Description: Two sediment cores retrieved at the northern slope of Sakhalin Island, Sea of Okhotsk, were analyzed for biogenic opal, organic carbon, carbonate, sulfur, major element concentrations, mineral contents, and dissolved substances including nutrients, sulfate, methane, major cations, humic substances, and total alkalinity. Down-core trends in mineral abundance suggest that plagioclase feldspars and other reactive silicate phases (olivine, pyroxene, volcanic ash) are transformed into smectite in the methanogenic sediment sections. The element ratios Na/Al, Mg/Al, and Ca/Al in the solid phase decrease with sediment depth indicating a loss of mobile cations with depth and producing a significant down-core increase in the chemical index of alteration. Pore waters separated from the sediment cores are highly enriched in dissolved magnesium, total alkalinity, humic substances, and boron. The high contents of dissolved organic carbon in the deeper methanogenic sediment sections (50–150 mg dm−3) may promote the dissolution of silicate phases through complexation of Al3+ and other structure-building cations. A non-steady state transport-reaction model was developed and applied to evaluate the down-core trends observed in the solid and dissolved phases. Dissolved Mg and total alkalinity were used to track the in-situ rates of marine silicate weathering since thermodynamic equilibrium calculations showed that these tracers are not affected by ion exchange processes with sediment surfaces. The modeling showed that silicate weathering is limited to the deeper methanogenic sediment section whereas reverse weathering was the dominant process in the overlying surface sediments. Depth-integrated rates of marine silicate weathering in methanogenic sediments derived from the model (81.4–99.2 mmol CO2 m−2 year−1) are lower than the marine weathering rates calculated from the solid phase data (198–245 mmol CO2 m−2 year−1) suggesting a decrease in marine weathering over time. The production of CO2 through reverse weathering in surface sediments (4.22–15.0 mmol CO2 m−2 year−1) is about one order of magnitude smaller than the weathering-induced CO2 consumption in the underlying sediments. The evaluation of pore water data from other continental margin sites shows that silicate weathering is a common process in methanogenic sediments. The global rate of CO2 consumption through marine silicate weathering estimated here as 5–20 Tmol CO2 year−1 is as high as the global rate of continental silicate weathering.

Description: Highlights • Deep-sea mineral exploration and exploitation licenses have been issued recently. • Mining will modify the abiotic and biotic environment. • At directly mined sites, species are removed and cannot resist disturbance. • Recovery is highly variable in distinct ecosystems and among benthic taxa. • Community changes may persist over geological time-scales at directly mined sites. Abstract With increasing demand for mineral resources, extraction of polymetallic sulphides at hydrothermal vents, cobalt-rich ferromanganese crusts at seamounts, and polymetallic nodules on abyssal plains may be imminent. Here, we shortly introduce ecosystem characteristics of mining areas, report on recent mining developments, and identify potential stress and disturbances created by mining. We analyze species’ potential resistance to future mining and perform meta-analyses on population density and diversity recovery after disturbances most similar to mining: volcanic eruptions at vents, fisheries on seamounts, and experiments that mimic nodule mining on abyssal plains. We report wide variation in recovery rates among taxa, size, and mobility of fauna. While densities and diversities of some taxa can recover to or even exceed pre-disturbance levels, community composition remains affected after decades. The loss of hard substrata or alteration of substrata composition may cause substantial community shifts that persist over geological timescales at mined sites.

Description: Natural gas hydrates are considered a potential resource for gas production on industrial scales. Gas hydrates contribute to the strength and stiffness of the hydrate-bearing sediments. During gas production, the geomechanical stability of the sediment is compromised. Due to the potential geotechnical risks and process management issues, the mechanical behavior of the gas hydrate-bearing sediments needs to be carefully considered. In this study, we describe a coupling concept that simplifies the mathematical description of the complex interactions occurring during gas production by isolating the effects of sediment deformation and hydrate phase changes. Central to this coupling concept is the assumption that the soil grains form the load-bearing solid skeleton, while the gas hydrate enhances the mechanical properties of this skeleton. We focus on testing this coupling concept in capturing the overall impact of geomechanics on gas production behavior though numerical simulation of a high-pressure isotropic compression experiment combined with methane hydrate formation and dissociation. We consider a linear-elastic stress-strain relationship because it is uniquely defined and easy to calibrate. Since, in reality, the geomechanical response of the hydrate-bearing sediment is typically inelastic and is characterized by a significant shear-volumetric coupling, we control the experiment very carefully in order to keep the sample deformations small and well within the assumptions of poroelasticity. The closely coordinated experimental and numerical procedures enable us to validate the proposed simplified geomechanics-to-flow coupling, and set an important precursor toward enhancing our coupled hydro-geomechanical hydrate reservoir simulator with more suitable elastoplastic constitutive models.

