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Rapid and profound climatic and environmental changes have been predicted for the Antarctic Peninsula with so far unknown impact on the biogeochemistry of the continental shelves. In this study, we investigate benthic carbon sedimentation, remineralization and iron cycling using sediment cores retrieved on a 400 mile transect with contrasting sea ice conditions along the eastern shelf of the Antarctic Peninsula. Sediments at comparable water depths of 330-450 m showed sedimentation and remineralization rates of organic carbon, ranging from 2.5-13 and 1.8-7.2 mmol C m-2 d-1, respectively. Both rates were positively correlated with the occurrence of marginal sea ice conditions (5-35% ice cover) along the transect, suggesting a favorable influence of the corresponding light regime and water column stratification on algae growth and sedimentation rates. From south to north, the burial efficiency of organic carbon decreased from 58% to 27%, while bottom water temperatures increased from -1.9 to -0.1 °C. Net iron reduction rates, as estimated from pore-water profiles of dissolved iron, were significantly correlated with carbon degradation rates and contributed 0.7-1.2% to the total organic carbon remineralization. Tightly coupled phosphate-iron recycling was indicated by significant covariation of dissolved iron and phosphate concentrations, which almost consistently exhibited P/Fe flux ratios of 0.26. Iron efflux into bottom waters of 0.6-4.5 µmol Fe m-2 d-1 was estimated from an empirical model. Despite the deep shelf waters, a clear bentho-pelagic coupling is indicated, shaped by the extent and duration of marginal sea ice conditions during summer, and likely to be affected by future climate change.

We investigated sediments from three different depositional environments along the northern Argentine continental margin to assess the main processes controlling sediment deposition since the last glacial period. Further, we evaluated how different depositional conditions affect (bio)geochemical processes within sediments. Sediment cores were collected during expedition SO260 in 2018[1]. Two sites are located at ~1100 m water depth north and south of the Mar del Plata Canyon (N- and S-Middle Slope Site). Another site is situated at the lower continental slope at 3600 m water depth (Lower Slope Site). Reliable age constraints of sediments deposited during the last glaciation at the Argentine margin are difficult to obtain due limited amounts of carbonate. We overcame this issue by combining radio-isotope analyses (14C,230Thex) with sedimentological, geochemical and magnetic data demonstrating that all sites experienced distinct changes over time. Both, N- and S-Middle Slope Sites, record at least the last 30 ka. The S-Middle Slope Site is dominated by continuously organic carbon-starved and winnowed sandy deposits, which according to geochemical and magnetic data leads to insignificant sulfate reduction and sulfidation of iron (oxyhydr)oxides. Glacial sedimentation rates at the Middle Slope increase northwards suggesting a decrease in bottom-current strength. The N-Middle Slope Site records a transition from the last glacial period, dominated by organic carbon-starved sands, to the early deglacial period when mainly silty and organic carbon-rich sediments were deposited between 14-15 ka BP. Concurrently, glacial sedimentation rates of ~50 cm/ka significantly increased to 120 cm/ka. We propose that this high sedimentation rate relates to lateral sediment re-deposition by current-driven focusing as response to sea level rise. Towards the Holocene, sedimentation rates strongly decreased to 8 cm/ka. We propose that the distinct decrease in sedimentation rates and change

The Polar Southern Ocean (PSO) provides an excess amount of macro-nutrients but productivity is largely limited by the availability of essential micro-nutrients, namely iron, manganese, zinc and others. Seasonal patches of increased productivity off major ice shelfs around Antarctica suggest that local sources of these deficient micro-nutrients must be present. With this session contribution we present a new study on marine ice from the Filchner-Ronne Ice Shelf (FRIS) as a potential source of iron and other limiting micro-nutrients for the Atlantic sector of the PSO. Marine ice is formed via partial melting of meteoric shelf ice near the grounding line of large ice shelves (e.g. FRIS). During this process small refrozen ice platelets accumulate in a layer of over 100 m thickness underneath the ice shelf to form marine ice containing high amounts of particulate material. In a project funded by the German Research Foundation (DFG) within the priority program SPP1158, we analyse 2 marine ice cores (B13: 62m, B15: 167m of marine ice) recovered in the 1990’s from the FRIS on their geochemical compositions. The coring location of B13 was about 40 km away from the shelf ice edge and B15 was drilled another 136 km further inland along the reconstructed flow line of B13. Due to shelf ice migration over the last 30 years, their locations have shifted about 30 km towards the shelf ice edge. First results show dissolved Fe (dFe) and Mn (dMn) concentrations ranging between 30 and 300 nMol and particulate Fe (pFe) of 20 to 120 µMol (0.2 to 1.4 µMol for pMn). These concentrations are orders of magnitude higher than the ones currently found in the PSO for those elements. Basal melting and ice-berg calving of marine ice with the accompanied release of these essential trace metals could therefore fuel local productivity in regions with large extent of shelf ice. With our study we aim to evaluate marine ice as potentially overlooked source for limiting micro-nutrients that could expla

