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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.

Vast amounts of methane hydrates are potentially stored in sediments along the continental margins, owing their stability to low temperature – high pressure conditions. Global warming could destabilize these hydrates and cause a release of methane (CH4) into the water column and possibly the atmosphere. Since the Arctic has and will be warmed considerably, Arctic bottom water temperatures and their future evolution projected by a climate model were analyzed. The resulting warming is spatially inhomogeneous, with the strongest impact on shallow regions affected by Atlantic inflow. Within the next 100 years, the warming affects 25% of shallow and mid‐depth regions containing methane hydrates. Release of methane from melting hydrates in these areas could enhance ocean acidification and oxygen depletion in the water column. The impact of methane release on global warming, however, would not be significant within the considered time span. Key Points Arctic bottom water temperatures will rise under climate warming Methane hydrates will be released in the coming decades The release will be limited in the next decades and lead to ocean acidification

Benthic fluxes of dissolved ferrous iron (Fe2+) and phosphate (TPO₄) were quantified by in situ benthic chamber incubations and pore-water profiles along a depth transect (11°S, 80–1000 m) across the Peruvian oxygen minimum zone (OMZ). Bottom-water O₂ levels were < 2 μmol L−1 down to 500-m water depth, and increased to ~ 40 μmol L−1 at 1000 m. Fe2+ fluxes were highest on the shallow shelf (maximum 316 mmol m−2 yr−1), moderate (15.4 mmol m−2 yr−1) between 250 m and 600 m, and negligible at deeper stations. In the persistent OMZ core, continuous reduction of Fe oxyhydroxides results in depletion of sedimentary Fe :Al ratios. TPO₄ fluxes were high (maximum 292 m−2 yr−1) throughout the shelf and the OMZ core in association with high organic carbon degradation rates. Ratios between organic carbon degradation and TPO4 flux indicate excess release of P over C when compared to Redfield stoichiometry. Most likely, this is caused by preferential P release from organic matter, dissolution of fish debris, and/or P release from microbial mat communities, while Fe oxyhydroxides can only be inferred as a major P source on the shallow shelf. The benthic fluxes presented here are among the highest reported from similar, oxygen-depleted environments and highlight the importance of sediments underlying anoxic water bodies as nutrient sources to the ocean. The shelf is particularly important as the periodic passage of coastal trapped waves and associated bottom-water oxygenation events can be expected to induce a transient biogeochemical environment with highly variable release of Fe2+ and TPO₄.

Carbon cycling in Peruvian margin sediments (11 and 12° S) was examined at 16 stations, from 74 m water depth on the middle shelf down to 1024 m, using a combination of in situ flux measurements, sedimentary geochemistry and modelling. Bottom water oxygen was below detection limit down to ca. 400 m and increased to 53 μM at the deepest station. Sediment accumulation rates decreased sharply seaward of the middle shelf and subsequently increased at the deep stations. The organic carbon burial efficiency (CBE) was unusually low on the middle shelf (<20%) when compared to an existing global database, for reasons which may be linked to episodic ventilation of the bottom waters by oceanographic anomalies. Deposition of reworked, degraded material originating from sites higher up on the slope is proposed to explain unusually high sedimentation rates and CBE (>60%) at the deep oxygenated sites. In line with other studies, CBE was elevated under oxygen-deficient waters in the mid-water oxygen minimum zone. Organic carbon rain rates calculated from the benthic fluxes alluded to efficient mineralisation of organic matter in the water column compared to other oxygen-deficient environments. The observations at the Peruvian margin suggest that a lack of oxygen does not greatly affect the degradation of organic matter in the water column but promotes the preservation of organic matter in 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 inpCO2 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.

