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Mass accumulation rates of sediments[g/cm2/yr] or sedimentation rates[cm/yr] on the seafloor are important to understand various benthic properties, like the rate of carbon sequestration in the seafloor and seafloor geomechanical stability. Several machine learning models, such as random forests, and k-Nearest Neighbours have been proposed for the prediction of geospatial data in marine geosciences, but face significant challenges such as the limited amount of labels for training purposes, skewed data distribution, a large number of features etc. Previous model predictions show deviation in the global sediment budget, a parameter used to determine a model's predicitve validity, revealing the lack of accurate representation of sedimentation rate by the state of the art models. Here we present a semi-supervised deep learning methodology to improve the prediction of sedimentation rates, making use of around 9x106 unlabelled data points. The semi-supervised neural network implementation has two parts: an unsupervised pretraining using an encoder-decoder network. The encoder with the optimized weights from the unsupervised training is then taken out and fitted with layers that lead to the target dimension. This network is then fine-tuned with 2782 labelled data points, which are observed sedimentation rates from peer-reviewed sources. The fine-tuned model then predicts the rate and quantity of sediment accumulating on the ocean floor, globally.The developed semi-supervised neural network provide better predictions than supervised models trained only on labelled data. The predictions from the semi-supervised neural network are compared with that of the supervised neural network with and without dimensionality reduction(using Principle Component Analysis).

In Marine Geology, scientists persistently perform extensive experiments to measure diverse features across the globe, hence to estimate environmental changes. For example, Mass Accumulation Rate (MAR) and Sedimentation Rate (SR) are measured by marine geologists at various oceanographic locations and are largely reported in research publications but have not been compiled in any central database. Furthermore, every MAR and SR observation normally carries i) exact locational information (Longitude and Latitude), ii) the method of measurement (stratigraphy, 210Pb), iii) a numerical value and units (2.4 g/m2/yr), iv) temporal feature (e.g. hundred years ago). The contextual information attached to MAR and SR observations is heterogeneous and manual approaches for information extraction from text are infeasible. It is also worth mentioning that MAR and SR are not denoted in standard international (SI) units.We propose the comprehensive end-to-end framework GEOTEK (Geological Text to Knowledge) to extract targeted information from marine geology publications. The proposed framework comprises three modules. The first module carries a document relevance model alongside a PDF extractor, capable of filtering relevant sources using metadata, and the extraction module extracts text, tables, and metadata respectively. The second module mainly comprises of two information extractors, namely Geo-Quantities and Geo-Spacy, particularly trained on text from the Marine Geology domain. Geo-Quantities is capable of extracting relevant numerical information from the text and covers more than 100 unit variants for MAR and SR, while Geo-Spacy extracts a set of relevant named entities as well as locational entities, which are further processed to obtain respective geocode boundaries. The third module, the Heterogeneous Information Linking module (HIL), processes exact spatial information from tables and captions and forms links to the previously extracted measurements. Finally, the all-linked information is populated in an interactive map view.

Bottom trawling represents the most widespread anthropogenic physical disturbance to shelf sea sediments. While trawling-induced mortality in benthic fauna has been extensively investigated, its impacts on ecosystem functioning and carbon cycling at regional scales remain unclear. Using the North Sea as an example, we address these issues by synthesizing a high-resolution dataset of bottom trawling impact on sediments, feeding this dataset into a 3-dimensional physical–biogeochemical model to estimate trawling-induced changes in biomass, bioturbation and sedimentary organic carbon, and assessing model results with field samples. Results suggest a trawling-induced net reduction in macrobenthic biomass by 10-27%. Trawling-induced resuspension and reduction of bioturbation jointly and accumulatively reduce the regional sedimentary organic carbon sequestration capacity by 21-67%, equivalent to 0.58-1.84 Mt CO2 yr-1. Our study emphasizes the need for proper management of trawling on muddy seabeds, if the natural capacity of shelf seas for carbon sequestration should be conserved and restored.

High alkalinity values observed in coastal seas promote the uptake of CO2 from the atmosphere. However, the alkalinity budget of coastal areas and marginal seas is poorly understood, even though some of the recently observed alkalinity enhancement can be ascribed to riverine fluxes and anaerobic processes in shelf sediments. Here, we investigate the alkalinity budget of the Baltic Sea to identify previously unrecognized alkalinity sources. We quantify the generation of alkalinity and dissolved calcium (Ca) in this marginal sea applying simple mass balance calculations. Using this approach, we identify alkalinity and Ca sources of approximately 324 Gmol yr-1 and 122 Gmol yr-1, respectively, that cannot be ascribed to the riverine input. The magnitude of the Ca source suggests that a major fraction of the excess alkalinity (244 Gmol yr-1) is induced by the dissolution of calcium carbonate (CaCO3). A review of available field data shows that carbonate-bearing rocks at the coast and the seabed of the Baltic Sea are rapidly eroded and may provide sufficient CaCO3 to close the Ca budget. Hence, dissolution of eroded CaCO3 is the most likely source for the Ca enrichment observed in Baltic Sea water. This hypothesis is supported by mass accumulation rates of sediments derived from radioisotope data that are evaluated to derive a basin-wide rate of mud to muddy sand accumulation at the bottom of the Baltic Sea. The resulting value (139 Tg yr-1) exceeds current estimates of riverine particle fluxes into the Baltic Sea by more than one order of magnitude and confirms that rates of till erosion are sufficiently high to account for the Ca and most of the alkalinity excess in Baltic Sea water. Finally, we show that deliberate addition of CaCO3 to sediments deposited in the Baltic Sea could neutralize significant amounts of CO2 and help to achieve net-zero greenhouse gas emissions in the Baltic region.

A new box model is employed to simulate the oxygen-dependent cycling of nutrients in the Peruvian oxygen minimum zone (OMZ). Model results and data for the present state of the OMZ indicate that dissolved iron is the limiting nutrient for primary production and is provided by the release of dissolved ferrous iron from shelf and slope sediments. Most of the removal of reactive nitrogen occurs by anaerobic oxidation of ammonium where ammonium is delivered by aerobic organic nitrogen degradation. Model experiments simulating the effects of ocean deoxygenation and warming show that the productivity of the Peruvian OMZ will increase due to the enhanced release of dissolved iron from shelf and slope sediments. A positive feedback loop rooted in the oxygen-dependent benthic iron release amplifies, both, the productivity rise and oxygen decline in ambient bottom waters. Hence, a 1% decline in oxygen supply reduces oxygen concentrations in sub-surface waters of the continental margin by 22%. The trend towards enhanced productivity and amplified deoxygenation will continue until further phytoplankton growth is limited by the loss of reactive nitrogen. Under nitrogen-limitation, the redox state of the OMZ is stabilized by negative feedbacks. A further increase in productivity and transition to sulfidic conditions is only possible if the rate of nitrogen fixation increases drastically under anoxic conditions. Such a transition would lead to a wide-spread accumulation of toxic sulfide with detrimental consequences for fishery yields in the Peruvian OMZ that currently provides a significant fraction of the global fish catch.

Carbon cycle history Marine carbon includes organic and inorganic components, both of which must be accounted for to understand the global carbon cycle. Paytan et al. assembled a record of stable strontium isotopes ( 88 Sr and 86 Sr) derived from pelagic marine barite and used it to reconstruct changes in the deposition and burial of biogenic calcium carbonate in marine sediments. These data, when combined with measurements of 87 Sr/ 86 Sr, can help to reveal past changes in the sources and sinks of strontium, as well as variations in carbonate deposition that affect the carbon cycle. Science , this issue p. 1346

Gas hydrate recycling is an important process in natural hydrate systems worldwide. The recycling of hydrates often leads to high hydrate saturation close to the base of the gas hydrate stability zone (GHSZ). However, to date it remains enigmatic how free gas is recycled back into the GHSZ and what the controlling factors are. Here we use a 1D compositional multi-phase flow model to investigate the dominant mechanisms that control natural gas hydrate recycling. As case study, we apply the numerical model to study hydrate recycling at the Green Canyon Site 955 in the Gulf of Mexico, where high sedimentation rates are thought to drive vigorous hydrate dissociation and re-invasion of free gas into the stability zone. Our novel results suggest that hydrate recycling is a highly dynamic process in which hydrates form and dissociate at surprisingly rapid rates with an inherent cyclicity. These cycles can be divided into three phases of 1) gas accumulation phase, 2) gas breakthrough phase and 3) uninhibited hydrate build-up phase. During the first phase hydrates are dissociating and free gas accumulates below. After the free gas saturation reaches a threshold value (given by the mutual effects of entry pressure, bulk permeability, and relative permeability function), gas breaks through the barrier of the remaining hydrate layer. Controlled by permeability and kinetic rate a new hydrate layer forms. In the absence of external perturbations to the GHSZ, gas migration leads to a distinct hydrate layer with a convex distribution of hydrate saturation. Such a hydrate layer acts like a converging-diverging `nozzle' for the gas flow, when gas enters the hydrate layer, it decelerates until it reaches the peak hydrate saturation (i.e. the nozzle throat), and then accelerates until it exits the hydrate layer on the other side. This nozzling effect, together with the hydrate dissociation kinetics, leads to the cyclic behavior of hydrate recycling. We suggest that the evident cyclicity of burial-driven gas hydrate build-up process provides a new advanced understanding of natural gas hydrate recycling process, and free gas invasion mechanisms into the GHSZ.