Biogeochemical processes in subseafloor sediments can notably change over geological timescales due to variations in oceanographic, climatic and/or depositional conditions. To improve the understanding of changing biogeochemical processes on longer timescales, we investigated ~1.2 km deep and up to 120°C hot subseafloor sediments from the Nankai Trough offshore Japan (Site C0023), drilled during International Ocean Discovery Program Expedition 370 (Temperature Limit of the Deep Biosphere off Muroto)1. Over the past 15 Ma, the sediments have moved several hundreds of kilometers from the Shikoku Basin to the Nankai Trough due to tectonic motion of the Philippine Sea plate2. During this migration, the depositional, geochemical and thermal conditions have significantly changed. By combining geochemical data, sedimentation rates and reactive transport modeling, we reconstructed the evolution of biogeochemical processes in sediments at Site C0023. A distinctive feature at Site C0023 is an inverse sulfate-methane transition (SMT) at ~730 m depth with a broad sulfate-methane overlap zone of ~100 m, suggesting inefficient anaerobic oxidation of methane (AOM). This depth interval corresponds to a temperature of 80° to 85°C, which coincides with the known temperature limit of AOM-performing microbial communities3,4. Our model results demonstrate that the inverse SMT was formed at ~2.5 Ma after the onset of biogenic methanogenesis and AOM as a consequence of enhanced organic carbon burial. Depth-integrated AOM rates derived from the model markedly decrease since the beginning of trench-style deposition and the associated rapid heating of the sediments at ~0.4 Ma, indicating that the microbial activity of AOM-performing communities at the inverse SMT has already started to cease and the SMT is about to disappear. This successive fading of the SMT and, thus, a decrease in the efficiency of the microbial methane sink is ultimately related to the temperature increase beyond the thr

Permeable sandy sediments cover 50-60% of the global continental shelf and are important bioreactors that regulate organic matter (OM) turnover and nutrient cycling in the coastal ocean. In sands, the dynamic porewater advection can cause rapid mass transfer and variable redox conditions, thus affecting OM remineralization pathways as well as the recycling of iron and phosphorus. In this study, North Sea sands were incubated in flow-through reactors (FTRs) to investigate biogeochemical processes under porewater advection and changing redox conditions. We found that the average rate of anaerobic OM remineralization was 12 times lower than the aerobic pathway, and Fe(III) oxyhydroxides were found as the major electron acceptors during 34 days of anoxic incubation. Abundant reduced Fe in the solid phase (expressed as Fe(II)) was measured before extensive Fe2+ release into porewater, and most of the reduced Fe (~96%) remained in the solid phase throughout the anoxic incubation. Fe(II) retained in the solid phase, either through the formation of authigenic Fe(II)-bearing minerals or adsorption, was easily re-oxidized upon exposure to O2 . Excessive P release (apart from OM remineralization) started at the beginning of the anoxic incubation and accelerated after the release of Fe2+ with a constant P/Fe2+ ratio of 0.26. After 34 days of anoxic incubation, porewater was re-oxygenated and >99% of released P was coprecipitated through Fe2+ oxidation (so-called “Fe2+ curtain”). Our results demonstrate that Fe(III)/Fe(II) in the solid phase can serve as relatively immobile and rechargeable “redox battery” under dynamic porewater advection. Due to frequent oscillation of redox conditions, the Fe “redox battery” is characteristic for permeable sediments and plays an important role in coastal OM turnover. We also suggest that P liberated before Fe2+ release can escape the “Fe2+ curtain” in porewater advection, thus potentially increasing net benthic P efflux from permeable sedimen

We investigated sediments from three different depositional environments along the northern Argentine continental margin to assess the main processes controlling sediment deposition since the last glacial period. Further, we evaluated how different depositional conditions affect (bio)geochemical processes within sediments. Sediment cores were collected during expedition SO260 in 2018[1]. Two sites are located at ~1100 m water depth north and south of the Mar del Plata Canyon (N- and S-Middle Slope Site). Another site is situated at the lower continental slope at 3600 m water depth (Lower Slope Site). Reliable age constraints of sediments deposited during the last glaciation at the Argentine margin are difficult to obtain due limited amounts of carbonate. We overcame this issue by combining radio-isotope analyses (14C,230Thex) with sedimentological, geochemical and magnetic data demonstrating that all sites experienced distinct changes over time. Both, N- and S-Middle Slope Sites, record at least the last 30 ka. The S-Middle Slope Site is dominated by continuously organic carbon-starved and winnowed sandy deposits, which according to geochemical and magnetic data leads to insignificant sulfate reduction and sulfidation of iron (oxyhydr)oxides. Glacial sedimentation rates at the Middle Slope increase northwards suggesting a decrease in bottom-current strength. The N-Middle Slope Site records a transition from the last glacial period, dominated by organic carbon-starved sands, to the early deglacial period when mainly silty and organic carbon-rich sediments were deposited between 14-15 ka BP. Concurrently, glacial sedimentation rates of ~50 cm/ka significantly increased to 120 cm/ka. We propose that this high sedimentation rate relates to lateral sediment re-deposition by current-driven focusing as response to sea level rise. Towards the Holocene, sedimentation rates strongly decreased to 8 cm/ka. We propose that the distinct decrease in sedimentation rates and change