Greenhouse warmth during the Cretaceous period was interrupted by several intervals of cooling. Marine sediment analyses and biogeochemical modelling suggest that a decline in the abundance of planktonic foraminifera and nannoconids 116–114 million years ago was linked to sea surface cooling. Most of the marine biotic crises that occurred during the hot Mesozoic era have been linked to episodes of extreme warmth 1 , 2 . Others, however, may have occurred during cooler intervals that interrupted Cretaceous greenhouse warmth 3 , 4 , 5 . There are some indications of cooling in the late Aptian 6 , 7 , 8 (116–114 Myr ago), but it has not been definitively linked to biotic crisis. Here we assess the timing and magnitude of late Aptian cooling and its association with biotic crises using a suite of geochemical and micropalaeontological assessments from a marine sediment core from the North Atlantic Ocean as well as global biogeochemical modelling. Sea surface temperatures derived from the TEX 86 proxy suggest that surface waters cooled by about 5 °C during the two million years, coincident with a positive δ 13 C excursion of approximately 2‰ in carbonates and organic carbon. Surface productivity was enhanced during this period, but the abundance of planktonic foraminifera and nannoconid phytoplankton declined. Our simulations with a biogeochemical model indicate that the δ 13 C excursion associated with the cooling could be explained by the burial of about 812,000 gigatons of carbon over 2.5 million years. About 50% of the this carbon burial occurred in the Atlantic, Southern and Tethys ocean basins. We conclude that global cooling during greenhouse conditions can cause perturbations to marine ecosystems and biogeochemical cycles at scales comparable to those associated with global warming.

Marine carbon dioxide removal (mCDR) and geological carbon storage in the marine environment (mCS) promise to help mitigate global climate change alongside drastic emission reductions. However, the implementable potential of mCDR and mCS depends, apart from technology readiness, also on site-specific conditions. In this work, we explore different options for mCDR and mCS, using the German context as a case study. We challenge each option to remove 10 Mt CO₂ yr⁻¹, accounting for 8%–22% of projected hard-to-abate and residual emissions of Germany in 2045. We focus on the environmental, resource, and infrastructure requirements of individual mCDR and mCS options at specific sites, within the German jurisdiction when possible. This serves as an entry point to discuss main uncertainty factors and research needs beyond technology readiness, and, where possible, cost estimates, expected environmental effects, and monitoring approaches. In total, we describe 10 mCDR and mCS options; four aim at enhancing the chemical carbon uptake of the ocean through alkalinity enhancement, four aim at enhancing blue carbon ecosystems' sink capacity, and two employ geological off‐shore storage. Our results indicate that five out of 10 options would potentially be implementable within German jurisdiction, and three of them could potentially meet the challenge. Our exercise serves as an example on how the creation of more tangible and site-specific CDR options can provide a basis for the assessment of socio-economic, ethical, political, and legal aspects for such implementations. The approach presented here can easily be applied to other regional or national CDR capacity considerations.

This study presents benthic data from 12 samplings from February to December 2010 in a 28 m deep channel in the southwest Baltic Sea. In winter, the distribution of solutes in the porewater was strongly modulated by bioirrigation which efficiently flushed the upper 10 cm of sediment, leading to concentrations which varied little from bottom water values. Solute pumping by bioirrigation fell sharply in the summer as the bottom waters became severely hypoxic (< 2 μM O2). At this point the giant sulfide-oxidizing bacteria Beggiatoa was visible on surface sediments. Despite an increase in O2 following mixing of the water column in November, macrofauna remained absent until the end of the sampling. Contrary to expectations, metabolites such as dissolved inorganic carbon, ammonium and hydrogen sulfide did not accumulate in the upper 10 cm during the hypoxic period when bioirrigation was absent, but instead tended toward bottom water values. This was taken as evidence for episodic bubbling of methane gas out of the sediment acting as an abiogenic irrigation process. Porewater–seawater mixing by escaping bubbles provides a pathway for enhanced nutrient release to the bottom water and may exacerbate the feedback with hypoxia. Subsurface dissolved phosphate (TPO4) peaks in excess of 400 μM developed in autumn, resulting in a very large diffusive TPO4 flux to the water column of 0.7 ± 0.2 mmol m−2 d−1. The model was not able to simulate this TPO4 source as release of iron-bound P (Fe–P) or organic P. As an alternative hypothesis, the TPO4 peak was reproduced using new kinetic expressions that allow Beggiatoa to take up porewater TPO4 and accumulate an intracellular P pool during periods with oxic bottom waters. TPO4 is then released during hypoxia, as previous published results with sulfide-oxidizing bacteria indicate. The TPO4 added to the porewater over the year by organic P and Fe–P is recycled through Beggiatoa, meaning that no additional source of TPO4 is needed to explain the TPO4 peak. Further experimental studies are needed to strengthen this conclusion and rule out Fe–P and organic P as candidate sources of ephemeral TPO4 release. A measured C/P ratio of < 20 for the diffusive flux to the water column during hypoxia directly demonstrates preferential release of P relative to C under oxygen-deficient bottom waters. This coincides with a strong decrease in dissolved inorganic N/P ratios in the water column to ~ 1. Our results suggest that sulfide oxidizing bacteria could act as phosphorus capacitors in systems with oscillating redox conditions, releasing massive amounts of TPO4 in a short space of time and dramatically increasing the internal loading of TPO4 to the overlying water.