Enhanced weathering of mafic and ultra-mafic minerals has been suggested as a strategy for carbon dioxide removal (CDR) and a contribution to achieve a balance between global CO2 sources and sinks (net zero emission). This study was designed to assess CDR by dissolution of ultramafic sand (UMS) in artificial seawater (ASW). Fine grained UMS with an olivine content of ~75% was reacted in ASW for up to 134 days at 1 bar and 21.5–23.9°C. A decline in total alkalinity (TA) was observed over the course of the experiments. This unexpected result indicates that TA removal via precipitation of cation-rich authigenic phases exceeded the production of TA induced by olivine dissolution. The TA decline was accompanied by a decrease in dissolved inorganic carbon and Ca concentrations presumably induced by CaCO3 precipitation. Temporal changes in dissolved Si, Ca, Mg, and TA concentrations observed during the experiments were evaluated by a numerical model to identify secondary mineral phases and quantify rates of authigenic phase formation. The modeling indicates that CaCO3, FeOOH and a range of Mg-Si-phases were precipitated during the experiments. Chemical analysis of precipitates and reacted UMS surfaces confirmed that these authigenic phases accumulated in the batch reactors. Nickel released during olivine dissolution, a potential toxic element for certain organisms, was incorporated in the secondary phases and is thus not a suitable proxy for dissolution rates as proposed by earlier studies. The overall reaction stoichiometry derived from lab experiments was applied in a box model simulating atmospheric CO2 uptake in a continental shelf setting induced by olivine addition. The model results indicate that CO2 uptake is reduced by a factor of 5 due to secondary mineral formation and the buffering capacity of seawater. In comparable natural settings, olivine addition may thus be a less efficient CDR method than previously believed.

Serpentine alteration is recognized as an important process for element cycling, however, related silicon fluxes are unknown. Pore fluids from serpentinite seamounts sampled in the Mariana forearc region during IODP Expedition 366 were investigated for their Si, B, and Sr isotope signatures (δ 30 Si, δ 11 B, and 87 Sr/ 86 Sr, respectively) to study serpentinization in the mantle wedge and shallow serpentine alteration to authigenic clays by seawater. While serpentinization in the mantle wedge caused no significant Si isotope fractionation, implying closed system conditions, serpentine alteration by seawater led to the formation of authigenic phyllosilicates, causing the highest natural fluid δ 30 Si values measured to date (up to +5.2 ± 0.2‰). Here we show that seafloor alteration of serpentinites is a source of Si to the ocean with extremely high fluid δ 30 Si values, which can explain anomalies in the marine Si budget like in the Cascadia Basin and which has to be considered in future investigations of the global marine Si cycle.

Oceanic anoxic events (OAEs) document major perturbations of the global carbon cycle with repercussions for the Earth's climate and ocean circulation that are relevant to understanding future climate trends. Here, we compare the onset and development of Cretaceous OAE1a and OAE2 in two drill cores with unusually high sedimentation rates from the Vocontian Basin (southern France) and Tarfaya Basin (southern Morocco). OAE1a and OAE2 exhibit remarkable similarities in the evolution of their carbon isotope (δ13C) records, with long-lasting negative excursions preceding the onset of the main positive excursions, supporting the view that both OAEs were triggered by massive emissions of volcanic CO2 into the atmosphere. However, there are substantial differences, notably in the durations of individual phases within the δ13C positive excursions of both OAEs. Based on analysis of cyclic sediment variations, we estimate the duration of individual phases within OAE1a and OAE2. We identify (1) a precursor phase (negative excursion) lasting ∼430 kyr for OAE1a and ∼130 kyr for OAE2, (2) an onset phase of ∼390 and ∼70 kyr, (3) a peak phase of ∼600 and ∼90 kyr, (4) a plateau phase of ∼1340 and ∼200 kyr, and (5) a recovery phase of ∼380 and ∼440 kyr. The total duration of the positive δ13C excursion is estimated at 2700 kyr for OAE1a and 790 kyr for OAE2, and that of the main carbon accumulation phase is estimated at 980 and 180 kyr. The long-lasting peak, plateau and recovery phases imply fundamental changes in global nutrient cycles either (1) by submarine basalt–seawater interactions, (2) through excess nutrient inputs to the oceans by increasing continental weathering and river discharge, or (3) through nutrient recycling from the marine sediment reservoir. We investigated the role of phosphorus in the development of carbon accumulation by analysing phosphorus speciation across OAE2 and the mid-Cenomanian Event (MCE) in the Tarfaya Basin. The ratios of organic carbon and total nitrogen to reactive phosphorus (Corg∕Preact and Ntotal∕Preact) prior to OAE2 and the MCE hover close to or below the Redfield ratio characteristic of marine organic matter. Decreases in reactive phosphorus resulting in Corg∕Preact and Ntotal∕Preact above the Redfield ratio during the later phase of OAE2 and the MCE indicate leakage from the sedimentary column into the water column under the influence of intensified and expanded oxygen minimum zones. These results suggest that a positive feedback loop, rooted in the benthic phosphorus cycle, contributed to increased marine productivity and carbon burial over an extended period of time during OAEs.

Carbon dioxide (CO2) capture and storage (CCS) has been discussed as a potentially significant mitigation option for the ongoing climate warming. Natural CO2 release sites serve as natural laboratories to study subsea CO2 leakage in order to identify suitable analytical methods and numerical models to develop best-practice procedures for the monitoring of subseabed storage sites. We present a new model of bubble (plume) dynamics, advection-dispersion of dissolved CO2, and carbonate chemistry. The focus is on a medium-sized CO2 release from 294 identified small point sources around Panarea Island (South-East Tyrrhenian Sea, Aeolian Islands, Italy) in water depths of about 40–50 m. This study evaluates how multiple CO2 seep sites generate a temporally variable plume of dissolved CO2. The model also allows the overall flow rate of CO2 to be estimated based on field measurements of pH. Simulations indicate a release of ∼6900 t y–1 of CO2 for the investigated area and highlight an important role of seeps located at >20 m water depth in the carbon budget of the Panarea offshore gas release system. This new transport-reaction model provides a framework for understanding potential future leaks from CO2 storage sites.

The major processes that determine the distribution of methane (CH4) in anoxic marine sediments are methanogenesis and the anaerobic oxidation of methane (AOM), with organoclastic sulfate reduction exerting an important secondary control. However, the factors leading to the distribution of stable carbon isotopes (δ13C) of CH4 are currently poorly understood, in particular the commonly-observed minimum in δ13C-CH4 at the sulfate-methane transition (SMT) where AOM rates reach maximum values. Conventional isotope systematics predict 13C-enrichment of CH4 in the SMT due to preferential 12CH4 consumption by AOM. Two hypotheses put forward to explain this discrepancy are the addition of 12C-enriched CH4 to porewaters by methanogenesis in close proximity to AOM, and enzymatically-mediated carbon isotope equilibrium between forward and backward AOM at low concentrations of sulfate. To examine this in more detail, field data including δ13C of CH4 and dissolved inorganic carbon (DIC) from the continental margin offshore southwestern Taiwan were simulated with a reaction-transport model. Model simulations showed that the minima in δ13C-CH4 and δ13C-DIC in the SMT could only be simulated with carbon isotope equilibrium during AOM. The potential for carbon cycling between methanogenesis and AOM in and just below the SMT was insignificant due to very low rates of methanogenesis. Backward AOM also gives rise to a pronounced kink in the δ13C-DIC profile several meters below the SMT that has been observed in previous studies. We suggest that this kink marks the true base of the SMT where forward and backward AOM are operating at very low rates, possibly sustained by cryptic sulfur cycling or barite dissolution.