Rapid and profound climatic and environmental changes have been predicted for the Antarctic Peninsula with so far unknown impact on the biogeochemistry of the continental shelves. In this study, we investigate benthic carbon sedimentation, remineralization and iron cycling using sediment cores retrieved on a 400 mile transect with contrasting sea ice conditions along the eastern shelf of the Antarctic Peninsula. Sediments at comparable water depths of 330-450 m showed sedimentation and remineralization rates of organic carbon, ranging from 2.5-13 and 1.8-7.2 mmol C m-2 d-1, respectively. Both rates were positively correlated with the occurrence of marginal sea ice conditions (5-35% ice cover) along the transect, suggesting a favorable influence of the corresponding light regime and water column stratification on algae growth and sedimentation rates. From south to north, the burial efficiency of organic carbon decreased from 58% to 27%, while bottom water temperatures increased from -1.9 to -0.1 °C. Net iron reduction rates, as estimated from pore-water profiles of dissolved iron, were significantly correlated with carbon degradation rates and contributed 0.7-1.2% to the total organic carbon remineralization. Tightly coupled phosphate-iron recycling was indicated by significant covariation of dissolved iron and phosphate concentrations, which almost consistently exhibited P/Fe flux ratios of 0.26. Iron efflux into bottom waters of 0.6-4.5 µmol Fe m-2 d-1 was estimated from an empirical model. Despite the deep shelf waters, a clear bentho-pelagic coupling is indicated, shaped by the extent and duration of marginal sea ice conditions during summer, and likely to be affected by future climate change.

Volcanic ash significantly contributes to marine sediments, especially in regions with active onshore volcanoes. Alteration of volcanic ash releases bicarbonate and cations, which drive precipitation of authigenic carbonate and clay minerals. Furthermore, volcanic ashes are commonly enriched in reactive iron (Fe[III]), suggesting that ash alteration as a source of reactants plays an important role in (bio-)geochemical processes in marine sediments. Volcanic ash layers are ubiquitous in sediments of Site C0023, which was established down to 1180 m below seafloor (mbsf) in the Nankai Trough off Japan during International Ocean Discovery Program Expedition 370. Shipboard measurements show a release of dissolved Fe between 200 and 600 mbsf, coinciding with a high abundance of ash layers [1]. The release of Fe can be related to microbial reduction of structural Fe(III) in smectite promoting the smectite-to-illite transition, as recently proposed [2]. By combining shipboard pore-water data with sequential extractions of reactive Fe pools on ash layers and surrounding mud rock and stable Fe isotope (δ56Fe) analyses, we elucidate the role of ash alteration on (bio-)geochemical cycling at Site C0023. Our results demonstrate that reactive Fe(III) is unexpectedly lower in ash layers compared to the surrounding mud rock (0.6 and 1.2 wt%, respectively). This indicates that (1) Fe(III) originally deposited with tephra has either been used or (2) Fe(III) in tephra is generally lower due to a different chemical composition in the volcanic source material. The δ56Fe signature of hydroxylamine-extracted Fe, which represents easily reducible Fe-oxides and Fe bound in phyllosilicates, is isotopically light (-0.08 to -0.42‰) compared to terrestrial background values (~0.09‰; [3]). This suggests that this pool is diagenetically overprinted by the precipitation of authigenic smectite formed as a result of ash alteration and/or secondary Fe-oxides. Pore-water Fe is extremely negative with

The Argentina Continental Margin represents a unique geologic setting to study interactions between bottom currents and sediment deposition as well as their impact on (bio)geochemical processes, particularly the cycling of iron (Fe). Our aim was to determine (1) how different depositional conditions control post-depositional (bio)geochemical processes and (2) how stable Fe isotopes (δ56Fe) of pore water and solid phases are affected accordingly. Furthermore, we (3) evaluated the applicability of δ56Fe of solid Fe pools as a proxy to trace past diagenetic alteration of Fe, which might be decoupled from current redox conditions. Sediments from two different depositional environments were sampled during RV SONNE expedition SO260: a site dominated by contouritic deposition on a terrace (Contourite Site) and the lower continental slope (Slope Site) dominated by hemipelagic sedimentation. Sequentially extracted sedimentary Fe [1] and δ56Fe analyses of extracts and pore water [2,3] were combined with sedimentological, radioisotope, geochemical and magnetic data. Our study presents the first sedimentary δ56Fe dataset at the Argentina Continental Margin. The depositional conditions differed between and within both sites as evidenced by variable grain sizes, organic carbon contents and sedimentation rates. At the Contourite Site, non-steady state pore-water conditions and diagenetic overprint occurs in the post-oxic zone and the sulfate-methane transition (SMT). In contrast, pore-water profiles at the Slope Site suggest that currently steady-state conditions prevail, leading to a strong diagenetic overprint of Fe oxides at the SMT. Pore-water δ56Fe values at the Slope Site are mostly negative, which is typical for on-going microbial Fe reduction. At the Contourite Site the pore-water δ56Fe values are mostly positive and range between -0.35‰ to 1.82‰. Positive δ56Fe values are related to high sulfate reduction rates that dominate over Fe reduction in the post-oxic zone. The HS

Antarctic shelf regions are potential carbon and nutrient cycling hotspots where rapid climatic changes are projected to affect seasonal sea ice cover, water column stratification, and thus surface primary production and associated fluxes of organic carbon to the seafloor. Here, we report on surface sediment oxygen profiles and respective fluxes in combination with pore water profiles of dissolved iron (DFe) and phosphate (PO43-) from 7 stations along a 400 mile transect with variable sea ice cover and water column stratification from the East Antarctic Peninsula to the west of South Orkney Islands. Our results show that sea ice concentrations and stratification of the upper water column decreased across the transect. We defined a marginal sea ice index of 5-35% sea ice cover which was positively correlated with the benthic carbon mineralization rate. C-mineralization rates increased gradually between the heavy ice-covered station and the marginal sea ice stations from 1.1 to 7.3 mmol C m-2 d-1, respectively. The rates decreased again to 1.8 mmol C m-2 d-1 at the ice-free station, likely attributed to a deeper water column mixed layer depth, which decreases primary production and thus organic carbon export to the sediment. Iron cycling in the sediment was elevated at the marginal sea ice stations where Fe-reduction led to DFe fluxes in the pore water of up to 0.379 mmol DFe m-2 d-1, while moderate (0.068 mmol DFe m-2 d-1) and negligible fluxes were observed at ice-free and ice-covered stations, respectively. In pore waters, concentrations of DFe and PO43- were significantly correlated with almost identical flux ratios of 0.33 mol PO43- per mol DFe for most of the stations, indicating a strong control of the iron cycling on the phosphate release to the water column. The high benthic DFe and PO43- fluxes highlight the importance of sediments underlying the marginal ice zone as source for limiting nutrients to the shelf waters.