Description: Research and regulations must be integrated to protect seafloor biota from future mining impacts Summary: As human use of rare metals has diversified and risen with global development, metal ore deposits from the deep ocean floor are increasingly seen as an attractive future resource. Japan recently completed the first successful test for zinc extraction from the deep seabed, and the number of seafloor exploration licenses filed at the International Seabed Authority (ISA) has tripled in the past 5 years. Seafloor-mining equipment is being tested, and industrial-scale production in national waters could start in a few years. We call for integrated scientific studies of global metal resources, the fluxes and fates of metal uses, and the ecological footprints of mining on land and in the sea, to critically assess the risks of deep-sea mining and the chances for alternative technologies. Given the increasing scientific evidence for long-lasting impacts of mining on the abyssal environment, precautionary regulations for commercial deep-sea mining are essential to protect marine ecosystems and their biodiversity.

Description: Due to the strong interest in geochemical CO2-fluid-rock interaction in the context of geological storage of CO2 a growing number of research groups have used a variety of different experimental ways to identify important geochemical dissolution or precipitation reactions and – if possible – quantify the rates and extent of mineral or rock alteration. In this inter-laboratory comparison the gas-fluid-mineral reactions of three samples of rock-forming minerals have been investigated by 11 experimental labs. The reported results point to robust identification of the major processes in the experiments by most groups. The dissolution rates derived from the changes in composition of the aqueous phase are consistent overall, but the variation could be reduced by using similar corrections for changing parameters in the reaction cells over time. The comparison of experimental setups and procedures as well as of data corrections identified potential improvements for future gas-fluid-rock studies.

Description: Highlights • A stack of four BSRs were identified in levee deposits of the Danube deep-sea fan. • The multiple BSRs are not caused by overpressure compartments. • The multiple BSRs reflect stages of stable sealevel lowstands during glacial times. • Gas underneath the previous GHSZ does not start to migrate for thousands of years. Abstract High-resolution 2D seismic data reveal the character and distribution of up to four stacked bottom simulating reflectors (BSR) within the channel-levee systems of the Danube deep-sea fan. The theoretical base of the gas hydrate stability zone (GHSZ) calculated from regional geothermal gradients and salinity data is in agreement with the shallowest BSR. For the deeper BSRs, BSR formation due to overpressure compartments can be excluded because the necessary gas column would exceed the vertical distance between two overlying BSRs. We show instead that the deeper BSRs are likely paleo BSRs caused by a change in pressure and temperature conditions during different limnic phases of the Black Sea. This is supported by the observation that the BSRs correspond to paleo seafloor horizons located in a layer between a buried channel-levee system and the levee deposits of the Danube channel. The good match of the observed BSRs and the BSRs predicted from deposition of these sediment layers indicates that the multiple BSRs reflect stages of stable sealevel lowstands possibly during glacial times. The observation of sharp BSRs several 10,000 of years but possibly up to 300,000 yr after they have left the GHSZ demonstrates that either hydrate dissociation does not take place within this time frame or that only small amounts of gas are released that can be transported by diffusion. The gas underneath the previous GHSZ does not start to migrate for several thousands of years.