Highlights • next to organic matter degradation, bioirrigation and bottom water percolation through permeable surface sediments enhances benthic TPO43- and Fe2+ release • changes in bottom water oxygenation induce slight changes benthic TPO43- and Fe2+ release rates measured in 2011 and 2014 • deoxygenation experiments imply enhanced TPO43- and Fe2+ release at ongoing deoxygenation in the Mauritanian OMZ Abstract Benthic fluxes of total dissolved phosphate (TPO43-), dissolved iron (Fe2+), and dissolved inorganic carbon (DIC) were determined in situ using benthic chambers at nine stations along a depth transect between 47 and 1108 m water depth at 18 °N off Mauritania (NW Africa) during the upwelling season in 2014 (RV Meteor cruise M107). Bottom water oxygen (O2) concentrations were always ≥ 25 µM, and all fluxes (TPO43-, Fe2+, DIC) were consistently directed from the sediments into the bottom water. The highest benthic TPO43- release of 0.2 ± 0.07 mmol m2 d-1 was found at 47 m water depth (50 µM O2). The highest diffusive Fe2+ flux of 0.03 mmol m2 d-1, determined from porewater Fe2+ concentrations, occurred at 67 m water depth (27 µM O2). This was much lower than the detrital Fe supply as indicated by constant Fe/Al ratios along the depth transect. TPO43- release rates decreased concurrently with DIC flux and water depth. A difference of up to one order of magnitude between benthic chamber and diffusive TPO43- fluxes indicated that the total TPO43- release was strongly enhanced by bioirrigation. The observed fluxes were similar to those measured during an earlier cruise in 2011, generally indicating comparable release rates during both upwelling seasons. Furthermore, ex situ oxygen manipulation experiments showed an increase of the nutrient release (e.g. TPO43-, Fe2+) after seven days of anoxic bottom water conditions. The fluxes were enhanced by a factor of 1.4 for P and 7.3 for Fe compared to the measured release under natural conditions and reached values as high as those measured in the anoxic oxygen minimum zone off Peru. Our observations support the hypothesis that increasing deoxygenation of the oceans will likely enhance sedimentary TPO43- and Fe2+ release and thus contribute to a positive feedback mechanism with increasing nutrient levels and increased ocean productivity.

Cruise MSM57-1/-2 was funded by the German Research Foundation ( DFG ), the Research Center/Excellence Cluster “The Ocean in the Earth System” at MARUM–Center for Marine and Environmental Sciences, University of Bremen and funds from CAGE. This work is partly supported by the Research Council of Norway (RCN) through Petromaks2-NORCRUST (project number 255150 ) and the Centre of Excellence funding scheme for CAGE (project number 223259 ). APF’s contribution was part of the SEAMSTRESS project supported by starting grants from the Tromsø Research Foundation and the Research Council of Norway (grant nr. 2878659 ). Seafloor seepage sites along the Vestnesa Ridge off west-Svalbard have been, for decades, a natural laboratory for the studies of fluid flow and gas hydrate dynamics along passive continental margins. The lack of ground truth evidence for fluid composition and gas hydrate abundance deep in the sediment sequence however prohibits us from further assessing the current model of pockmark evolution from the region. A MARUM-MeBo 70 drilling cruise in 2016 aims to advance our understanding of the system by recovering sediments tens of meters below seafloor from two active pockmarks along Vestnesa Ridge. We report pore fluid composition data focusing on dissolved chloride, stable isotopes of water (δ18O and δD), and the isotopic composition of dissolved boron (δ11B). From one of the seepage sites, we detect a saline formation water with two layers where gas hydrates were recovered. This saline formation pore fluid is characterized by elevated chloride concentrations (up to 616 mM), high B/Cl ratios (9 × 10−4 mol/mol), high δ18O and δD isotopic signatures (+0.6‰ and +3.8‰, respectively) and low δ11B signatures (+35.0‰), which collectively hint to a high temperature modification at great depths. Based on the dissolved chloride concentration profiles, we estimated up to 47% of pore space occupied by gas hydrate in the sediments shallower than 11.5 mbsf. The observation of bubble fabric in the recovered gas hydrates suggests formation during past periods of intensive gaseous methane seepage. The presence of these gas hydrates without associated positive anomalies in dissolved chloride concentrations however suggests that the decomposition of gas hydrate is as fast as its formation. Such a state of gas hydrates can be attributed to a relatively low methane supply transported by the saline formation water at present. Our findings based on pore fluid composition corroborate previous inferences along Vestnesa Ridge that fluids sustaining seepage have migrated from great depths and that the variable gaseous and aqueous phases through the gas hydrate stability zone control the distributions of authigenic carbonates and gas hydrates. Publisher PDF

Iron is a key micronutrient controlling phytoplankton growth in vast regions of the global ocean. Despite its importance, uncertainties remain high regarding external iron source fluxes and interna...

An extensive data set of biogenic silica (BSi) fluxes is presented for the Peruvian oxygen minimum zone (OMZ) at 11°S and 12°S. Each transect extends from the shelf to the upper slope (∼1,000 m) and dissects the permanently anoxic waters between ∼200 and 500 m water depth. BSi burial (2,100 mmol m−2 yr−1) and recycling fluxes (3,300 mmol m−2 yr−1) were highest on the shelf with mean preservation efficiencies (34% ± 15%) that exceed the global mean of 10%–20%. BSi preservation was highest on the inner shelf (up to 56%), decreasing to 7% and 12% under anoxic waters and below the OMZ, respectively. The data suggest that the main control on BSi preservation is the rate at which reactive BSi is transported away from undersaturated surface sediments by burial and bioturbation to the underlying saturated sediment layers where BSi dissolution is thermodynamically and/or kinetically inhibited. BSi burial across the entire Peruvian margin between 3°S to 15°S and down to 1,000 m water depth is estimated to be 0.1–0.2 Tmol yr−1; equivalent to 2%–7% of total burial on continental margins. Existing global data permit a simple relationship between BSi rain rate to the seafloor and the accumulation of unaltered BSi, giving the possibility to reconstruct rain rates and primary production from the sediment archive in addition to benthic Si turnover in global models., Key Points: Biogenic silica (BSi) preservation is high on the shelf and low under predominantly anoxic bottom waters BSi burial across the Peruvian margin down to 1,000 m water depth accounts for up to 7% of the global burial on continental margins Existing global data permit a simple relationship between BSi accumulation and rain rate, Deutsche Forschungsgemeinschaft (DFG) http://dx.doi.org/10.13039/501100001659

Highlights • Overview on geochemical composition of pore water and solid phase of sediments on the Azores Plateau. • Evidence for deep marine hydrothermal activity on the Azores Plateau. • Pore water data suggest ongoing anaerobic oxidation of methane and carbonate recrystallization. The Azores Plateau is an active magmatic region in the Central North Atlantic Ocean. In this study, we present a comprehensive data set of major element compositions and 87Sr/86Sr ratios of pore waters from surface sediments (0–9 mbsf) of the Azores Plateau. Based on distinct geochemical signatures we can separate normal marine from hydrothermally affected sediments. Normal marine sediments can further be differentiated by their ash content. Pore waters of ash rich gravity cores (GCs) do not show any deviations from seawater values except of a minor increase in Sr. In contrast, ash poor GCs generally show a trend for decreasing Ca with increasing depth, accompanied by a minor SO4 decrease and a more pronounced Sr increase. We suggest that these deviations are caused by processes such as anaerobic oxidation of methane and carbonate recrystallization. At four additional sample locations we observed a decrease in Mg and SO4 accompanied by a Ca increase in the pore waters, a pattern typical for hydrothermal fluids. The existence of hydrothermal systems in this region are corroborated by multi-channel seismic data, suggesting that sill or dyke intrusions are present in the subsurface close to the core locations. Overall, our observations offer preliminary indications for the existence of submarine hydrothermal systems on the Azores Plateau away from the Mid- Atlantic Ridge.