Diagenesis can have a major impact on sedimentary mineralogy. Primary magnetic mineral assemblages can be modified significantly by dissolution or by formation of new magnetic minerals during early or late diagenesis. At International Ocean Discovery Program Site C0023, which was drilled in the protothrust zone of the Nankai Trough during Expedition 370, offshore of Shikoku Island, Japan, non-steady state conditions have produced a complex sequence of magnetic overprints. Detailed rock magnetic measurements, which characterize magnetic mineral assemblages in terms of abundance, grain size, and composition, were conducted to assess magnetic mineral alteration and diagenetic overprinting. Four magnetic zones (MZs) are identified down-core from ∼200 to 1100 meters below sea floor based on rock magnetic variations. MZ 1 is a high magnetic intensity zone that contains ferrimagnetic greigite, which formed at shallow depths and is preserved because of rapid sedimentation. MZs 2 and 4 are low magnetic intensity zones with fewer magnetic minerals, mainly coarse-grained (titano-)magnetite and hematite. This magnetic mineral assemblage is a remnant of a more complex assemblage that was altered diagenetically a few million years after deposition when the site entered the Nankai Trough. MZ 3 is a high magnetic intensity zone between MZs 2 and 4. It contains authigenic single-domain magnetic particles that probably formed from fluids that circulated through faults in the accretionary prism. Varying sediment supply and organic matter input through time, burial temperature, and tectonic fluid circulation are the primary drivers of magnetic mineral assemblage variations.

Biogeochemical processes in subseafloor sediments are closely coupled to global element cycles. To improve the understanding of changes in biogeochemical conditions on geological timescales, we investigate sediment cores from a 1180 m deep hole in the Nankai Trough offshore Japan (Site C0023) drilled during International Ocean Discovery Program Expedition 370. During its tectonic migration from the Shikoku Basin to the Nankai Trough over the past 15 Ma, Site C0023 has experienced significant changes in depositional, thermal, and geochemical conditions. By combining pore-water, solid-phase, and rock magnetic data, we demonstrate that a transition from organic carbon-starved conditions with predominantly aerobic respiration to an elevated carbon burial environment with increased sedimentation occurred at ∼2.5 Ma. Higher rates of organic carbon burial in consequence of increased nutrient supply and productivity likely stimulated the onset of anaerobic electron-accepting processes during organic carbon degradation. A significant temperature increase by ∼50°C across the sediment column associated with trench-style sedimentation since ∼0.5 Ma could increase the bioavailability of organic matter and enhance biogenic methanogenesis. The resulting shifts in reaction fronts led to diagenetic transformation of iron (oxyhydr)oxides into pyrite in the organic carbon-starved sediments several millions of years after burial. We also show that high amounts of reducible iron(III) which can serve as electron acceptor for microbial iron(III) reduction are preserved and still available as phyllosilicate-bound Fe. This is the first study that shows the evolution of long-term variations of (bio-)geochemical processes along tectonic migration of ocean floor, thereby altering the primary sediment composition long after deposition.

Colonization of newly ice-free areas by marine benthic organisms intensifies burial of macroalgae detritus in Potter Cove coastal surface sediments (Western Antarctic Peninsula). Thus, fresh and labile macroalgal detritus serves as primary organic matter (OM) source for microbial degradation. Here, we investigated the effects on post-depositional microbial iron reduction in Potter Cove using sediment incubations amended with pulverized macroalgal detritus as OM source, acetate as primary product of OM degradation and lepidocrocite as reactive iron oxide to mimic in situ conditions. Humic substances analogue anthraquinone-2,6-disulfonic acid (AQDS) was also added to some treatments to simulate potential for electron shuttling. Microbial iron reduction was promoted by macroalgae and further enhanced by up to 30-folds with AQDS. Notably, while acetate amendment alone did not stimulate iron reduction, adding macroalgae alone did. Acetate, formate, lactate, butyrate and propionate were detected as fermentation products from macroalgae degradation. By combining 16S rRNA gene sequencing and RNA stable isotope probing, we reconstructed the potential microbial food chain from macroalgae degraders to iron reducers. Psychromonas, Marinifilum, Moritella, and Colwellia were detected as potential fermenters of macroalgae and fermentation products such as lactate. Members of class deltaproteobacteria including Sva1033, Desulfuromonas, and Desulfuromusa together with Arcobacter (former phylum Epsilonbacteraeota, now Campylobacterota) acted as dissimilatory iron reducers. Our findings demonstrate that increasing burial of macroalgal detritus in an Antarctic fjord affected by glacier retreat intensifies early diagenetic processes such as iron reduction. Under scenarios of global warming, the active microbial populations identified above will expand their environmental function, facilitate OM remineralisation, and contribute to an increased release of iron and CO2 from sediments. Such