Description: The formation of mud volcanoes in the Gulf of Cadiz is closely linked to diapirism in the deep subsurface. The Mercator mud volcano (MMV) is a rare example where diapiric emplacement, in addition to being key for upward fluid migration, is also an important zone for fluid and mineral diagenesis. The most intriguing findings in the near-surface muds of the MMV are extremely high salinities of up to 5.2 M of NaCl from diapiric and evaporitic halite dissolution and the occurrence of authigenic gypsum and anhydrite crystals, both of which have not been observed to date in the Gulf of Cadiz. Employing a thermodynamic model we elucidate how the interplay of temperature pulses, strong salinity gradients, and fluid flow dynamically drive mineral dissolution and re-formation. The strong increase in salinity in the pore fluids has important implications for thermodynamic equilibria by significantly lowering the activity of water, thereby raising the gypsum–anhydrite transition zone from 〉1 km to about 400 m sediment depth at the MMV. This transition is further shifted to immediately below the seafloor during intervals of active mud and fluid expulsion when the MV surface temperature is heated up to at least 30 °C. As a consequence, precipitation of authigenic gypsum near the sediment surface (1–2 mbsf) has been linked to the dissolution of evaporites below the MMV. More precisely, the mechanisms generating supersaturation in the ascending gypsum-saturated MMV fluids are (1) the slow and constant cooling of these fluids along the geothermal gradient during their ascent leading to formation of ubiquitous micro-crystals and (2) the more rapid cooling after a heat pulse or transport from greater and warmer depth during an active mud volcano phase leading to the precipitation of cm-scale gypsum crystals or even fist-size concretions. The MMV fluids approaching the salt diapir from farther below have experienced a genesis similar to those of other mud volcanoes in the Gulf of Cadiz located above deep-rooted faults. These processes include clay mineral dewatering, thermogenic degradation of organic matter and deep high-temperature leaching of terrigenous sediments or continental crust.

Description: Geochemical data (CH4, SO42−, I−, Cl−, particulate organic carbon (POC), δ13C-CH4, and δ13C-CO2) are presented from the upper 30 m of marine sediment on a tectonic submarine accretionary wedge offshore southwest Taiwan. The sampling stations covered three ridges (Tai-Nan, Yung-An, and Good Weather), each characterized by bottom simulating reflectors, acoustic turbidity, and different types of faulting and anticlines. Sulfate and iodide concentrations varied little from seawater-like values in the upper 1–3 m of sediment at all stations; a feature that is consistent with irrigation of seawater by gas bubbles rising through the soft surface sediments. Below this depth, sulfate was rapidly consumed within 5–10 m by anaerobic oxidation of methane (AOM) at the sulfate-methane transition. Carbon isotopic data imply a mainly biogenic methane source. A numerical transport-reaction model was used to identify the supply pathways of methane and estimate depth-integrated turnover rates at the three ridges. Methane gas ascending from deep layers, facilitated by thrusts and faults, was by far the dominant term in the methane budget at all sites. Differences in the proximity of the sampling sites to the faults and anticlines mainly accounted for the variability in gas fluxes and depth-integrated AOM rates. By comparison, methane produced in situ by POC degradation within the modeled sediment column was unimportant. This study demonstrates that the geochemical trends in the continental margins offshore SW Taiwan are closely related to the different geological settings.

Description: Highlights • High abundance of active anaerobic methanotrophs in sediments of the blowout crater suggests adaptation to methane seepage within at most two decades. • Fast exchange processes in permeable surface sediments prevent sulfate depletion and probably methane-derived carbonate precipitation. • Methane seepage impacts isotopic and assemblage composition of benthic foraminifera. Abstract Methane emissions from marine sediments are partly controlled by microbial anaerobic oxidation of methane (AOM). AOM provides a long-term sink for carbon through precipitation of methane-derived authigenic carbonates (MDAC). Estimates on the adaptation time of this benthic methane filter as well as on the establishment of related processes and communities after an onset of methane seepage are rare. In the North Sea, considerable amounts of methane have been released since 20 years from a man-made gas blowout offering an ideal natural laboratory to study the effects of methane seepage on initially “pristine” sediment. Sediment cores were taken from the blowout crater and a reference site (50 m distance) in 2011 and 2012, respectively, to investigate porewater chemistry, the AOM community and activity, the presence of authigenic carbonates, and benthic foraminiferal assemblages. Potential AOM activity (up to 3060 nmol cm−3 sediment d−1 or 375 mmol m−2 d−1) was detected only in the blowout crater up to the maximum sampling depth of 18 cm. CARD-FISH analyzes suggest that monospecific ANME-2 aggregates were the only type of AOM organisms present, showing densities (up to 2.2*107 aggregates cm−3) similar to established methane seeps. No evidence for recent MDAC formation was found using stable isotope analyzes (δ13C and δ18O). In contrast, the carbon isotopic signature of methane was recorded by the epibenthic foraminifer Cibicides lobatulus (δ13C −0.66‰). Surprisingly, the foraminiferal assemblage in the blowout crater was dominated by Cibicides and other species commonly found in the Norwegian Channel and fjords, indicating that these organisms have responded sensitively to the specific environmental conditions at the blowout. The high activity and abundance of AOM organisms only at the blowout site suggests adaptation to a strong increase in methane flux in the order of at most two decades. High gas discharge dynamics in permeable surface sediments facilitate fast sulfate replenishing and stimulation of AOM. The accompanied prevention of total alkalinity build-up in the porewater thereby appears to inhibit the formation of substantial methane-derived authigenic carbonate at least within the given time window.