The Permian/Triassic boundary approximately 251.9 million years ago marked the most severe environmental crisis identified in the geological record, which dictated the onwards course for the evolution of life. Magmatism from Siberian Traps is thought to have played an important role, but the causational trigger and its feedbacks are yet to be fully understood. Here we present a new boron-isotope-derived seawater pH record from fossil brachiopod shells deposited on the Tethys shelf that demonstrates a substantial decline in seawater pH coeval with the onset of the mass extinction in the latest Permian. Combined with carbon isotope data, our results are integrated in a geochemical model that resolves the carbon cycle dynamics as well as the ocean redox conditions and nitrogen isotope turnover. We find that the initial ocean acidification was intimately linked to a large pulse of carbon degassing from the Siberian sill intrusions. We unravel the consequences of the greenhouse effect on the marine environment, and show how elevated sea surface temperatures, export production and nutrient input driven by increased rates of chemical weathering gave rise to widespread deoxygenation and sporadic sulfide poisoning of the oceans in the earliest Triassic. Our findings enable us to assemble a consistent biogeochemical reconstruction of the mechanisms that resulted in the largest Phanerozoic mass extinction. The end-Permian mass extinction was linked with ocean acidification due to carbon degassing associated with Siberian Trap emplacement, according to boron isotopes from fossil shells and reconstruction of the carbon cycle.

Highlights • The SUGAR project has developed and tested various methods for gas production from marine gas hydrates from micro to field scale. • Numerical simulations improved the understanding of processes on molecular to reservoir scale. • Depressurization is a promising technology for exploiting gas hydrate deposits in the Danube Delta. • The injection of CO2 or CO2–N2 is not a suitable method for the exploitation of gas hydrate deposits in the Danube Delta. Abstract One important scientific objective of the national research project SUGAR – Submarine Gas Hydrate Reservoirs was the development, improvement, and test of innovative concepts for the production of methane from natural gas hydrate reservoirs. Therefore, different production methods, such as the thermal stimulation using in situ combustion, the chemical stimulation via injection of CO2 as a gaseous, liquid or supercritical phase and depressurization were tested alone or in combination at different scales. In the laboratory experiments these ranged from pore and hydrate grain scale to 425-L reactor volume, whereas numerical models were applied to describe the related processes from molecular to reservoir scale. In addition, the numerical simulations also evaluated the feasibility and efficiency of the application of these methods in selected areas, such as the Danube Paleodelta in the Black Sea, addressing the two dominant methane hydrate reservoir settings, buried channel-levee and turbidite systems. It turned out, that the injection of CO2 or a CO2–N2 gas mixture is not applicable for the Danube Paleodelta in the Black Sea, because the local pressure and temperature conditions are too close to the equilibrium conditions of both, the CO2 hydrate and a CO2–N2 mixed hydrate stability fields. Experiments using thermal stimulation and depressurization showed promising results but also some issues, such as sufficient heat transfer. In summary it can be said that the applicability and efficiency of each method has to be proven for each specific hydrate reservoir conditions. Based on the results obtained by numerical simulations the most promising and safe method for the production of CH4 from hydrate bearing sediments in the Danube Paleodelta would be the depressurization technique. This study summarizes the main experimental and modeling results.

The eastern tropical South Pacific (ETSP) represents one of the most productive areas in the ocean that is characterized by a pronounced oxygen minimum zone (OMZ). Particulate organic matter (POM) that sinks out of the euphotic zone is supplied to the anoxic sediments and utilized by microbial communities. The degradation of POM is associated with dissolved organic matter (DOM) production and reworking. The release of recalcitrant DOM to the overlying waters may represent an important organic matter escape mechanism from remineralization within sediments but received little attention in OMZ regions so far. Here, we combine measurements of dissolved organic carbon (DOC) and dissolved organic nitrogen (DON) with DOM optical properties in the form of chromophoric (CDOM) and fluorescent (FDOM) DOM from pore waters and near-bottom waters of the ETSP off Peru. We evaluate diffusion–driven fluxes and net in situ fluxes of DOC and DON in order to investigate processes affecting DOM cycling at the sediment–water interface along a transect 12° S. To our knowledge, these are the first data for sediment release of DON and pore water CDOM and FDOM for the ETSP off Peru. Pore-water DOC and DON accumulated with increasing sediment depth, suggesting an imbalance between DOM production and remineralization within sediments. High DON accumulation resulted in very low pore water DOC / DON ratios (> 1) which could be caused by either an imbalance in DOC and DON remineralization, or to the presence of an additional nitrogen source. Diffusion driven fluxes of DOC and DON exhibited high spatial variability. They varied from 0.2–0.1 mmol m−2 d−1 to 2.52–1.3 mmol m−2 d−1 and from −0.042–0.02 mmol m−2 d−1 to 3.32–1.7 mmol m−2 d−1, respectively. Generally low net in situ DOC and DON fluxes as well as steepening of spectral slope (S) of CDOM and accumulation of humic-like FDOM at the near-bottom waters over time indicated active microbial DOM utilization at the sediment–water interface, potentially stimulated by nitrate (NO3−) and nitrite (NO2−). The microbial DOC utilization rates, estimated in our study, may be sufficient to support denitrification rates of 0.2–1.4 mmol m−2 d−1, suggesting that sediment release of DOM contributes substantially to nitrogen loss processes in the ETSP off Peru.

Gas hydrate dynamics and the fluid flow systems from two active pockmarks along Vestnesa Ridge (offshore west Svalbard) were investigated through the pore fluid geochemistry obtained during the 2016 MARUM-MeBo 70 drilling cruise. Based on the pore water chloride concentration profiles from Lunde and Lomvi pockmarks, we estimated up to 47% pore space occupied by gas hydrate in the sediments shallower than 11.5 mbsf. These gas hydrates were formed during periods of gaseous methane seepage, but are now in a state of dynamic equilibrium sustained by a relatively low methane supply at present. We detect a saline formation pore fluid around nine meters below seafloor from one of the seepage sites in Lunde pockmark. This formation pore fluid has elevated dissolved chloride concentrations and B/Cl ratios, higher δO and δD isotopic signatures of water and lower δB signatures, which collectively hint to a high temperature modification of this fluid at great depths. By integrating our findings with the previous work from Vestnesa Ridge, we show that the variable fluid phases (gaseous vs. aqueous fluid) and migration pathways are controlled by the sediment properties, such as buried carbonate crusts, and the state of fluid reservoirs.

Highlights • Physical properties obtained from core and log data at the Danube deep sea fan are reported. • Core-log-seismic integration defines stratigraphic framework at the S2 channel. • All data suggest no gas hydrate is present at drill sites within uncertainties of methods employed. Abstract Drilling, coring, and geophysical logging were performed with the MARUM-MeBo200 seafloor drilling rig to investigate gas hydrate occurrences of the Danube deep sea fan, off Romania, Black Sea. Three sites within a channel-levee complex were investigated. Geophysical log data of P-wave velocity, electrical resistivity, and spectral gamma ray are combined with core-derived physical properties of porosity, magnetic susceptibility, and bulk density. Core- and log physical property data are used to define a time-depth conversion by synthetic seismogram modeling, which is then used to interpret the seismic data. Individual polarity reversed reflectors within the stratigraphic column drilled are linked to reduction in P-wave velocity and bulk density. Those reflectors (and associated reflection packages) are accompanied by distinct and systematic changes in sediment porosity, magnetic susceptibility, and electrical resistivity. Overall, the sediments at drill site GeoB22605 (MeBo-17) represent the younger (upper) levee sequence of the channel, that has been eroded at drill site GeoB22603 (MeBo-16). Splicing seismic data across the channel from the East (MeBo-16) to the West (MeBo-17) demonstrates the continuation of reflectors underneath the channel. The upper ∼50 m below seafloor (mbsf) at site MeBo-16 do not stratigraphically belong to the same sequence of the (deeper) levee-deposits. Above the marked erosional unconformity, sediments at Site MeBo-16 are likely derived by a mixture of repeated slump-events (identified as seismically transparent units) interbedded with hemi-pelagic sedimentation. Similarly, sediments within the upper ∼20 mbsf at Site MeBo-17 are not stratigraphically the same levee-deposits, but are derived by a mixture of slump-events (also seen in the marked seafloor amphitheatre architecture of a large failure complex extending further upslope) and hemi-pelagic sedimentation. All observations combined show that the seismically observed stratigraphic pattern represents a reflectivity sequence mostly driven by variations in density (porosity) and correspondingly by changes in P-wave velocity and electrical resistivity. All observations from the geophysical log- and core, as well as geochemical data do show no evidence for the presence of any significant gas hydrates within the drilled/cored sequences.