At Hydrate Ridge (HR), Cascadia convergent margin, surface sediments contain massive gas hydrates formed from methane that ascends together with fluids along faults from deeper reservoirs. Anaerobic oxidation of methane (AOM), mediated by a microbial consortium of archaea and sulfate-reducing bacteria, generates high concentrations of hydrogen sulfide in the surface sediments. The production of sulfide supports chemosynthetic communities that gain energy from sulfide oxidation. Depending on fluid flow, the surface communities are dominated either by the filamentous sulfur bacteriaBeggiatoa(high advective flow), the clamCalyptogena(low advective flow), or the bivalveAcharax(diffusive flow). We analyzed surface sediments (0 to 10 cm) populated by chemosynthetic communities for AOM, sulfate reduction (SR) and the distribution of the microbial consortium mediating AOM. Highest AOM rates were found at theBeggiatoafield with an average rate of 99 mmol m–2d–1integrated over 0 to 10 cm. These rates are among the highest AOM rates ever observed in methane-bearing marine sediments. At theCalyptogenafield, AOM rates were lower (56 mmol m–2d–1). At theAcharaxfield, methane oxidation was extremely low (2.1 mmol m–2d–1) and was probably due to aerobic oxidation of methane. SR was fueled largely by methane at flow-impacted sites, but exceeded AOM in some cases, most likely due to sediment heterogeneity. At theAcharaxfield, SR was decoupled from methane oxidation and showed low activity. Aggregates of the AOM consortium were abundant at the fluid-impacted sites (between 5.1 × 1012and 7.9 × 1012aggregates m–2) but showed low numbers at theAcharaxfield (0.4 × 1012aggregates m–2). A transport-reaction model was applied to estimate AOM atBeggiatoafields. The model agreed with the measured depth-integrated AOM rates and the vertical distribution. AOM represents an important methane sink in the surface sediments of HR, consuming between 50 and 100% of the methane transported by advection.

A simple prognostic tool for gas hydrate (GH) quantification in marine sediments is presented based on a diagenetic transport-reaction model approach. One of the most crucial factors for the application of diagenetic models is the accurate formulation of microbial degradation rates of particulate organic carbon (POC) and the coupled formation of biogenic methane. Wallmann et al. (2006) suggested a kinetic formulation considering the ageing effects of POC and accumulation of reaction products (CH4, CO2) in the pore water. This model is applied to data sets of several ODP sites in order to test its general validity. Based on a thorough parameter analysis considering a wide range of environmental conditions, the POC accumulation rate (POCar in g/m2/yr) and the thickness of the gas hydrate stability zone (GHSZ in m) were identified as the most important and independent controls for biogenic GH formation. Hence, depth-integrated GH inventories in marine sediments (GHI in g of CH4 per cm2 seafloor area) can be estimated as: GHI = a · POCar · GHSZb · exp (– GHSZc/POCar/d) + e with a = 0.00214, b = 1.234, c = –3.339,         d = 0.3148, e = –10.265. The transfer function gives a realistic first order approximation of the minimum GH inventory in low gas flux (LGF) systems. The overall advantage of the presented function is its simplicity compared to the application of complex numerical models, because only two easily accessible parameters need to be determined.