2 cm down to a maximum depth of 30 cm. Sediments of parallel cores were cut at the same depth resolution for solid-phase contents. Pore-water analyses of trace element such as dissolved iron (DFe) and manganese (DMn), dissolved inorganic carbon (DIC), hydrogen sulfide (H2S) and nutrients such as ammonium (NH4+), phosphate (PO4³), nitrate (NO3-), nitrite (NO2-) and silicate (SiO3²−) were measured. For solid-phase analyses, freeze-dried and ground sediment samples were measured for TOC and TN. At 5 stations, Al, Fe, Mn, P and S content was measured after total acid digestion. At the same 5 stations, excess 210Pb was measured in freeze-dried and homogenized sediments.