(Bio-)geochemical processes in subseafloor sediments are closely coupled to global element cycles. To gain an improved understanding of changes in (bio-)geochemical conditions on geological timescales, we investigate sediment cores from a 1180 m deep hole in the Nankai Trough offshore Japan (Site C0023). The sediment cores were taken during International Ocean Discovery Program (IODP) Expedition 370 (Temperature Limit of the Deep Biosphere off Muroto), which aimed at exploring the prerequisites and limits of deep microbial life [1]. Over the past 15 Ma, Site C0023 has moved ~750 km relative to its present-day geographic position from the central Shikoku Basin to the Nankai Trough due to motion of the Philippine Sea plate [2]. During its tectonic migration, Site C0023 has experienced significant changes in depositional and thermal conditions as well as resulting (bio-)geochemical processes. By combining a large set of complementary pore-water, solid-phase and rock magnetic data with sedimentation rates and sediment ages, our aim is to (1) reconstruct the evolution of (bio-)geochemical processes, especially the cycling of iron, along the tectonic migration, and to (2) investigate if iron(III) minerals are still available to serve as energy substrate for microbial respiration in the deep sediments. Our results demonstrate that a transition from organic carbon-starved conditions with predominantly aerobic respiration processes to an elevated carbon burial environment with increased sedimentation occurred at ~2.5 Ma. Higher rates of organic carbon burial as a consequence of an increased nutrient supply and primary productivity likely stimulated the onset of organoclastic iron and sulfate reduction, biogenic methanogenesis and anaerobic oxidation of methane. A significant temperature increase by 50°C across the sediment column associated with trench-style sedimentation since 0.5 Ma potentially increased the bioavailability of organic matter and enhanced biogenic methane p

The area around the Antarctic Peninsula is projected to undergo rapid climatic changes affecting seasonal sea ice cover, water column stratification, terrestrial meltwater run-off, and related nutrient input and thus the conditions for primary production and organic carbon export. The impact of such environmental changes on benthic microbial communities is poorly understood. In this study, we investigated the impact of different sea ice cover and redox conditions on microbial community compositions from 7 different stations (330–450 m water depth) along a 400-mile transect from the eastern shelf of the Antarctic Peninsula to the west of the South Orkney Islands. Two deep stations (3000 m depth) were sampled for comparison. Samples were collected from 6 different intervals down to a depth of 16 cm. The diversity and composition of microbial communities were determined by 16S ribosomal RNA (rRNA) gene sequencing. Redox conditions in sediments with long ice-free periods showed that iron and sulfate reduction are dominant anaerobic pathways for carbon mineralization. In contrast, sediments at a heavily ice-covered station were dominated by the aerobic pathway, which accounted for >94 % of the total carbon degradation. Our results reveal that the microbial community composition at the station under heavy ice-cover differs significantly from stations under low ice-cover and tends to cluster separately, suggesting that sea ice cover is the main driver for changes in microbial community composition in the shelf sediments. Further, the frequency of marginal sea ice conditions (here defined as 5-35% sea ice cover) is significantly different between stations (p 0.001) and can explain 5 to 13% of the variation between microbial communities. The bacterial communities at stations under low ice-cover co-varied significantly with TOC content and porewater concentrations of ammonia, dissolved iron, and sulfide. This was reflected in the microbial community composition, where station

The area around the Antarctic Peninsula is projected to undergo rapid climatic changes affecting seasonal sea ice cover, water column stratification, terrestrial meltwater run-off, and related nutrient input and thus the conditions for primary production and organic carbon export. The impact of such environmental changes on benthic microbial communities is poorly understood. In this study, we investigated the impact of different sea ice cover and redox conditions on microbial community compositions from 7 different stations (330–450 m water depth) along a 400-mile transect from the eastern shelf of the Antarctic Peninsula to the west of the South Orkney Islands. Two deep stations (3000 m depth) were sampled for comparison. Samples were collected from 6 different intervals down to a depth of 16 cm. The diversity and composition of microbial communities were determined by 16S ribosomal RNA (rRNA) gene sequencing. Redox conditions in sediments with long ice-free periods showed that iron and sulfate reduction are dominant anaerobic pathways for carbon mineralization. In contrast, sediments at a heavily ice-covered station were dominated by the aerobic pathway, which accounted for >94 % of the total carbon degradation. Our results reveal that the microbial community composition at the station under heavy ice-cover differs significantly from stations under low ice-cover and tends to cluster separately, suggesting that sea ice cover is the main driver for changes in microbial community composition in the shelf sediments. Further, the frequency of marginal sea ice conditions (here defined as 5-35% sea ice cover) is significantly different between stations (p 0.001) and can explain 5 to 13% of the variation between microbial communities. The bacterial communities at stations under low ice-cover co-varied significantly with TOC content and porewater concentrations of ammonia, dissolved iron, and sulfide. This was reflected in the microbial community composition, where station

