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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.

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.

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.

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.

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.

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.

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.

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.

Literature data on benthic dissolved iron (DFe) fluxes (µmol m−2 d−1), bottom water oxygen concentrations (O2BW, μM), and sedimentary carbon oxidation rates (COX, mmol m−2 d−1) from water depths ranging from 80 to 3700 m were assembled. The data were analyzed with a diagenetic iron model to derive an empirical function for predicting benthic DFe fluxes: inline image where γ (= 170 µmol m−2 d−1) is the maximum flux for sediments at steady state located away from river mouths. This simple function unifies previous observations that COX and O2BW are important controls on DFe fluxes. Upscaling predicts a global DFe flux from continental margin sediments of 109 ± 55 Gmol yr−1, of which 72 Gmol yr−1 is contributed by the shelf ( 2000 m) of 41 ± 21 Gmol yr−1 is unsupported by empirical data. Previous estimates of benthic DFe fluxes derived using global iron models are far lower (approximately 10–30 Gmol yr−1). This can be attributed to (i) inadequate treatment of the role of oxygen on benthic DFe fluxes and (ii) improper consideration of continental shelf processes due to coarse spatial resolution. Globally averaged DFe concentrations in surface waters simulated with the intermediate-complexity University of Victoria Earth System Climate Model were a factor of 2 higher with the new function. We conclude that (i) the DFe flux from marginal sediments has been underestimated in the marine iron cycle and (ii) iron scavenging in the water column is more intense than currently presumed.

Carbon cycling in Peruvian margin sediments (11° S and 12° S) was examined at 16 stations from 74 m on the inner shelf down to 1024 m water depth by means of in situ flux measurements, sedimentary geochemistry and modeling. Bottom water oxygen was below detection limit down to ca. 400 m and increased to 53 μM at the deepest station. Sediment accumulation rates and benthic dissolved inorganic carbon fluxes decreased rapidly with water depth. Particulate organic carbon (POC) content was lowest on the inner shelf and at the deep oxygenated stations (< 5%) and highest between 200 and 400 m in the oxygen minimum zone (OMZ, 15–20%). The organic carbon burial efficiency (CBE) was unexpectedly low on the inner shelf (< 20%) when compared to a global database, for reasons which may be linked to the frequent ventilation of the shelf by oceanographic anomalies. CBE at the deeper oxygenated sites was much higher than expected (max. 81%). Elsewhere, CBEs were mostly above the range expected for sediments underlying normal oxic bottom waters, with an average of 51 and 58% for the 11° S and 12° S transects, respectively. Organic carbon rain rates calculated from the benthic fluxes alluded to a very efficient mineralization of organic matter in the water column, with a Martin curve exponent typical of normal oxic waters (0.88 ± 0.09). Yet, mean POC burial rates were 2–5 times higher than the global average for continental margins. The observations at the Peruvian margin suggest that a lack of oxygen does not affect the degradation of organic matter in the water column but promotes the preservation of organic matter in marine sediments.