Over the last two decades sea bed drilling technology has proven to provide a valuable complement to the services of classical drill ships. Especially for shallow drillings up to 200 mbsf and when working in remote areas difficult to access, sea bed drill rigs are a cost-effective alternative. Recent developments especially concerning borehole logging techniques add to the capabilities of sea bed drilling technology.The MARUM-MeBo is a robotic drilling system that is developed since 2004 at the MARUM Center for Marine Environmental Sciences at the University of Bremen (Freudenthal and Wefer, 2013). The drill rig is deployed on the sea bed and remotely controlled from the vessel. It is used for core drilling in soft sediments as well as hard rocks in the deep sea. Especially since an upgrade in 2007/2008 for the use of wireline drilling technique, the first-generation drill rig MARUM-MeBo70 with a drilling capacity of about 70 m was successfully deployed on more than 15 research expeditions. Since 2014 the second-generation drill rig MARUM-MeBo200 with an increased drilling capacity of up to 200 m below sea floor is successfully in operation.In this presentation we focus on results of three recent drilling campaigns, exemplifying the exploitation of the potential of the sea bed drilling technology:In early 2017 the MeBo70 was deployed from the ice breaking vessel RV POLARSTERN on the West Antarctic shelf (Gohl et al., 2017), an area difficult to access by a drill ship. We were able to recover a sedimentary sequence of the upper Cretaceous time period as one of the very few terrigenous records from this time in Antarctica. This sequence indicates that about 92 to 83 Mio years ago at a paleolatitude of about 82°S this area was covered by a temperate coastal rain forest, making any Antarctic ice sheet formation at this time period unlikely (Klages et al., in press). Also, in 2017 the MeBo70 was deployed in the Arctic off Svalbard. Next to coring a temperature probe was used to assess in situ temperatures and local geothermal gradients (Riedel et al. 2018). Combining these temperature data with the porewater geochemistry of the drilled cores Wallmann et al (2018) were able to prove the effect of isostatic rebound after deglaciation on gas hydrate dissociation. In late 2017 the MeBo200 was deployed in the Black Sea. Geophysical borehole log data of P-wave velocity, electrical resistivity, and spectral gamma ray were combined with core-derived physical properties of porosity, magnetic susceptibility, and bulk density and compared with seismic data of the region (Riedel et al., in press). This study shows the potential of core-log seismic integration for shallow drilling campaigns conducted with a sea bed drill rig. References:Freudenthal, T and Wefer, G (2013) Geoscientific Instrumentation, Methods and Data Systems, 2(2). 329-337. doi:10.5194/gi-2-329-2013Gohl, K, et al. (2017) Geochemistry, Geophysics, Geosystems, 18, 4235–4250. https://doi.org/10.1002/2017GC007081Klages, JP et al. (in press) Nature, 2019-10-14805BRiedel, M et al. (2018) Geochemistry, Geophysics, Geosystems, 19, 1165–1177. doi:10.1002/2017GC007288Riedel, M et al. (in press) Marine and Petroleum Geology, doi.org/10.1016/j.marpetgeo.2019.104192Wallmann, K et al. (2018) Nature Communications, 9:83, DOI: 10.1038/s41467-017-02550-9

Benthic fluxes of dissolved silicon (Si) from sediments into the water column are driven by the dissolution of biogenic silica (bSiO2) and terrigenous Si minerals and modulated by the precipitation of authigenic Si phases. Each of these processes has a specific effect on the isotopic composition of silicon dissolved in sediment pore fluids, such that the determination of pore fluid δ30Si values can help to decipher the complex Si cycle in surface sediments. In this study, the δ30Si signatures of pore fluids and bSiO2 in the Guaymas Basin (Gulf of California) were analyzed, which is characterized by high bSiO2 accumulation and hydrothermal activity. The δ30Si signatures were investigated in the deep basin, in the vicinity of a hydrothermal vent field, and at an anoxic site located within the pronounced oxygen minimum zone (OMZ). The pore fluid δ30Sipf signatures differ significantly depending on the ambient conditions. Within the basin, δ30Sipf is essentially uniform, averaging +1.2±0.1 ‰ (1 SD). Pore fluid δ30Sipf values from within the OMZ are significantly lower (0.0±0.5 ‰, 1 SD), while pore fluids close to the hydrothermal vent field are higher (+2.0±0.2 ‰, 1SD). Reactive transport modeling results show that the δ30Sipf is mainly controlled by silica dissolution (bSiO2 and terrigenous phases) and Si precipitation (authigenic aluminosilicates). Precipitation processes cause a shift to high pore fluid δ30Sipf signatures, most pronounced at the hydrothermal site. Within the OMZ, however, additional dissolution of isotopically depleted Si minerals (e.g., clays) facilitated by high mass accumulation rates of terrigenous material (MARterr) is required to promote the low δ30Sipf signatures, while precipitation of authigenic aluminosilicates seems to be hampered by high water ∕ rock ratios. Guaymas OMZ δ30Sipf values are markedly different from those of the Peruvian OMZ, the only other marine OMZ setting where Si isotopes have been investigated to constrain early diagenetic processes. These differences highlight the fact that δ30Sipf signals in OMZs worldwide are not alike and each setting can result in a range of δ30Sipf values as a function of the environmental conditions. We conclude that the benthic silicon cycle is more complex than previously thought and that additional Si isotope studies are needed to decipher the controls on Si turnover in marine sediment and the role of sediments in the marine silicon cycle.

We report on the geochemistry of hydrocarbons and pore waters down to 62.5 mbsf, collected by drilling with the MARUM‐MeBo70 and by gravity coring at the Lunde pockmark in the Vestnesa Ridge. Our data document the origin and transformations of volatiles feeding gas emissions previously documented in this region. Gas hydrates are present where a fracture network beneath the pockmark focusses migration of thermogenic hydrocarbons characterized by their C1/C2+ and stable isotopic compositions (δ2H‐CH4, δ13C‐CH4). Measured geothermal gradients (~80°C km‐1) and known formation temperatures (>70°C) suggest that those hydrocarbons are formed at depths >800 mbsf. A combined analytical/modeling approach, including concentration and isotopic mass balances, reveals that pockmark sediments experience diffuse migration of thermogenic hydrocarbons. However, at sites without channeled flow this appears to be limited to depths > ~50 mbsf. At all sites we document a contribution of microbial methanogenesis to the overall carbon cycle that includes a component of secondary carbonate reduction (CR) – i.e. reduction of dissolved inorganic carbon (DIC) generated by anaerobic oxidation of methane (AOM) in the uppermost methanogenic zone. AOM and CR rates are spatially variable within the pockmark and are highest at high‐flux sites. These reactions are revealed by 13C‐DIC depletions at the sulfate‐methane interface at all sites. However, 13C‐CH4 depletions are only observed at the low methane flux sites because changes in the isotopic composition of the overall methane pool are masked at high‐flux sites. 13C‐depletions of TOC suggest that at seeps sites, methane‐derived carbon is incorporated into de novo synthesized biomass.