Diagenesis can have a major impact on sedimentary mineralogy. Primary magnetic mineral assemblages can be modified significantly by dissolution or by formation of new magnetic minerals during early or late diagenesis. At International Ocean Discovery Program Site C0023, which was drilled in the protothrust zone of the Nankai Trough during Expedition 370, offshore of Shikoku Island, Japan, non-steady state conditions have produced a complex sequence of magnetic overprints. Detailed rock magnetic measurements, which characterize magnetic mineral assemblages in terms of abundance, grain size, and composition, were conducted to assess magnetic mineral alteration and diagenetic overprinting. Four magnetic zones (MZs) are identified down-core from ∼200 to 1100 meters below sea floor based on rock magnetic variations. MZ 1 is a high magnetic intensity zone that contains ferrimagnetic greigite, which formed at shallow depths and is preserved because of rapid sedimentation. MZs 2 and 4 are low magnetic intensity zones with fewer magnetic minerals, mainly coarse-grained (titano-)magnetite and hematite. This magnetic mineral assemblage is a remnant of a more complex assemblage that was altered diagenetically a few million years after deposition when the site entered the Nankai Trough. MZ 3 is a high magnetic intensity zone between MZs 2 and 4. It contains authigenic single-domain magnetic particles that probably formed from fluids that circulated through faults in the accretionary prism. Varying sediment supply and organic matter input through time, burial temperature, and tectonic fluid circulation are the primary drivers of magnetic mineral assemblage variations.

Antarctic shelf regions are potential carbon and nutrient cycling hotspots where rapid climatic changes are projected to affect seasonal sea ice cover, water column stratification, and thus surface primary production and associated fluxes of organic carbon to the seafloor. Here, we report on surface sediment oxygen profiles and respective fluxes in combination with pore water profiles of dissolved iron (DFe) and phosphate (PO43-) from 7 stations along a 400 mile transect with variable sea ice cover and water column stratification from the East Antarctic Peninsula to the west of South Orkney Islands. Our results show that sea ice concentrations and stratification of the upper water column decreased across the transect. We defined a marginal sea ice index of 5-35% sea ice cover which was positively correlated with the benthic carbon mineralization rate. C-mineralization rates increased gradually between the heavy ice-covered station and the marginal sea ice stations from 1.1 to 7.3 mmol C m-2 d-1, respectively. The rates decreased again to 1.8 mmol C m-2 d-1 at the ice-free station, likely attributed to a deeper water column mixed layer depth, which decreases primary production and thus organic carbon export to the sediment. Iron cycling in the sediment was elevated at the marginal sea ice stations where Fe-reduction led to DFe fluxes in the pore water of up to 0.379 mmol DFe m-2 d-1, while moderate (0.068 mmol DFe m-2 d-1) and negligible fluxes were observed at ice-free and ice-covered stations, respectively. In pore waters, concentrations of DFe and PO43- were significantly correlated with almost identical flux ratios of 0.33 mol PO43- per mol DFe for most of the stations, indicating a strong control of the iron cycling on the phosphate release to the water column. The high benthic DFe and PO43- fluxes highlight the importance of sediments underlying the marginal ice zone as source for limiting nutrients to the shelf waters.

Biogeochemical processes in subseafloor sediments are closely coupled to global element cycles. To improve the understanding of changes in biogeochemical conditions on geological timescales, we investigate sediment cores from a 1180 m deep hole in the Nankai Trough offshore Japan (Site C0023) drilled during International Ocean Discovery Program Expedition 370. During its tectonic migration from the Shikoku Basin to the Nankai Trough over the past 15 Ma, Site C0023 has experienced significant changes in depositional, thermal, and geochemical conditions. By combining pore-water, solid-phase, and rock magnetic data, we demonstrate that a transition from organic carbon-starved conditions with predominantly aerobic respiration to an elevated carbon burial environment with increased sedimentation occurred at ∼2.5 Ma. Higher rates of organic carbon burial in consequence of increased nutrient supply and productivity likely stimulated the onset of anaerobic electron-accepting processes during organic carbon degradation. A significant temperature increase by ∼50°C across the sediment column associated with trench-style sedimentation since ∼0.5 Ma could increase the bioavailability of organic matter and enhance biogenic methanogenesis. The resulting shifts in reaction fronts led to diagenetic transformation of iron (oxyhydr)oxides into pyrite in the organic carbon-starved sediments several millions of years after burial. We also show that high amounts of reducible iron(III) which can serve as electron acceptor for microbial iron(III) reduction are preserved and still available as phyllosilicate-bound Fe. This is the first study that shows the evolution of long-term variations of (bio-)geochemical processes along tectonic migration of ocean floor, thereby altering the primary sediment composition long after deposition.

(Bio-)geochemical processes in subseafloor sediments are closely coupled to global element cycles. To gain an improved understanding of changes in (bio-)geochemical conditions on geological timescales, we investigate sediment cores from a 1180 m deep hole in the Nankai Trough offshore Japan (Site C0023). The sediment cores were taken during International Ocean Discovery Program (IODP) Expedition 370 (Temperature Limit of the Deep Biosphere off Muroto), which aimed at exploring the prerequisites and limits of deep microbial life [1]. Over the past 15 Ma, Site C0023 has moved ~750 km relative to its present-day geographic position from the central Shikoku Basin to the Nankai Trough due to motion of the Philippine Sea plate [2]. During its tectonic migration, Site C0023 has experienced significant changes in depositional and thermal conditions as well as resulting (bio-)geochemical processes. By combining a large set of complementary pore-water, solid-phase and rock magnetic data with sedimentation rates and sediment ages, our aim is to (1) reconstruct the evolution of (bio-)geochemical processes, especially the cycling of iron, along the tectonic migration, and to (2) investigate if iron(III) minerals are still available to serve as energy substrate for microbial respiration in the deep sediments. Our results demonstrate that a transition from organic carbon-starved conditions with predominantly aerobic respiration processes to an elevated carbon burial environment with increased sedimentation occurred at ~2.5 Ma. Higher rates of organic carbon burial as a consequence of an increased nutrient supply and primary productivity likely stimulated the onset of organoclastic iron and sulfate reduction, biogenic methanogenesis and anaerobic oxidation of methane. A significant temperature increase by 50°C across the sediment column associated with trench-style sedimentation since 0.5 Ma potentially increased the bioavailability of organic matter and enhanced biogenic methane p

