Description: Specific trace metal contents that can record the environment at the time of deposition are commonly applied as tracers (proxies) to reconstruct ancient oceanic conditions. However, microbial processes can alter the primary trace metal signal of the sediments during sediment burial. To investigate trace metal cycling during early diagenesis, geochemical analyses were performed via bag-incubations on samples collected from two giant box corers retrieved during RV SONNE Expedition SO260, funded by the MARUM-Center for Marine Environmental Sciences at the University of Bremen. The cores were retrieved off-shore Argentina, one from the head of the Mar del Plata Canyon and the other from a coral mound. Collected sediments are dominantly silt to fine grained sand but include dropstones and coral fragments as well. Our data show strong changes in the pore-water trace metal concentrations in the samples from the Mar del Plata Canyon. For example, molybdenum (Mo) increases by more than 5000 nM within 8 months. In samples from the coral mound box core, pore-water Mo increases by more than 1000 nM in the first 4 months before decreasing again likely due to the onset of sulfate reduction and, consequently, the formation of hydrogen sulfide leading to the (co-)precipitation of Mo. Our data indicate that the reductive dissolution of iron and manganese oxides leads to the release of associated trace metals at different time points for each site. The observed changes are likely related to sediment composition and physical properties. Sediments sampled at the coral mound site include coral fragments, increasing overall porosity and permeability providing more space for fluid circulation and to host microbial communities. Therefore, our data suggest that trace metal cycling is closely related to physical properties including pore space, permeability, and grain size that affect how much area is available for microbial communities.

Description: Rare earth elements (REE), such as the lanthanides, yttrium and scandium together with neodymium isotopes (εNd) are useful tracers in geochemistry to characterise sediment provenances. Furthermore, they can help to comprehend other elemental fluxes from land to sea. However, input mechanisms of REE into seawater are still being investigated to better understand REE cycling. Particularly, shelves in glacial areas are subject to environmental transformations due to modern climate change. Retreating glaciers expose relatively reactive sediments which are ideal to study aquatic geochemical processes governing REE distribution. We have collected filtered (0.45 µm) seawater from the Kongsfjord (Svalbard) and meltwater samples from the glaciers draining into the fjord for REE and εNd. Samples were analysed for REE on a ThermoFisher® Element2 after an offline pre-concentration using a seaFAST®. The REE were quantified with a known amount of thulium (Tm) as an internal standard prior to pre-concentration. With a neglectable fractionation amongst REE on the seaFAST column, this method allows an efficient and accurate quantification of such elements. Neodymium isotopes will be analysed at a later stage to better understand the provenance of the meltwater distributaries. The distributions of REE in the meltwater show clear enrichment of MREE and low HREE/LREE, in particular close to one land terminating glacier front on the Brogger-peninsula, typical for freshwater. Patterns from the fjord show a seawater distribution with high HREE/LREE and low Ce/Ce* in the deep outer fjord. Lower salinity surface waters are enriched in REE and show lower HREE/LREE than deep waters. Surface samples in the outer fjord show highest REE concentrations, suggesting that at this location REE inputs from the large tidewater glacier Kronebreen at the head of Kongsfjorden are subordinated to the inputs by smaller glaciers draining meltwater over proglacial sediments from the Brogger-peninsula.

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.

Description: Microorganisms in marine subsurface sediments substantially contribute to global biomass.Sediments warmer than 40°C account for roughly half the marine sediment volume, but theprocesses mediated by microbial populations in these hard-to-access environments are poorlyunderstood. We investigated microbial life in up to 1.2-kilometer-deep and up to 120°C hotsediments in the Nankai Trough subduction zone. Above 45°C, concentrations of vegetativecells drop two orders of magnitude and endospores become more than 6000 times more abundantthan vegetative cells. Methane is biologically produced and oxidized until sediments reach 80°to 85°C. In 100° to 120°C sediments, isotopic evidence and increased cell concentrationsdemonstrate the activity of acetate-degrading hyperthermophiles. Above 45°C, populated zonesalternate with zones up to 192 meters thick where microbes were undetectable

Description: Elevated dissolved iron concentrations in the methanic zone are typical geochemical signatures of rapidly accumulating marine sediments. These sediments are often characterized by co-burial of iron oxides with recalcitrant aromatic organic matter of terrigenous origin. Thus far, iron oxides are predicted to either impede organic matter degradation, aiding its preservation, or identified to enhance organic carbon oxidation via direct electron transfer. Here, we investigated the effect of various iron oxide phases with differing crystallinity (magnetite, hematite, and lepidocrocite) during microbial degradation of the aromatic model compound benzoate in methanic sediments. In slurry incubations with magnetite or hematite, concurrent iron reduction, and methanogenesis were stimulated during accelerated benzoate degradation with methanogenesis as the dominant electron sink. In contrast, with lepidocrocite, benzoate degradation, and methanogenesis were inhibited. These observations were reproducible in sediment-free enrichments, even after five successive transfers. Genes involved in the complete degradation of benzoate were identified in multiple metagenome assembled genomes. Four previously unknown benzoate degraders of the genera Thermincola (Peptococcaceae, Firmicutes), Dethiobacter (Syntrophomonadaceae, Firmicutes), Deltaproteobacteria bacteria SG8_13 (Desulfosarcinaceae, Deltaproteobacteria), and Melioribacter (Melioribacteraceae, Chlorobi) were identified from the marine sediment-derived enrichments. Scanning electron microscopy (SEM) and catalyzed reporter deposition fluorescence in situ hybridization (CARD-FISH) images showed the ability of microorganisms to colonize and concurrently reduce magnetite likely stimulated by the observed methanogenic benzoate degradation. These findings explain the possible contribution of organoclastic reduction of iron oxides to the elevated dissolved Fe2+ pool typically observed in methanic zones of rapidly accumulating coastal and continental margin sediments.