We emphasize the importance of marine silicate weathering (MSiW) reactions in anoxic sediment as fundamental in generating alkalinity and cations needed for carbonate precipitation and preservation along continental margins. We use a model that couples thermodynamics with aqueous geochemistry to show that the CO2 released during methanogenesis results in a drop in pH to 6.0; unless these protons are buffered by MSiW, carbonate minerals will dissolve. We present data from two regions: the India passive margin and the active subduction zone off Japan, where ash and/or rivers supply the reactive silicate phase, as reflected in strontium isotope data. Offshore India and Korea, alteration of continent-derived silicates results in pore water enriched in radiogenic 87Sr, with 87Sr/86Sr ratios as high as 0.7095 and 0.7104, respectively. Off Japan, strontium in pore water influenced by ash alteration is depleted in 87Sr, with 87Sr/86Sr as low as 0.7065. Carbonate minerals formed by alkalinity and cations generated through MSiW carry these strontium isotopic signals, and are typically dolomite, siderite, and Fe-rich calcite. These contrast with the aragonite and high-magnesium calcite that form during anaerobic oxidation of methane and incorporate the coeval seawater 87Sr/86Sr signal. We show that MSiW is necessary for authigenic carbonate formation and preservation along continental margins, which remove carbon from Earth’s surface at rates previously estimated to be at least 1012 mol yr−1. In addition, these authigenic carbonates are of relevance to studies of the deep biosphere, fluid flow, seismogenesis, slope stability, and reservoir characteristics.

Our study presents a basin-scale 3D modeling solution, quantifying and exploring gas hydrate accumulations in the marine environment around the Green Canyon (GC955) area, Gulf of Mexico. It is the first modeling study that considers the full complexity of gas hydrate formation in a natural geological system. Overall, it comprises a comprehensive basin re-construction, accounting for depositional and transient thermal history of the basin, source rock maturation, petroleum components generation, expulsion and migration, salt tectonics and associated multi-stage fault development. The resulting 3D gas hydrate distribution in the Green Canyon area is consistent with independent borehole observations. An important mechanism identified in this study and leading to high gas hydrate saturation (> 80 vol. %) at the base of the gas hydrate stability zone (GHSZ), is the recycling of gas hydrate and free gas enhanced by high Neogene sedimentation rates in the region. Our model predicts the rapid development of secondary intra-salt mini-basins situated on top of the allochthonous salt deposits which leads to significant sediment subsidence and an ensuing dislocation of the lower GHSZ boundary. Consequently, large amounts of gas hydrates located in the deepest parts of the basin dissociate and the released free methane gas migrates upwards to recharge the GHSZ. In total, we have predicted the gas hydrate budget for the Green Canyon area that amounts to ∼3,256 Mt of gas hydrate which is equivalent to ∼340 Mt of carbon (∼7 x 1011 m3 of CH4 at STP conditions), and consists mostly of biogenic hydrates.

Serpentine alteration is recognized as an important process for element cycling, however, related silicon fluxes are unknown. Pore fluids from serpentinite seamounts sampled in the Mariana forearc region during IODP Expedition 366 were investigated for their Si, B, and Sr isotope signatures (δ30Si, δ11B, and 87Sr/86Sr, respectively) to study serpentinization in the mantle wedge and shallow serpentine alteration to authigenic clays by seawater. While serpentinization in the mantle wedge caused no significant Si isotope fractionation, implying closed system conditions, serpentine alteration by seawater led to the formation of authigenic phyllosilicates, causing the highest natural fluid δ30Si values measured to date (up to +5.2 ± 0.2‰). Here we show that seafloor alteration of serpentinites is a source of Si to the ocean with extremely high fluid δ30Si values, which can explain anomalies in the marine Si budget like in the Cascadia Basin and which has to be considered in future investigations of the global marine Si cycle., The Si cycle is important to ocean productivity and nutrient cycling, however there are uncertainties in global budgets. Here the authors use a multi-isotope approach on seafloor sediments and pore fluids, finding that an unappreciated source of Si to the ocean is the degradation of seafloor serpentinites.

Carbon dioxide (CO

Highlights • We present a 5 myr record of biogeochemical cycling in a Cretaceous upwelling area. • A novel quantitative approach for the evaluation of Fe speciation proxies was applied. • Ferruginous proxy signature reflects intense chemical weathering rather than anoxia. • Water column redox conditions evolved from oxic to nitrogenous to euxinic before OAE2. • Smaller seawater nitrate inventory facilitated sedimentary H2S release and euxinia. Abstract Oceanic Anoxic Events (OAEs) in Earth's history are regarded as analogues for current and future ocean deoxygenation, potentially providing information on its pacing and internal dynamics. In order to predict the Earth system's response to changes in greenhouse gas concentrations and radiative forcing, a sound understanding of how biogeochemical cycling differs in modern and ancient marine environments is required. Here, we report proxy records for iron (Fe), sulfur and nitrogen cycling in the Tarfaya upwelling system in the Cretaceous Proto-North Atlantic before, during and after OAE2 (∼93 Ma). We apply a novel quantitative approach to sedimentary Fe speciation, which takes into account the influence of terrigenous weathering and sedimentation as well as authigenic Fe (non-terrigenous, precipitated onsite) rain rates on Fe-based paleo-redox proxies. Generally elevated ratios of reactive Fe (i.e., bound to oxide, carbonate and sulfide minerals) to total Fe (FeHR/FeT) throughout the 5 million year record are attributed to transport-limited chemical weathering under greenhouse climate conditions. Trace metal and nitrogen isotope systematics indicate a step-wise transition from oxic to nitrogenous to euxinic conditions over several million years prior to OAE2. Taking into consideration the low terrigenous sedimentation rates in the Tarfaya Basin, we demonstrate that highly elevated FeHR/FeT from the mid-Cenomanian through OAE2 were generated with a relatively small flux of additional authigenic Fe. Evaluation of mass accumulation rates of reactive Fe in conjunction with the extent of pyritization of reactive Fe reveals that authigenic Fe and sulfide precipitation rates in the Tarfaya Basin were similar to those in modern upwelling systems. Because of a smaller seawater nitrate inventory, however, chemolithoautotrophic sulfide oxidation with nitrate was less efficient in preventing hydrogen sulfide release into the water column. As terrigenous weathering and sediment flux determine how much authigenic Fe is required to generate an anoxic euxinic or ferruginous proxy signature, we emphasize that both have to be taken into account when interpreting Fe-based paleo-redox proxies.

Periodic changes in sediment composition are usually ascribed to insolation forcing controlled by Earth’s orbital parameters. During the Cretaceous Thermal Maximum at 97–91 Myr ago (Ma), a 37–50-kyr-long cycle that is generally believed to reflect obliquity forcing dominates the sediment record. Here, we use a numerical ocean model to show that a cycle of this length can be generated by marine biogeochemical processes without applying orbital forcing. According to our model, the restricted proto-North Atlantic and Tethys basins were poorly ventilated and oscillated between iron-rich and sulfidic (euxinic) states. The Panthalassa Basin was fertilized by dissolved iron originating from the proto-North Atlantic. Hence, it was less oxygenated while the proto-North Atlantic was in an iron-rich state and better oxygenated during euxinic periods in the proto-North Atlantic. This redox see-saw was strong enough to create significant changes in atmospheric $$p_{\mathrm {CO}_2}$$ . We conclude that most of the variability in the mid-Cretaceous ocean–atmosphere system can be ascribed to the internal redox see-saw and its response to external orbital forcing. An internal redox see-saw between the Panthalassa Basin and the proto-North Atlantic can explain cyclic changes in the sediment record throughout the Cretaceous Thermal Maximum 97 to 91 million years ago, according to simulations with a numerical ocean model.

