Description: The weathering of silicate minerals exposed on the continents is the largest sink of atmospheric CO2 on time scales of millions of years. The rate of this process is positively correlated with global mean temperature and atmospheric CO2 concentration, resulting in a negative feedback that stabilizes Earths’ climate (Berner, 2004). Detrital silicates derived from the physical denudation of the continents are a major component of marine sediments (Li and Schoonmaker, 2003). However, their geochemical behaviour is poorly understood and they are considered to be unimportant to the long-term carbon cycle. We show that in organic matter-rich sediments of the Sea of Okhotsk detrital silicates undergo intense weathering. This process is likely favoured by microbial activity, which lowers pore water pH and releases dissolved humic substances, and by the freshness of detrital silicates which originate from the cold, poorly weathered Amur River basin. Numerical simulations of early diagenesis show that submarine weathering rates in our study area are comparable to average continental weathering rates (Gaillardet et al., 1999). Furthermore, silicate weathering seems to be widespread in organic matter-rich sediments of continental margins, suggesting the existence of a significant CO2 sink there. These findings imply a greater efficiency of the silicate weathering engine also at low surface temperatures, resulting in a weakening of the negative feedback between pCO2, climate evolution and silicate weathering.

Description: Submarine mud volcanism is an important pathway for transfer of deep-sourced fluids enriched in hydrocarbons and other elements into the ocean. Numerous mud volcanoes (MVs) have been discovered along oceanic plate margins, and integrated elemental fluxes are potentially significant for oceanic chemical budgets. Here, we present the first detailed study of the spatial variation in fluid and chemical fluxes at the Carlos Ribeiro MV in the Gulf of Cadiz. To this end, we combine analyses of the chemical composition of pore fluids with a 1-D transport-reaction model to quantify fluid fluxes, and fluxes of boron, lithium and methane, across the sediment–seawater interface. The pore fluids are significantly depleted in chloride, but enriched in lithium, boron and hydrocarbons, relative to seawater. Pore water profiles of sulphate, hydrogen sulphide and total alkalinity indicate that anaerobic oxidation of methane occurs at 34–180 cm depth below seafloor. Clay mineral dehydration, and in particular the transformation of smectite to illite, produces pore fluids that are depleted in chloride and potassium. Profiles of boron, lithium and potassium are closely related, which suggests that lithium and boron are released from the sediments during this transformation. Pore fluids are expelled into the water column by advection; fluid flow velocities are 4 cm yr−1 at the apex of the MV but they rapidly decrease to 0.4 cm yr−1 at the periphery. The associated fluxes of boron, lithium and methane vary between 7–301, 0.5–6 and 0–806 mmol m−2 yr−1, respectively. We demonstrate that fluxes of Li and B due to mud volcanism may be important on a global scale, however, release of methane into the overlying water column is suppressed by microbial methanotrophy.

Description: Four seep sites located within an -20 km2 area offshore Georgia (Batumi seep area, Pechori Mound, Iberia Mound, and Colkheti Seep) show characteristic differences with respect to element concentrations, and oxygen, hydrogen, strontium, and chlorine isotope signatures in pore waters, as well as impregnation of sediments with petroleum and hydrocarbon potential. All seep sites have active gas seepage, near surface authigenic carbonates and gas hydrates. Cokheti Seep, Iberia Mound, and Pechori Mound are characterized by oil-stained sediments and gas seepage decoupled from deep fluid advection and bottom water intrusion induced by gas bubble release. Pechori Mound is further characterized by deep fluid advection of lower salinity pore fluids. The Pechori Mound pore fluids are altered by mineral/water reactions at elevated temperatures (between 60 and 110°C) indicated by heavier oxygen and lighter chlorine isotope values, distinct Li and B enrichment, and K depletion. Strontium isotope ratios indicate that fluids originate from late Oligocene strata. This finding is supported by the occurrence of hydrocarbon impregnations within the sediments. Furthermore, light hydrocarbons and high molecular weight impregnates indicate a predominant thermogenic origin for the gas and oil at Pechori Mound, Iberia Mound, and Colkheti Seep. C15+ hydrocarbons at the oil seeps are allochtonous, whereas those at the Batumi seep area are autochthonous. The presence of oleanane, an angiosperm biomarker, suggests that the hydrocarbon source rocks belong to the Maikopian Formation. In summary, all investigated seep sites show a high hydrocarbon potential and hydrocarbons of Iberia Mound, Colkheti Seep, and Pechori Mound are predominantly of thermogenic origin. However, only at the latter seep site advection of deep pore fluids is indicated.