Description: The flux of methane, a potent greenhouse gas, from the seabed is largely controlled by anaerobic oxidation of methane (AOM) coupled to sulfate reduction (S-AOM) in the sulfate methane transition (SMT). S-AOM is estimated to oxidize 90 % of the methane produced in marine sediments and is governed by a consortium of anaerobic methanotrophic archaea (ANME) and sulfate reducing bacteria. An additional methane sink, i.e., iron oxide coupled AOM (Fe-AOM), has been suggested to be active in the methanic zone of marine sediments. Geochemical signatures below the SMT such as high dissolved iron, low to undetectable sulfate and high methane concentrations, together with the presence of iron oxides are taken as prerequisites for this process. So far, neither has Fe-AOM been proven in marine sediments nor have the governing key microorganisms been identified. Here, using a multidisciplinary approach, we show that Fe-AOM occurs in iron oxide-rich methanic sediments of the Helgoland Mud Area (North Sea). When sulfate reduction was inhibited, different iron oxides facilitated AOM in long-term sediment slurry incubations but manganese oxide did not. Especially magnetite triggered substantial Fe-AOM activity and caused an enrichment of ANME-2a archaea. Methane oxidation rates of 0.095 ± 0.03 nmol cm 3 d 1 attributable to Fe-AOM were obtained in short-term radiotracer experiments. The decoupling of AOM from sulfate reduction in the methanic zone further corroborated that AOM was iron oxide-driven below the SMT. Thus, our findings prove that Fe-AOM occurs in methanic marine sediments containing mineral-bound ferric iron and is a previously overlooked but likely important component in the global methane budget. This process has the potential to sustain microbial life in 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 (O2bw), 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 O2bw 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 O2bw 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 O2bw, 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 Antarctic continental shelf represents roughly 11% of the world’s continental-shelf area and exhibits the highest area-based primary production rates in the Southern Ocean. On the shelf, primary production strongly varies depending on light conditions, sea ice cover, mixing depth and nutrient availability. In regions impacted by global warming, such as the Antarctic Peninsula, these conditions are changing. The retreat of sea ice and the availability of previously ice covered areas for marine primary production has important repercussions on nutrient and carbon fluxes. In this study, we investigated benthic remineralization processes along a cryopelagic productivity gradient from year-round heavy ice conditions through the marginal ice zone to mainly ice-free conditions at the Western shelf of the Weddell Sea (East Antarctic Peninsula). Carbon mineralization rates were derived from pore-water profiles of oxygen, nitrate, ammonium, dissolved manganese and dissolved iron. Pore water samples were obtained from sediment cores retrieved by multi-coring at water depths between 330 to 455 m. Two deep stations (3000 m depth) were sampled for comparison. While yearly sea ice cover decreased from 80 to 30% between the stations, benthic carbon oxidation rates increased from 1.0 to 7.6 mmol C m-2 d-1 and the total organic carbon contents ranged from 0.15 to 1.5 wt.%. The low rates at heavy ice covered shelf stations were comparable to those of deep sea stations further north. Carbon mineralization rates showed that aerobic respiration accounted for 60-95% of the total carbon degradation. Anaerobic degradation was dominated by denitrification and iron reduction at stations with high sea ice cover, while sulfate reduction was present only at stations with less sea ice cover. Pore water Fe2+ concentrations reached up to 50 μmol/L near the sediment surface and up to 670 μmol/L at about 4 cm depth, which can lead to a substantial release of Fe2+ to the water column and to a subsequent increase of the iron limited primary production. In summary, the results indicate that future sea ice retreat may lead to a significant increase of benthic carbon mineralization with a subsequent enhancement of the benthic iron efflux.

Description: Glaciers and ice sheets export significant amounts of silicon (Si) to downstream ecosystems, impacting local and potentially global biogeochemical cycles. Recent studies have shown Si in Arctic glacial meltwaters to have an isotopically distinct signature when compared to non-glacial rivers. This is likely linked to subglacial weathering processes and mechanochemical reactions. However, there are currently no silicon isotope (d30Si) data available from meltwater streams in Antarctica, limiting the current inferences on global glacial silicon isotopic composition and its drivers. To address this gap, we present dissolved silicon (DSi), d30SiDSi, and major ion data from meltwater streams draining a polythermal glacier in the region of the West Antarctic Peninsula (WAP; King George Island) and a cold-based glacier in East Antarctica [Commonwealth Stream, McMurdo Dry Valleys (MDV)]. These data, alongside other global datasets, improve our understanding of how contrasting glacier thermal regime can impact upon Si cycling and therefore the d30SiDSi composition. We find a similar d30SiDSi composition between the two sites, with the streams on King George Island varying between -0.23 and C1.23h and the Commonwealth stream varying from -0.40 to C1.14h. However, meltwater streams in King George Island have higher DSi concentrations, and the two glacial systems exhibit opposite DSi–d30SiDSi trends. These contrasts likely result from differences in weathering processes, specifically the role of subglacial processes (King George Island) and, supraglacial processes followed by instream weathering in hyporheic zones (Commonwealth Stream). These findings are important when considering likely changes in nutrient fluxes from Antarctic glaciers under climatic warming scenarios and consequent shifts in glacial thermal regimes.