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A few thousand (2,612) seeps are releasing microbial methane bubbles from the seafloor at the Aquitaine Shelf edge (Bay of Biscay) at shallow water depths (140–220 m). This methane contributes to the formation of meter‐scale subcircular carbonate structures, which are (sub)outcropping over 375 km2. Based on in situ flow rate measurements and acoustic data, and assuming steady and continuous fluxes over time, the methane entering the water column is estimated at 144 Mg/yr. Microbial methane circulation has been ongoing for at least a few thousand years. This discovery highlights the importance of microbial methane generation, disconnected from deep thermogenic sources and gas hydrates, at continental shelves. The shelf edge may be viewed as a focus area for methane circulation and release and related diagenesis, all having an impact on the shaping of continental shelves and potentially on the oceanic and atmospheric carbon budget. Plain Language Summary: At the Aquitaine Shelf of the Bay of Biscay (Northeast Atlantic Ocean), the recent acoustic, chemical, and visual investigations of microbial methane release at the seafloor have led to the discovery of a vast fluid system. This methane escapes as bubbles from the seafloor into the seawater at 2,612 sites, all located at shallow water depths (140–220 m) along the edge of the continental shelf. Methane‐derived authigenic carbonates that are by‐products of gas seepage cover the (sub)seafloor over a large area of 375 km2. These carbonates form subcircular meter‐scale pavements and mounds, less than 2 m in height above the surrounding seafloor. Based on the growth rate of authigenic carbonates, it can be inferred that methane circulation has occurred for at least a few thousand years. The amount of methane released from the Aquitaine Shelf seafloor into the water column, estimated at 144 t/yr, questions the fate of the methane in the ocean and its possible passage to the atmosphere with therefore consequent potential contribution to the oceanic and atmospheric carbon budget over time. Key Points: Up to 2,612 gas bubbling sites at the Aquitaine Shelf edge release 144 Mg/yr of microbial methane into the water columnMethane‐derived authigenic (sub)outcropping carbonates cover 375 km2Methane‐rich fluids have been circulating for at least a few thousand years [ABSTRACT FROM AUTHOR]

Abstract In this preliminary study, we investigate living (stained) foraminifera from the Sea of Marmara. We focus on the faunal composition and geochemical signatures (trace elements, carbon and oxygen stable isotopes) in foraminiferal tests at two deep-sea sites (329 and ~ 1240 m depth respectively). Documented by ROV observations and sampling, both study areas are heterogeneous (including bacterial mats and carbonate concretions), proximal to cold seeps and consist of dysoxic bottom water (O 2 < 20 µmol/L). The prevailing dysoxia at both study areas restricts foraminiferal diversity to very low values (S < 9, H' < 0.97). Stress-tolerant species Bolivina vadescens and Globobulimina affinis dominate living faunas at both sites. The highest foraminiferal standing stock is recorded at the shallowest site underneath a spreading bacterial mat. No benthic foraminifera from either site possess geochemical signatures of methane seepage. Our biogeochemical results show that use of foraminiferal Mn/Ca ratios as a proxy for bottom water oxygenation depends strongly on regional physiography, sedimentary processes and water column structure. [ABSTRACT FROM AUTHOR]

Abstract Cold seeps along the North Anatolian fault in the Sea of Marmara (Turkey) were explored during submersible dives of the Marsite cruise in November 2014 when sediments, pore waters and carbonate crusts were sampled at active fluid seeping sites. In this study, we investigate the mineralogy, carbon and oxygen isotopic compositions and the lipid biomarkers of a carbonate crust from the western Tekirdağ basin of the Sea of Marmara. This crust exhibits a laminated domal structure that resembles stromatolite. The mineralogy of authigenic seep-carbonate is mostly represented by aragonite associated with minor amounts of high-magnesian calcite. The abundance of pyrite associated with the authigenic seep-carbonate points to very intense bacterial sulfate reduction. The carbon (−42.6‰ to −34.4‰) and oxygen (−1.5‰ to +1.1‰) isotopic compositions of the authigenic seep-carbonate crust indicate that carbonate precipitation was related to anaerobic oxidation of methane and occurred in mixtures of bottom seawater with brackish water expelled from the underlying sediments. Abundant microbial lipid biomarkers with negative δ13C values (−121‰ to −96‰), confirm that anaerobic oxidation of methane (AOM) coupled with sulfate reduction, was mediated by methanotrophic archaea (ANME) and sulfate reducing bacteria (SRB). Diagnostic lipid fingerprints indicate that ANME-2 archaea and associated SRB were the prevalent AOM-mediating consortia, which characterize moderate to high methane flow at this site. Moreover, changes in microbial lipid distribution within the carbonate crust suggest a variation in the intensity of methane emission. [ABSTRACT FROM AUTHOR]