Description: Extensive methane hydrate layers are formed in the near-surface sediments of the Cascadia margin. An undissociated section of such a layer was recovered at the base of a gravity core (i.e. at a sediment depth of 120 cm) at the southern summit of Hydrate Ridge. As a result of salt exclusion during methane hydrate formation, the associated pore waters show a highly elevated chloride concentration of 809 mM. In comparison, the average background value is 543 mM. A simple transport-reaction model was developed to reproduce the Cl- observations and quantify processes such as hydrate formation, methane demand, and fluid flow. From this first field observation of a positive Cl- anomaly, high hydrate formation rates (0.15–1.08 mol cm-2 a-1) were calculated. Our model results also suggest that the fluid flow rate at the Cascadia accretionary margin is constrained to 45–300 cm a-1. The amount of methane needed to build up enough methane hydrate to produce the observed chloride enrichment exceeds the methane solubility in pore water. Thus, most of the gas hydrate was most likely formed from ascending methane gas bubbles rather than solely from CH4 dissolved in the pore water.

Description: As a result of extensive hydrocarbon exploration, the North Sea hosts several thousand abandoned wells; many believed to be leaking methane. However, how much of this greenhouse gas is emitted into the water column and ultimately reaches the atmosphere is not known. Here, we investigate three abandoned wells at 81-93m water depth in the Norwegian sector of the North Sea, all of which show gas seepage into the bottom water. The isotopic signature of the emanating gas points towards a biogenic origin and hence to gas pockets in the sedimentary overburden above the gas reservoirs that the wells were drilled into. Video-analysis of the seeping gas bubbles and direct gas flow measurements resolved initial bubble sizes ranging between 3.2 and 7.4mm in diameter with a total seabed gas flow between 1 and 19 tons of CH4 per year per well. Estimated total annual seabed emissions from all three wells of ~24 tons are similar to the natural seepage rates at Tommeliten, suggesting that leaky abandoned wells represent a significant source of methane into North Sea bottom waters. However, the bubble-driven direct methane transport into the atmosphere was found to be negligible (〈2%) due to the small bubble sizes and the water depth at which they are released.

Description: This study combines sediment geochemical analysis, in situ benthic lander deployments and numerical modeling to quantify the biogeochemical cycles of carbon and sulfur and the associated rates of Gibbs energy production at a novel methane seep. The benthic ecosystem is dominated by a dense population of tube-building ampharetid polychaetes and conspicuous microbial mats were unusually absent. A 1D numerical reaction-transport model, which allows for the explicit growth of sulfide and methane oxidizing microorganisms, was tuned to the geochemical data using a fluid advection velocity of 14 cm yr−1. The fluids provide a deep source of dissolved hydrogen sulfide and methane to the sediment with fluxes equal to 4.1 and 18.2 mmol m−2 d−1, respectively. Chemosynthetic biomass production in the subsurface sediment is estimated to be 2.8 mmol m−2 d−1 of C biomass. However, carbon and oxygen budgets indicate that chemosynthetic organisms living directly above or on the surface sediment have the potential to produce 12.3 mmol m−2 d−1 of C biomass. This autochthonous carbon source meets the ampharetid respiratory carbon demand of 23.2 mmol m−2 d−1 to within a factor of 2. By contrast, the contribution of photosynthetically-fixed carbon sources to ampharetid nutrition is minor (3.3 mmol m−2 d−1 of C). The data strongly suggest that mixing of labile autochthonous microbial detritus below the oxic layer sustains high measured rates of sulfate reduction in the uppermost 2 cm of the sulfidic sediment (100–200 nmol cm−3 d−1). Similar rates have been reported in the literature for other seeps, from which we conclude that autochthonous organic matter is an important substrate for sulfate reducing bacteria in these sediment layers. A system-scale energy budget based on the chemosynthetic reaction pathways reveals that up to 8.3 kJ m−2 d−1 or 96 mW m−2 of catabolic (Gibbs) energy is dissipated at the seep through oxidation reactions. The microorganisms mediating sulfide oxidation and anaerobic oxidation of methane (AOM) produce 95% and 2% of this energy flux, respectively. The low power output by AOM is due to strong bioenergetic constraints imposed on the reaction rate by the composition of the chemical environment. These constraints provide a high potential for dissolved methane efflux from the sediment (12.0 mmol m−2 d−1) and indicates a much lower efficiency of (dissolved) methane sequestration by AOM at seeps than considered previously. Nonetheless, AOM is able to consume a third of the ascending methane flux (5.9 mmol m−2 d−1 of CH4) with a high efficiency of energy expenditure (35 mmol CH4 kJ−1). It is further proposed that bioenergetic limitation of AOM provides an explanation for the non-zero sulfate concentrations below the AOM zone observed here and in other active and passive margin sediments.