Highlights • Amazon shelf sediments take up seawater potassium (K) due to reverse weathering. • Amazon shelf sediments release terrigenous phosphorus (P) during resuspension. • Updated estimates of sedimentary K uptake and P release on Amazon shelf are presented. • Sedimentary K uptake on Amazon shelf corresponds to 13% of global riverine K input. • Sedimentary P release is ~5 times higher than dissolved P discharge of Amazon River. Abstract In this study, we identify and quantify processes that lead to sedimentary potassium (K) sequestration and phosphorus (P) release on the Amazon shelf. To this end, seven short sediment cores were recovered from the Amazon shelf during R/V Meteor cruise M147. All of the sediment cores investigated in this study are characterized by elevated K to aluminum (Al) ratios compared to Amazon riverine suspended matter, which indicates that seawater K+ is incorporated into the solid phase on the entire Amazon shelf. Pore water silica (Si) profiles are characterized by irregularly increasing concentrations and plateaus, thus, deviating from the asymptotic shape that is typically found in continental margin sediments. At one site, a dissolved Si plateau coincides with a K+ minimum suggesting that these solutes are incorporated into authigenic minerals, a process referred to as reverse weathering. Previous flux estimates for elements that participate in reverse weathering on the Amazon shelf were derived from pore water diffusive fluxes, reaction rates estimated from sediment incubations and solid phase extractions. In this study, we took an alternative approach, which is based on the concentration difference between shelf sediments and river suspended particles. The resulting K flux due to reverse weathering of 1.7 ∙ 1011 mol yr−1 is in agreement with previous estimates and corresponds to 13% of the global riverine dissolved K+ input. Previous studies demonstrated that Amazon riverine particulate P is partly solubilized on the Amazon shelf. However, these results are exclusively based on sediment data close to the river mouth and no distinction between terrestrial and marine sediment components was made. Here, we quantify P release from Amazon shelf sediments by comparing terrestrial P concentrations in shelf sediments with P concentrations in river suspended particles. The resulting solubilized P flux of 2.2 ∙ 1010 mol yr−1 is about five to six times higher than previous estimates and about seven times the Amazon riverine dissolved P discharge. The magnitudes of the presented fluxes imply that the alteration of riverine shelf sediments significantly affects the mean concentrations of dissolved K+ and P in the global ocean.

Highlights • MeBo drilling in Danube fan down to 147 m recovered limnic to marine deposits. • Molecular and stable isotope characterization of light hydrocarbons, CO2, and H2O. • H and O isotopic compositions of pore water reflect paleoclimate variations. • Isotope relations prove microbial carbonate reduction as major methanogenic pathway. • Control of δ2H–CH4 by δ2H–H2O may lead to misinterpretation of methanogenic paths. Abstract We report on the geochemistry of light hydrocarbons and pore water in sediments down to 147 m below seafloor (mbsf), at two sites within the gas hydrate stability field of the Danube deep-sea fan, Black Sea. Sediments were drilled with MARUM-MeBo200 and comprise the transition from limnic to the recent marine stage. Stable C/N ratios (mean 5.1 and 5.6) and δ13C-Corg values (mean −25.8‰ V-PDB) suggest relatively uniform bulk organic matter compositions. In contrast, pore water δ2H and δ18O values varied considerably from approx. −120‰ to −30‰ V-SMOW and from −15‰ to −3‰ V-SMOW, respectively. These data pairs plot close to the ‘Global Meteoric Water Line’ and indicate paleo temperature variations. Depletions of pore water in 2H and 18O below 40 mbsf indicate low temperatures and likely reflect conditions during (the) last glacial period(s). Methane was much more abundant than the only other hydrocarbons found in notable concentrations, ethane and propane ((C1/(C2+C3) ≥20,000). Relatively constant δ13C–CH4 (~−70‰ V-PDB) and δ13C–C2H6 (~−52‰ V-PDB) values with depth indicate that methane and ethane are predominantly of microbial origin and that their formation was not limited by carbon availability. In contrast, δ2H–CH4 values varied in a large range (approx. −310 to −240‰ V-SMOW) with depth and positively correlated with trends observed for δ2H–H2O. Isotope separations (Δδ13C(CH4–CO2), Δδ2H(CH4–H2O)) substantiate that microbial carbonate reduction (CR) is the prevalent methanogenic pathway throughout the sediments irrespective of their geochemical history. Remarkably, in δ13C–CH4 – δ2H–CH4 diagrams widely used, samples characterized by δ2H–CH4 values more negative than approx. −250‰ plot out of the field assigned for pure CR. We conclude that assignments of microbial methanogenic pathways based on classical interpretations of δ13C–CH4 – δ2H–CH4 pairs can lead to misinterpretations, as severe 2H-depletions of methane formed through microbial CR can result from 2H-depletions of the pore water generated during low-temperature climatic periods.

Dissolved silicon isotope compositions have been analysed for the first time in pore waters (δ30SiPW) of three short sediment cores from the Peruvian margin upwelling region with distinctly different biogenic opal content in order to investigate silicon isotope fractionation behaviour during early diagenetic turnover of biogenic opal in marine sediments. The δ30SiPW varies between +1.1‰ and +1.9‰ with the highest values occurring in the uppermost part close to the sediment–water interface. These values are of the same order or higher than the δ30Si of the biogenic opal extracted from the same sediments (+0.3‰ to +1.2‰) and of the overlying bottom waters (+1.1‰ to +1.5‰). Together with dissolved silicic acid concentrations well below biogenic opal saturation, our collective observations are consistent with the formation of authigenic alumino-silicates from the dissolving biogenic opal. Using a numerical transport-reaction model we find that approximately 24% of the dissolving biogenic opal is re-precipitated in the sediments in the form of these authigenic phases at a relatively low precipitation rate of 56 μmol Si cm−2 yr−1. The fractionation factor between the precipitates and the pore waters is estimated at −2.0‰. Dissolved and solid cation concentrations further indicate that off Peru, where biogenic opal concentrations in the sediments are high, the availability of reactive terrigenous material is the limiting factor for the formation of authigenic alumino-silicate phases.

A diagenetic model is used to simulate the diagenesis and burial of particulate organic carbon (C org ) and phosphorus (P) in marine sediments underlying anoxic versus oxic bottom waters. The latter are physically mixed by animals moving through the surface sediment (bioturbation) and ventilated by burrowing, tube-dwelling organisms (bioirrigation). The model is constrained using an empirical database including burial ratios of C org with respect to organic P (C org :P org ) and total reactive P (C org :P reac ), burial efficiencies of C org and P org , and inorganic carbon-to-phosphorus regeneration ratios. If P org is preferentially mineralized relative to C org during aerobic respiration, as many previous studies suggest, then the simulated P org pool is found to be completely depleted. A modified model that incorporates the redox-dependent microbial synthesis of polyphosphates and P org (termed the microbial P pump) allows preferential mineralization of the bulk P org pool relative to C org during both aerobic and anaerobic respiration and is consistent with the database. Results with this model show that P burial is strongly enhanced in sediments hosting fauna. Animals mix highly labile P org away from the aerobic sediment layers where mineralization rates are highest, thereby mitigating diffusive PO 4 3− fluxes to the bottom water. They also expand the redox niche where microbial P uptake occurs. The model was applied to a hypothetical shelf setting in the early Paleozoic; a time of the first radiation of benthic fauna. Results show that even shallow bioturbation at that time may have had a significant impact on P burial. Our model provides support for a recent study that proposed that faunal radiation in ocean sediments led to enhanced P burial and, possibly, a stabilization of atmospheric O 2 levels. The results also help to explain C org :P org ratios in the geological record and the persistence of P org in ancient marine sediments.

We have developed and employed an Earth system model to explore the forcings of atmospheric pCO2 change and the chemical and isotopic evolution of seawater over the last glacial cycle. Concentrations of dissolved phosphorus (DP), reactive nitrogen, molecular oxygen, dissolved inorganic carbon (DIC), total alkalinity (TA), 13C-DIC, and 14C-DIC were calculated for 24 ocean boxes. The bi-directional water fluxes between these model boxes were derived from a 3-D circulation field of the modern ocean (Opa 8.2, NEMO) and tuned such that tracer distributions calculated by the box model were consistent with observational data from the modern ocean. To model the last 130 kyr, we employed records of past changes in sea-level, ocean circulation, and dust deposition. According to the model, about half of the glacial pCO2 drawdown may be attributed to marine regressions. The glacial sea-level low-stands implied steepened ocean margins, a reduced burial of particulate organic carbon, phosphorus, and neritic carbonate at the margin seafloor, a decline in benthic denitrification, and enhanced weathering of emerged shelf sediments. In turn, low-stands led to a distinct rise in the standing stocks of DIC, TA, and nutrients in the global ocean, promoted the glacial sequestration of atmospheric CO2 in the ocean, and added 13C- and 14C-depleted DIC to the ocean as recorded in benthic foraminifera signals. The other half of the glacial drop in pCO2 was linked to inferred shoaling of Atlantic meridional overturning circulation and more efficient utilization of nutrients in the Southern Ocean. The diminished ventilation of deep water in the glacial Atlantic and Southern Ocean led to significant 14C depletions with respect to the atmosphere. According to our model, the deglacial rapid and stepwise rise in atmospheric pCO2 was induced by upwelling both in the Southern Ocean and subarctic North Pacific and promoted by a drop in nutrient utilization in the Southern Ocean. The deglacial sea-level rise led to a gradual decline in nutrient, DIC, and TA stocks, a slow change due to the large size and extended residence times of dissolved chemical species in the ocean. Thus, the rapid deglacial rise in pCO2 can be explained by fast changes in ocean dynamics and nutrient utilization whereas the gradual pCO2 rise over the Holocene may be linked to the slow drop in nutrient and TA stocks that continued to promote an ongoing CO2 transfer from the ocean into the atmosphere.

