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The seismic characteristics of focused fluid-related features such as pockmarks and carbonate build-ups on the Nigerian continental slope have been investigated using complementary seismic data sets (reprocessed 3D exploration data and 2D Very High Resolution hull-mounted and near-bottom seismic data) coupled with the results of previous studies (sedimentological, geotechnical and geochemical analyses). The results show different types of fluid-related features within the hemipelagic phase of long duration (∼1 Myr) Turbidite/Hemipelagic cycles. They are the product of the disturbance of the hosting sediments following two main distinct processes: (1) no or low sediment deposition caused by fluid escape associated with seafloor settlement (benthic fauna, carbonate precipitation, gas hydrate formation) and (2) post-depositional erosion, caused either by fluid release (dewatering from underlying features such as channels and upward migration from a deep source) or by collapse (destabilisation of gas hydrates). The temporal evolution reveals a decrease in fluid flow during the hemipelagic deposition as witnessed by the decrease in methanogenic activity and by gas hydrate destabilisation. The spatial distribution of fluid-related features seems to be controlled by the type of fault (small fault or structural lineament). [ABSTRACT FROM AUTHOR]

Abstract: A novel variable-volume type high-pressure apparatus has been designed, constructed and used for gas hydrate investigations. The apparatus has an operating temperature ranging from 253 K to 473 K and pressure ranging from 0.1 MPa to 60 MPa. Its central component consists of a viewing windows cell to which several sensors or analytical instruments can be connected. At its present configuration, a Raman spectrometer and a gas chromatograph are connected for the study of the liquid (or solid) and the gas phases respectively. The apparatus was used for the study of two different systems. The first system was composed of carbon dioxide (CO2) and water for which the hydrate formation and dissolution has been investigated by injecting water into liquid CO2. The evolution of the system was monitored by means of visual observation in combination with Raman spectroscopy. The second system consists of thermogenic-like gases (i.e. synthetic natural gas) for which the hydrate formation and dissociation have additionally been investigated by monitoring the change of the vapour phase composition. The consequences of the destruction of the hydrate skin formed at the water–gas interface have been studied. Thus, an attempt has been made to study the importance of the interfacial contact layer between the gas phase and the aqueous phase for the hydrate growth process. In this paper, we describe in detail the apparatus, followed by the presentation of the results on both systems investigated. [Copyright &y& Elsevier]

Abstract: We describe a new apparatus suitable for measurements of the phase behaviour and phase properties of fluid mixtures under conditions of high-pressure. We propose a synthetic method for the determination of gas solubility, and present results for the system (CO2 +H2O). In addition, we report new measurements of the hydrate equilibrium curves in aqueous systems containing either pure carbon dioxide or mixed gases including CO2. For hydrates formed in the (CO2 +H2O) system, we find an enthalpy of dissociation of 77kJ·mol−1. This value was unchanged by the addition of mass fraction 0.043 of NaCl to the water. Compared with pure CO2, mixtures of CO2 with air exhibited markedly different dissociation pressures at given temperature, but were characterised by the same enthalpy of dissociation. However, two mixtures containing either nitrogen or methane and hydrogen both exhibited a higher enthalpy of dissociation, 106kJ·mol−1, consistent with these systems forming structure II hydrates. [Copyright &y& Elsevier]

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: For many trace elements, continental margins are the location of intense exchange processes between sediment and seawater, which control their distribution in the water column, but have yet to be fully understood. In this study, we have investigated the impact of fluid seepage at cold seeps on the marine cycle of neodymium. We determined dissolved and total dissolvable (TD) concentrations for REE and well-established tracers of fluid seepage (CH4, TDFe, TDMn), and Nd isotopic compositions in seawater samples collected above cold seeps and a reference site (i.e. away from any fluid venting area) from the Niger Delta margin. We also analyzed cold seep authigenic phases and various core-top sediment fractions (pore water, detrital component, easily leachable phases, uncleaned foraminifera) recovered near the hydrocast stations. Methane, TDFe and TDMn concentrations clearly indicate active fluid venting at the studied seeps, with plumes rising up to about 100m above the seafloor. Depth profiles show pronounced REE enrichments in the non-filtered samples (TD concentrations) within plumes, whereas filtered samples (dissolved concentrations) exhibit slight REE depletion in plumes relative to the overlying water column and display typical seawater REE patterns. These results suggest that the net flux of REE emitted into seawater at cold seeps is controlled by the presence of particulate phases, most probably Fe–Mn oxyhydroxides associated to resuspended sediments. At the reference site, however, our data reveal significant enrichment for dissolved REE in bottom waters, that clearly relates to diffusive benthic fluxes from surface sediments. Neodymium isotopic ratios measured in the water column range from εNd ~−15.7 to −10.4. Evidence that the εNd values for Antarctic Intermediate waters (AAIW) differed from those reported for the same water mass at open ocean settings shows that sediment/water interactions take place in the Gulf of Guinea. At each site, however, the bottom water εNd signature generally differs from that for cold seep minerals, easily leachable sediment phases, and detrital fractions from local sediments, ruling out the possibility that seepage of methane-rich fluids and sediment dissolution act as a substantial source of dissolved Nd to seawater in the Gulf of Guinea. Taken together, our data hence suggest that co-precipitation of Fe–Mn oxyhydroxide phases in sub-surface sediments leads to quantitative scavenging of dissolved REE at cold seeps, preventing their emission into bottom waters. Most probably, it is likely that diffusion from suboxic surface sediments dominates the exchange processes affecting the marine Nd cycle at the Niger Delta margin. [Copyright &y& Elsevier]