Description: Gashydrate sind eisähnliche Verbindungen, in denen Hydratbildner, z.B. Methan, in hoher Dichte gespeichert werden können. Methanhydrate sind nur bei hohen Drücken und tiefen Temperaturen sowie in Anwesenheit hoher Methankonzentrationen stabil. Diese Stabilitätsbedingungen sind unter bestimmten Voraussetzungen in marinen Sedimenten erfüllt, in denen Methan durch den mikrobiellen Abbau von abgelagerter Biomasse entsteht oder aus größeren Tiefen zugeführt wird. Die globale Menge an Methan in marinen Gashydraten überschreitet die Menge an Erdgas in konventionellen Lagerstätten vermutlich um ein Mehrfaches. Eine potenzielle Nutzung von Gashydraten als zukünftige Energiequelle wird daher gegenwärtig weltweit untersucht. Erste Feldtests in Permafrostregionen und marinen Lagerstätten haben gezeigt, dass eine Produktion von Methan aus Gashydraten prinzipiell möglich ist. Eine Förderung von Methan aus Gashydraten kann technisch realisiert werden mittels Druckabsenkung, durch thermische Stimulation oder chemische Aktivierung. Die Injektion von CO2, ebenfalls ein Hydratbildner, kann eine solche Aktivierung der natürlichen Hydrate bewirken und das Methan in der Hydratstruktur ersetzen. Infolgedessen erscheint eine verfahrenstechnische Kombination von Hydratabbau und CO2-Speicherung als besonders sinnvoll, da im Idealfall eine emissionsarme bis -freie Energiegewinnung ermöglicht würde. Untersuchungen zur Aufklärung mechanistischer und fluiddynamischer Aspekte der CH4-CO2-Hydratumwandlung sowie zur Entwicklung eines technischen Verfahrens werden in unterschiedlichen Hochdruckanlagen auf verschiedenen Skalen durchgeführt. Diese speziellen Systeme bieten die Möglichkeit, marine Druck-, Temperatur- und Durchflussbedingungen zu simulieren. Sie sind mit verschiedenen Sensoren und Messsystemen (z.B. CTD, IR, Raman, MRI) ausgerüstet, um den Prozessverlauf störungsfrei zu überwachen. Basierend auf derzeitigen Ergebnissen erscheint die Injektion von erwärmtem, überkritischem CO2 als vielversprechender technischer Baustein für die Verfahrensentwicklung. Die Zuführung von Wärmeenergie bewirkt die initiale Destabilisierung der Gashydrate und die Freisetzung von CH4, während nach Abkühlung das CO2 seinerseits Hydrate bildet und als feste, immobile Phase im Sediment zurückgehalten wird. Sowohl Methanproduktion als auch CO2-Speicherung sind dabei abhängig von der Reservoirtemperatur, so dass die Prozesseffizienz und -ausbeute bei mittleren Temperaturen (8°C) höher ist als bei niedrigeren (2°C) und höheren Temperaturen (10°C). Dies deutet darauf hin, dass der Gesamtprozess durch die Raten der jeweiligen Teilreaktionen der Hydratzersetzung und Hydratneubildung stark beeinflusst wird. Der experimentelle Vergleich unterschiedlicher Injektionsmodi zeigt, dass eine alternierende CO2-Injektion bestehend aus Injektions- und Reaktionsintervallen höhere Ausbeuten erreicht als eine kontinuierliche Injektion.