Description: Highlights • Gas release from wells may counteract efforts to mitigate greenhouse gas emissions. • An approach for assessing methane release from marine decommissioned wells. • This gas release largely depends on the presence of shallow gas accumulations. • Methane release from hydrocarbon wells represents a major source in the North Sea. Abstract Hydrocarbon gas emissions from with decommissioned wells are an underreported source of greenhouse gas emissions in oil and gas provinces. The associated emissions may partly counteract efforts to mitigate greenhouse gas emissions from fossil fuel infrastructure. We have developed an approach for assessing methane leakage from marine decommissioned wells based on a combination of existing regional industrial seismic and newly acquired hydroacoustic water column imaging data from the Central North Sea. Here, we present hydroacoustic data which show that 28 out of 43 investigated wells release gas from the seafloor into the water column. This gas release largely depends on the presence of shallow gas accumulations and their distance to the wells. The released gas is likely primarily biogenic methane from shallow sources. In the upper 1,000 m below the seabed, gas migration is likely focused along drilling-induced fractures around the borehole or through non-sealing barriers. Combining available direct measurements for methane release from marine decommissioned wells with our leakage analysis suggests that gas release from investigated decommissioned hydrocarbon wells is a major source of methane in the North Sea (0.9-3.7 [95% confidence interval = 0.7-4.2] kt yr−1 of CH4 for 1,792 wells in the UK sector of the Central North Sea). This means hydrocarbon gas emissions associated with marine hydrocarbon wells are not significant for the global greenhouse gas budget, but have to be considered when compiling regional methane budgets.

Description: Highlights • Combining porewater geochemistry, geochemical modeling and subsurface geophysical data in order to understand the fluid flow system of Kerch seep area. • This seep area is not in steady state. • Methane transport is in the form of gas bubbles not porewater advection. • High surface temperatures are the result of hydrate formation and not an indication for elevated geothermal gradients. • Modeling says this seep is young (〈500 years old). Abstract High-resolution 3D seismic data in combination with deep-towed sidescan sonar data and porewater analysis give insights into the seafloor expression and the plumbing system of the actively gas emitting Kerch seep area, which is located in the northeastern Black Sea in around 900 m water depth, i.e. well within the gas hydrate stability zone (GHSZ). Our analysis shows that the Kerch seep consists of three closely spaced but individual seeps above a paleo-channel-levee system of the Don Kuban deep-sea fan. We show that mounded seep morphology results from sediment up-doming due to gas overpressure. Each of the seeps hosts its own gas pocket underneath the domes which are fed with methane of predominantly microbial origin along narrow pipes through the GHSZ. Methane transport occurs dominantly in the form of gas bubbles decoupled from fluid advection. Elevated sediment temperatures of up to 0.3 °C above background values are most likely the result of gas hydrate formation within the uppermost 10 m of the sediment column. Compared to other seeps occurring within the GHSZ in the Black Sea overall only scarce gas indications are present in geoacoustic and geophysical data. Transport-reaction modeling suggests that the Kerch seep is a young seep far from steady state and probably not more than 500 years old.