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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

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

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 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