Colonization of newly ice-free areas by marine benthic organisms intensifies burial of macroalgae detritus in Potter Cove coastal surface sediments (Western Antarctic Peninsula). Thus, fresh and labile macroalgal detritus serves as primary organic matter (OM) source for microbial degradation. Here, we investigated the effects on post-depositional microbial iron reduction in Potter Cove using sediment incubations amended with pulverized macroalgal detritus as OM source, acetate as primary product of OM degradation and lepidocrocite as reactive iron oxide to mimic in situ conditions. Humic substances analogue anthraquinone-2,6-disulfonic acid (AQDS) was also added to some treatments to simulate potential for electron shuttling. Microbial iron reduction was promoted by macroalgae and further enhanced by up to 30-folds with AQDS. Notably, while acetate amendment alone did not stimulate iron reduction, adding macroalgae alone did. Acetate, formate, lactate, butyrate and propionate were detected as fermentation products from macroalgae degradation. By combining 16S rRNA gene sequencing and RNA stable isotope probing, we reconstructed the potential microbial food chain from macroalgae degraders to iron reducers. Psychromonas, Marinifilum, Moritella, and Colwellia were detected as potential fermenters of macroalgae and fermentation products such as lactate. Members of class deltaproteobacteria including Sva1033, Desulfuromonas, and Desulfuromusa together with Arcobacter (former phylum Epsilonbacteraeota, now Campylobacterota) acted as dissimilatory iron reducers. Our findings demonstrate that increasing burial of macroalgal detritus in an Antarctic fjord affected by glacier retreat intensifies early diagenetic processes such as iron reduction. Under scenarios of global warming, the active microbial populations identified above will expand their environmental function, facilitate OM remineralisation, and contribute to an increased release of iron and CO2 from sediments. Such

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 subs

The Argentina Continental Margin represents a unique geologic setting where fundamental interactions between bottom currents and sediment deposition as well as their impact on biogeochemical processes and element cycling, in particular iron, can be studied. The aims of this study were to investigate 1) the consequences of different depositional conditions on biogeochemical processes and 2) diagenetic cycling of Fe mineral phases in surface sediments. Furthermore, it was 3) studied how sedimentary stable Fe isotope signatures (δ56Fe) are affected during early diagenesis and finally 4) evaluated, under which conditions δ56Fe might be used as proxy for microbial Fe reduction in methanic sediments. During RV SONNE expedition SO260, carried out in the framework of the DFG-funded Cluster of Excellence “The Ocean in the Earth System”, surface sediments from two depositional environments were sampled each using gravity corer and multi corer. One study site is located on the lower continental slope at 3605 m water depth (Biogeochemistry Site), while the other site is situated in a contourite system on the Northern Ewing Terrace at 1078 m water depth (Contourite Terrace Site). Sequential Fe extractions were performed on the collected sediments to determine four operationally defined reactive Fe phases targeting Fe carbonates, (easily) reducible Fe (oxyhydr)oxides and hardly reducible Fe oxides [1]. Purification of extracts for δ56Fe analysis of the Fe carbonates and easily reducible Fe (oxyhydr)oxide fractions followed [2]. The dataset was combined with pore-water data obtained during the cruise and complemented by concentrations and stable carbon isotope signatures of dissolved methane determined post-cruise. The extent of the redox zonation and depth of the sulfate-methane-transition (SMT) differ between the two sites. It is suggested that sedimentation rates at the Biogeochemistry Site are low and that steady state conditions prevail, leading to a strong diagenetic overpri

The deep subseafloor biosphere represents one of the Earth’s largest, but also least understood ecosystems with diverse species and mostly uncharacterized microbial communities. International Ocean Discovery Program (IODP) Expedition 370 (Temperature Limit of the Deep Biosphere off Muroto) established Site C0023 down to 1180 mbsf in the Nankai Trough off Japan to explore the upper temperature limit of microbial life in the deep sedimentary biosphere [1]. Site C0023 is characterized by a complex lithostratigraphic and depositional history with strongly changing sedimentation rates. Volcanic ash layers are ubiquitous in all lithological units. However, the highest abundance of ash layers could be observed between 400 and 700 mbsf. Previous studies have shown that volcanic ashes represent hotspots for microbial life [2] and are commonly characterized by high Fe(III) and Mn(IV) contents [3]. Onboard measurements show a release of dissolved Fe in the depth interval associated with the highest abundance of ash layers [1]. Therefore, we hypothesized that the release is related to microbial Fe reduction fueled by the mineralogy of the volcanic ash. In order to identify the source and reaction pathway of the liberated Fe, we applied sequential extractions of differently reactive Fe oxide pools on mud rock and ash layer samples as well as stable iron isotope (δ56Fe) analyses on pore-water and solid-phase samples. Microbial Fe reduction leads to Fe isotope fractionation with an enrichment of light isotopes in the released Fe and a respective enrichment of heavy isotopes in the residual ferric substrate. Therefore, the δ56Fe signals of different reactive Fe pools and the pore water are used to identify the pools actually involved in microbial respiration processes. Our results show that the total Fe content in mud rock of Site C0023 is relatively constant at ~4.2 wt%. Reactive Fe oxides represent 25% of the total Fe. The bulk Fe content in the ash layers varies between 1.4 and