Abstract During the MARSITECruise expedition in November 2014 on board the RV Pourquoi Pas? , multidisciplinary sampling was carried out with the ROV Victor 6000 in order to investigate biogeochemical processes taking place at cold seep environments in the Sea of Marmara. Pore water, bottom water, sediment and authigenic carbonate samples were collected from two short push cores (MRS-DV5-PC04 − 8 cm, MRS-DV5-PC01 − 12.5 cm) at an active methane bubbling site in the southeastern part of the Çinarcik Basin. Sulfate sulfur and oxygen isotope data as well as sulfide isotope data indicate that sulfate-dependent anaerobic oxidation of methane is the dominant process in the sediments. This is confirmed by archaeal lipids diagnostic for anaerobic methane oxidizers detected with strong 13C-depletions. The available data even allows to distinguish the dominant AOM assemblages. Specific lipid patterns are consistent with a dominance of ANME-2 archaea within the microbial community. Abundant authigenic carbonates (mostly aragonite), found at all depths, show a narrow range in δ13C values between −27.69‰ and −33.40‰. The carbon isotopic composition of the dissolved inorganic carbon as well as strontium and calcium isotopes confirm that the current reaction zone (sulfate-methane transition zone) starts at the bottom of the core. All shallower carbonates are witnesses of paleo seepage activity. U-Th dating of four pure aragonite samples show the short time span that is preserved in core MRS-DV5-PC01 (235 ± 60 yr B.P.). Two major earthquakes of 1766 CE and 1754 CE in the Çinarcik Basin might potentially have triggered the increased seepage of methane at this location. [ABSTRACT FROM AUTHOR]

Composite activated carbon monoliths were prepared from polyfurfuryl alcohol-impregnated compressed expanded graphite (CEG) blocks by pyrolysis at 923 K followed by steam activation at 1073 K. The porous texture of these materials was analysed from physical adsorption measurements of N2 at 77 K and CO2 at 273 K. Pyrolysis gives rise to a nitrogen surface area higher than for many conventional carbonised precursors of active carbons. Activation develops even more the porosity. At low burn-offs, there is principally creation of new pores (including ultramicropores). At higher burn-offs (of the order of 40%), opening of preexisting pores takes place. The materials obtained are essentially microporous and exhibit a rather narrow pore size distribution. [Copyright &y& Elsevier]

• Δ13CH 3 D and Δ12CH 2 D 2 investigated in marine cold seeps from the Sea of Marmara. • Microbial/thermogenic samples show equilibrium temperatures up to 130 °C. • Non-enzymatic mechanism for isotope bond ordering to reservoirs temperatures. The measurement of methane clumped isotopologues (Δ 13 CH 3 D and Δ 12 CH 2 D 2) allows exploring isotope bond ordering within methane molecules, and may reveal equilibrium temperatures. Whether such temperature reflects the formation or re-equilibration temperature of the methane is not well understood, but would have critical implications for the use of methane clumped isotopologues as geo-thermometers. Here we investigate gas bubbles from vigorous emissions at cold seeps (n = 14) in the Sea of Marmara, Turkey. These cold seeps are sourced from deeper sedimentary reservoirs. Conventional geochemical tracers such as carbon and hydrogen bulk isotopic ratios (13C/12C and D/H) or n -alkane molecular ratios, suggest these gases reflect various degrees of mixing between thermogenic and microbial sources. Some samples would generally be considered purely microbial in origin (C 1 / C 2 + > 1500 ; δ 13 C < − 60 ‰). We report measurements of Δ 13 CH 3 D and Δ 12 CH 2 D 2 showing that a fraction of those gases are in internal thermodynamic equilibrium, with the abundances of the two mass-18 isotopologues indicating concordant temperatures of ∼90 °C and ∼130 °C. These concordant temperatures are recorded by gases of putative microbial and thermogenic origin; the temperatures of equilibration are irrespective of the formation mechanism of the gases. We conclude that the two high-temperatures recorded by Δ 13 CH 3 D and Δ 12 CH 2 D 2 are best explained by non-enzymatic re-equilibration at two local subsurface temperatures. First principles suggest that unequal rates of exchange are possible. Disequilibrium signatures where the two isotopologues yield discordant apparent temperatures are exhibited by other samples. In those cases the data define a trend of variable Δ 13 CH 3 D at nearly constant Δ 12 CH 2 D 2. These signatures are enigmatic, and we investigate and reject multiple possible explanations including mixing, diffusion or Anaerobic Oxidation of Methane. Different rates of re-equilibration between the two rare isotopologues are implied, although lacks experimental foundation at present. In general, all of these data point towards re-equilibration of the mass-18 methane isotopologues as an important process. [ABSTRACT FROM AUTHOR]