Previous studies have suggested that weathering and benthic phosphorus (P) fluxes, triggered by climate warming, can increase the oceanic P inventory on millennial time scales, promoting ocean productivity and deoxygenation. In this study, we assessed the major uncertainties in projected P inventories and their imprint on ocean deoxygenation using an Earth system model of intermediate complexity for a business-as-usual carbon dioxide (CO2) emission scenario until year 2300 and subsequent linear decline to zero emissions until year 3000. Model results suggest a large spread in the simulated oceanic P inventory due to uncertainties in (1) assumptions for weathering parameters, (2) the representation of bathymetry on slopes and shelves in the model bathymetry, (3) the parametrization of benthic P fluxes and (4) the representation of sediment P inventories. Our best estimate for changes in the global ocean P inventory by the year 5000 caused by global warming amounts to +30 % compared to pre-industrial levels. Weathering, benthic and anthropogenic fluxes of P contributed +25 %, +3 % and +2 % respectively. The total range of oceanic P inventory changes across all model simulations varied between +2 % and +60 %. Suboxic volumes were up to 5 times larger than in a model simulation with a constant oceanic P inventory. Considerably large amounts of the additional P left the ocean surface unused by phytoplankton via physical transport processes as preformed P. Nitrogen fixation was not able to adjust the oceanic nitrogen inventory to the increasing P levels or to compensate for the nitrogen loss due to increased denitrification. This is in contrast to palaeo reconstructions of large-scale deoxygenation events. We suggest that uncertainties in P weathering, nitrogen fixation and benthic P feedbacks need to be reduced to achieve more reliable projections of oceanic deoxygenation on millennial timescales.

The accumulation of gas hydrates in marine sediments is essentially controlled by the accumulation of particulate organic carbon (POC) which is microbially converted into methane, the thickness of the gas hydrate stability zone (GHSZ) where methane can be trapped, the sedimentation rate (SR) that controls the time that POC and the generated methane stays within the GHSZ, and the delivery of methane from deep-seated sediments by ascending pore fluids and gas into the GHSZ. Recently, Wallmann et al. (2012) presented transfer functions to predict the gas hydrate inventory in diffusion-controlled geological systems based on SR, POC and GHSZ thickness for two different scenarios: normal and full compacting sediments. We apply these functions to global data sets of bathymetry, heat flow, seafloor temperature, POC input and SR, estimating a global mass of carbon stored in marine methane hydrates from 3 to 455 Gt of carbon (GtC) depending on the sedimentation and compaction conditions. The global sediment volume of the GHSZ in continental margins is estimated to be 60–67 × 1015 m3, with a total of 7 × 1015 m3 of pore volume (available for GH accumulation). However, seepage of methane-rich fluids is known to have a pronounced effect on gas hydrate accumulation. Therefore, we carried out a set of systematic model runs with the transport-reaction code in order to derive an extended transfer function explicitly considering upward fluid advection. Using averaged fluid velocities for active margins, which were derived from mass balance considerations, this extended transfer function predicts the enhanced gas hydrate accumulation along the continental margins worldwide. Different scenarios were investigated resulting in a global mass of sub-seafloor gas hydrates of ~ 550 GtC. Overall, our systematic approach allows to clearly and quantitatively distinguish between the effect of biogenic methane generation from POC and fluid advection on the accumulation of gas hydrate, and hence, provides a simple prognostic tool for the estimation of large-scale and global gas hydrate inventories in marine sediments.

Oxygen minimum zones (OMZs) that impinge on continental margins favor the release of phosphorus (P) from the sediments to the water column, enhancing primary productivity and the maintenance or expansion of low-oxygen waters. A comprehensive field program in the Peruvian OMZ was undertaken to identify the sources of benthic P at six stations, including the analysis of particles from the water column, surface sediments, and pore fluids, as well as in situ benthic flux measurements. A major fraction of solid-phase P was bound as particulate inorganic P (PIP) both in the water column and in sediments. Sedimentary PIP increased with depth in the sediment at the expense of particulate organic P (POP). The ratio of particulate organic carbon (POC) to POP exceeded the Redfield ratio both in the water column (202 ± 29) and in surface sediments (303 ± 77). However, the POC to total particulate P (TPP = POP + PIP) ratio was close to Redfield in the water column (103 ± 9) and in sediment samples (102 ± 15). This suggests that the relative burial efficiencies of POC and TPP are similar under low-oxygen conditions and that the sediments underlying the anoxic waters on the Peru margin are not depleted in P compared to Redfield. Benthic fluxes of dissolved P were extremely high (up to 1.04 ± 0.31 mmol m−2 d−1), however, showing that a lack of oxygen promotes the intensified release of dissolved P from sediments, whilst preserving the POC / TPP burial ratio. Benthic dissolved P fluxes were always higher than the TPP rain rate to the seabed, which is proposed to be caused by transient P release by bacterial mats that had stored P during previous periods when bottom waters were less reducing. At one station located at the lower rim of the OMZ, dissolved P was taken up by the sediments, indicating ongoing phosphorite formation. This is further supported by decreasing porewater phosphate concentrations with sediment depth, whereas solid-phase P concentrations were comparatively high.

An edited version of this paper was published by AGU. Copyright 2018 American Geophysical Union. Source at https://doi.org/10.1002/2017GC007288. During expedition MARIA S. MERIAN MSM57/2 to the Svalbard margin offshore Prins Karls Forland, the seafloor drill rig MARUM‐MeBo70 was used to assess the landward termination of the gas hydrate system in water depths between 340 and 446 m. The study region shows abundant seafloor gas vents, clustered at a water depth of ∼400 m. The sedimentary environment within the upper 100 m below seafloor (mbsf) is dominated by ice‐berg scours and glacial unconformities. Sediments cored included glacial diamictons and sheet‐sands interbedded with mud. Seismic data show a bottom simulating reflector terminating ∼30 km seaward in ∼760 m water depth before it reaches the theoretical limit of the gas hydrate stability zone (GHSZ) at the drilling transect. We present results of the first in situ temperature measurements conducted with MeBo70 down to 28 mbsf. The data yield temperature gradients between ∼38°C km−1 at the deepest site (446 m) and ∼41°C km−1 at a shallower drill site (390 m). These data constrain combined with in situ pore‐fluid data, sediment porosities, and thermal conductivities the dynamic evolution of the GHSZ during the past 70 years for which bottom water temperature records exist. Gas hydrate is not stable in the sediments at sites shallower than 390 m water depth at the time of acquisition (August 2016). Only at the drill site in 446 m water depth, favorable gas hydrate stability conditions are met (maximum vertical extent of ∼60 mbsf); however, coring did not encounter any gas hydrates.

Source at: http://doi.org/10.1038/s41467-017-02550-9 Methane seepage from the upper continental slopes of Western Svalbard has previously been attributed to gas hydrate dissociation induced by anthropogenic warming of ambient bottom waters. Here we show that sediment cores drilled off Prins Karls Foreland contain freshwater from dissociating hydrates. However, our modeling indicates that the observed pore water freshening began around 8 ka BP when the rate of isostatic uplift outpaced eustatic sea-level rise. The resultant local shallowing and lowering of hydrostatic pressure forced gas hydrate dissociation and dissolved chloride depletions consistent with our geochemical analysis. Hence, we propose that hydrate dissociation was triggered by postglacial isostatic rebound rather than anthropogenic warming. Furthermore, we show that methane fluxes from dissociating hydrates were considerably smaller than present methane seepage rates implying that gas hydrates were not a major source of methane to the oceans, but rather acted as a dynamic seal, regulating methane release from deep geological reservoirs.