A number of studies have shown that iron reduction in marine sediments is not confined to sulfate- or sulfide-containing depths but may also affect deep methanic intervals. In particular dynamic depositional settings often show the release of dissolved iron below the sulphate-methane transition (SMT). The specific process behind this deep iron release is not well understood. It has been suggested that anaerobic oxidation of methane (AOM) mediated by Fe oxide reduction plays an important role. So there might be a close, so far unaccounted link between the Fe and C cycles in deep marine sediments. Here we present a compilation of inorganic geochemical data including δ56Fe values of pore water and reactive Fe fractions for sediments of the Helgoland mud area (North Sea) for which a coupling between deep iron reduction and AOM has been proposed [1]. The sediments show a shallow SMT and increasing dissolved Fe concentrations of up to 400 µM further below. High sedimentation rates led to a fast burial and preservation of reactive Fe (oxyhydr)oxides, enabling deep iron reduction as we observe it today. Isotopic fractionation of Fe has been demonstrated for DIR in culture experiments and in shallow marine sediments. Such studies build upon the principle that microbes preferentially utilize light Fe isotopes (54Fe) causing a fractionation between solid ferric and dissolved ferrous iron. For alternative biotic Fe reduction pathways in methanic environments, there are practically no data. We hypothesized that any microbially mediated iron reduction process would result in a similar preferential release of 54Fe and, thus, shift pore water δ56Fe towards negative values. Furthermore we hypothesized that the microbial utilization of a specific Fe (oxyhydr)oxide pool would result in a relative enrichment of 56Fe in the residual ferric substrate. Close to the sediment-water interface pore water δ56Fe in the mud area is generally negative and shows a downward trend towards positive v

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

Polar regions are critical for future climate evolution, and they experience major environmental changes. A particular focus of biogeochemical investigations in these regions lies on iron (Fe). This element drives primary productivity and, thus, the uptake of atmospheric CO2 in vast areas of the ocean. Due to the Fe-limitation of phytoplankton growth in the Southern Ocean, Antarctica is a key region for studying the change of iron fluxes as glaciers progressively melt away. The respective climate feedbacks can currently hardly be quantified because data availability is low, and iron transport and reaction pathways in Polar coastal and shelf areas are insufficiently understood. We show how novel stable Fe isotope techniques, in combination with other geochemical analyses, can be used to identify iron discharges from subglacial environments and how this will help us assessing short and long term impacts of glacier retreat on coastal ecosystems. Stable Fe isotopes (δ56Fe) may be used to trace Fe sources and reactions, but respective data availability is low. In addition, there is a need to constrain δ56Fe endmembers for different types of sediments, environments, and biogeochemical processes. δ56Fe data from pore waters and sequentially extracted solid Fe phases at two sites in Potter Cove (King George Island, Antarctica), a bay affected by fast glacier retreat, are presented. Close to the glacier front, sediments contain high amounts of easily reducible Fe oxides and show a dominance of ferruginous conditions compared to sediments close to the ice-free coast, where surficial oxic meltwater discharges and sulfate reduction dominates. We suggest that high amounts of reducible Fe oxides close to the glacier mainly derive from subglacial sources, where Fe liberation from comminuted material beneath the glacier is coupled to biogeochemical weathering. A strong argument for a subglacial source is the predominantly negative δ56Fe signature of reducible Fe oxides that remains

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.

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 in-stream 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.

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 (delta Si-30) 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), delta Si-30(DSi), 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 delta(30)Si(DSi)composition. We find a similar delta(30)Si(DSi)composition between the two sites, with the streams on King George Island varying between -0.23 and +1.23 parts per thousand and the Commonwealth stream varying from -0.40 to +1.14 parts per thousand. However, meltwater streams in King George Island have higher DSi concentrations, and the two glacial systems exhibit opposite DSi - delta(30)Si(DSi)trends. These contrasts likely result from differences in weathering processes, specifically the role of subglacial processes (King George Island) and, supraglacial processes followed by in-stream 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.

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 a

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

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.

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.

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.

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

Microorganisms in marine subsurface sediments substantially contribute to global biomass. Sediments warmer than 40°C account for roughly half the marine sediment volume, but the processes mediated by microbial populations in these hard-to-access environments are poorly understood. We investigated microbial life in up to 1.2-kilometer-deep and up to 120°C hot sediments in the Nankai Trough subduction zone. Above 45°C, concentrations of vegetative cells drop two orders of magnitude and endospores become more than 6000 times more abundant than 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 concentrations demonstrate the activity of acetate-degrading hyperthermophiles. Above 45°C, populated zones alternate with zones up to 192 meters thick where microbes were undetectable.

Microorganisms in marine subsurface sediments substantially contribute to global biomass. Sediments warmer than 40°C account for roughly half the marine sediment volume, but the processes mediated by microbial populations in these hard-to-access environments are poorly understood. We investigated microbial life in up to 1.2-kilometer-deep and up to 120°C hot sediments in the Nankai Trough subduction zone. Above 45°C, concentrations of vegetative cells drop two orders of magnitude and endospores become more than 6000 times more abundant than 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 concentrations demonstrate the activity of acetate-degrading hyperthermophiles. Above 45°C, populated zones alternate with zones up to 192 meters thick where microbes were undetectable.

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

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 a