Carbon dioxide (CO 2 ) and methane (CH 4 ) are two climate-sensitive components of gases migrating within sediments and emitted into the water column on continental margins. They are involved in several key biogeochemical processes entering into the global carbon cycle. In order to perform onboard measurements of both the molecular and stable carbon isotope ratios (δ 13 C) of CH 4 and CO 2 of natural gases during oceanic cruises, we have developed a novel approach coupling gas chromatography (GC) with cavity ring-down spectroscopy (CRDS). The coupled devices are connected to a small sample isotope module (SSIM) to form a system called GC-SSIM-CRDS. Small volumes of natural gas samples (<1 mL) are injected into the GC using a headspace autosampler or a gas-tight syringe to separate the chemical components using a Shincarbon ST packed column and for molecular quantification by thermal conductivity detection (TCD). Subsequently, CO 2 from the sample is trapped in a 7 mL loop at 32 °C before being transferred to the CRDS analyzer for sequential determination of the stable carbon isotope ratios of CH 4 and CO 2 in 24 min. The loop is an open column (without stationary phase). This approach does not require the use of adsorbents or cooling for the trapping step. Optimization of the separation step prior to analysis was focused on the influence of two key separation factors 1) the flow of the carrier gas and 2) the temperature of the oven. Our analytical system and the measurement protocol were validated on samples collected from gas seeps in the Sea of Marmara (Turkey). Our results show that the GC-SSIM-CRDS system provides a reliable determination of the molecular identification of CH 4 and CO 2 in complex natural gases, followed by the stable carbon isotope ratios of methane and carbon dioxide., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2021 Elsevier B.V. All rights reserved.)

Gas hydrates, a solid established by water and gas molecules, are widespread along the continental margins of the world. Their dynamics have mainly been regarded through the lens of temperature-pressure conditions. A fluctuation in one of these parameters may cause destabilization of gas hydrate-bearing sediments below the seafloor with implications in ocean acidification and eventually in global warming. Here we show throughout an example of the Black Sea, the world's most isolated sea, evidence that extensive gas hydrate dissociation may occur in the future due to recent salinity changes of the sea water. Recent and forthcoming salt diffusion within the sediment will destabilize gas hydrates by reducing the extension and thickness of their thermodynamic stability zone in a region covering at least 2800 square kilometers which focus seepages at the observed sites. We suspect this process to occur in other world regions (e.g., Caspian Sea, Sea of Marmara).

Over the past years, several studies have raised concerns about the possible interactions between methane hydrate decomposition and external change. To carry out such an investigation, it is essential to characterize the baseline dynamics of gas hydrate systems related to natural geological and sedimentary processes. This is usually treated through the analysis of sulfate-reduction coupled to anaerobic oxidation of methane (AOM). Here, we model sulfate reduction coupled with AOM as a two-dimensional (2D) problem including, advective and diffusive transport. This is applied to a case study from a deep-water site off Nigeria's coast where lateral methane advection through turbidite layers was suspected. We show by analyzing the acquired data in combination with computational modeling that a two-dimensional approach is able to accurately describe the recent past dynamics of such a complex natural system. Our results show that the sulfate-methane-transition-zone (SMTZ) is not a vertical barrier for dissolved sulfate and methane. We also show that such a modeling is able to assess short timescale variations in the order of decades to centuries.