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: Highlights • Sedimentary characteristics and geochemistry of tephra deposits are reported across 21 cores. • Four types of tephra lithofacies are distinguished. • Geomorphic sub-environments play a key role in tephra preservation. • Isolated semi-confined basin settings generally preserve the highest number of tephra deposits. • For eruptions VEI≥6 volcaniclastic sediments may swamp the marine system for centuries. Tephra (volcanic ash) deposits are important isochronous markers for correlating marine sediments or events recorded in marine sediment cores. However, the active tectonics that are commonly associated with volcanic activity at plate tectonicboundaries also drive large-scale deformation, leading to steep and variable local and regional bathymetry (e.g., ridges, basins and canyons systems). This complex bathymetry influences gravity-flow behaviour and paths, which can rework and redeposit tephras, resulting in stratigraphic complexities. Such as, the mis-identification of primary versus reworked tephra deposits, and in turn lead to the development of inaccurate chronostratigraphies. Here we present 36 tephra deposits from 21 shallow marine sediment cores that traverse the length of the southern and central margin of eastern North Island, New Zealand. Using major and trace element geochemical compositions for glass shards from the tephras, we correlate these deposits to three major rhyolitic eruptions from the Taupō Volcanic Zone (TVZ) approximately 200 km west, including; Taupō (1718 cal yrs. BP), Kaharoa (636 cal yrs. BP), and Kawakawa/Oruanui (KOT; 25.4 ka). Based on their morphology, depositional character and inferred emplacement mechanisms, the tephra deposits are grouped into four lithofacies types; (1) primary deposits, (2) volcaniclastic-rich turbidites, (3) blebs/pods of volcaniclastic-rich material, and (4) complex deposits. Primary deposits form syn-eruptively through airfall onto the ocean surface, settling over hours to days through the water column under diffuse vertical gravity currents. Volcaniclastic-rich turbidites are formed through secondary redeposition and entrainment by post-eruptive turbidity currents, while blebs/pods of material are interpreted to have formed by erosion and/or bioturbation. Complex deposits form through the interaction of all these mechanisms producing an overthickened array of primary and redeposited units within a single facies. Herein, we argue that redeposited units of volcaniclastic-rich turbidites or small blebs/pods can be used as tentative chronological markers if the geochemical composition of the glass shards have a homogeneous signature, i.e. a single eruptive source. Where the glass shards in redeposited units have mixed geochemical compositions, and are not stratigraphically associated with a primary deposit source, they cannot be used as chronological marker horizons. This emphasises the need for accurate and rigorous data reduction without overlooking the importance of data points that are statistical outliers. We also show that the highest preservation of tephra deposits is found in semi-confined isolated basin settings, including a wide range of deposit types. Due to erosive sediment flows that bypass through submarine distributary systems, these major sediment dispersal pathways preserve few volcaniclastic deposits. Our findings have important implications not only for identifying primary or redeposited characteristics in marine tephras for building accurate chronostratigraphies, but also as a guide geomorphic sub-environments with the best preservation of tephras in marine sedimentary systems.

Description: 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 CH4with a well-defined decrease in δ13C-CH4values indicative of microbial fractionation of carbon. The negative excursions in δ13C values of both DIC and CH4are similar to that observed by sulfate-driven AOM at low SO2−4concentrations, and can only be explained by the microbially-mediated carbon isotope equilibration between CH4and 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 0.4μmol cm−2yr−1, which accounts for ∼12% of total CH4removal 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 CH4consumption, which at this site is 3.0μmol cm−2yr−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.