Natural Gas Hydrates (NGH) collected during the Ghass cruise 2015 in the Western Black Sea onboard the R/V Pourquoi pas? are characterized by a suite of techniques. Gas Chromatography and Raman spectroscopy are used for the identification of the nature of the gas source, the hydrate structure and spatial variability of cage occupancies. The nature and source of hydrate forming gases primarily reveal a high methane content (99.6 mol%) and small amount of nitrogen (>0.29 mol%) and CO 2 (0.056 mol%). Isotopic analyses from the hydrate-bound methane and recently published results from Pape et al. (2020) clearly indicate a microbial source of gas supplying the hydrate deposit generated by the reduction of carbon. For the first time, Raman imaging spectroscopy was applied on NGH recovered in the Western Black Sea. The results show a heterogeneous distribution of the encapsulated guest molecules (CH 4 , N 2 and H 2 S), which is associated with a spatial variability of the guest-gas composition at the micron-scale. Some portions of the 2D-Raman images clearly exhibit a relative N 2 -enrichment (with a concentration exceeding 6 mol% N 2 at some positions), while H 2 S shows a rather minor contribution on all the spectral maps investigated. A correlation is then established between the composition of the gas in the NGH and its impact on the CH 4 cage occupancy, with a ratio of θ LC /θ SC (large cage/small cage) between ~ 0.5 and 1.26 depending on the positions analyzed. The departure from the expected ratio in pure methane hydrate is attributed to the preferential encasement of N 2 in the large cage of the NGH structure. In addition, the occurrence of carotenoids identified in sediment-rich zones show a minor impact on the CH 4 cage occupancies. The results are discussed within the context of natural gas resource estimates in NGH to emphasize how the measured cage occupancies may impact the volumetric conversion factor commonly used with other geologic parameters to determine the resource endowment and global volume of methane. The small-scale heterogeneities revealed by the 2D-Raman images point out the importance to better understand stages of hydrates formation in methane-rich seafloor environment. • NGH from Black Sea are investigated by gas chromatography and Raman spectroscopy. • The hydrates are structure sI and contain mainly CH 4 and small amounts of N 2 and CO 2. • CH 4 being generated by the reduction of CO 2. • 2D-Raman reveals spatial variability in guests' distribution and hydrate composition. • Raman imaging analysis shows a spatial variability of the cage occupancy. [ABSTRACT FROM AUTHOR]

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]

A range of plumbing systems has been identified in deep-water Nigeria by interpreting multi-scale seismic data sets (reprocessed 3D exploration seismic reflection data and 2D very high-resolution near-bottom seismic reflection data) as well as sedimentological and geochemical data obtained from a long sediment core recovered by the seafloor drill rig MARUM-MeBo70. The plumbing systems are characterized by diverse fault networks and lie above tectonic features including thrust/fold structures and strike-slip faults linked to gravity-driven deformation caused by underlying over-pressured shales. The plumbing systems are associated with fluid seeping structures at the seafloor such as pockmarks, mud volcanoes and seafloor zonations colonized by living benthic macrofauna typical of active fluid flow. The comparison of seismic stratigraphic sequences with climate and environmental proxies determined for sediments including lithology, element ratios such as Ca/Fe and Zr/Rb, sedimentation rates, and planktonic foraminifera δ18O records shows a control of short-term (0.1–0.4 Myr) and long-term (around 1 Myr) sedimentary cycles. During short-term fluctuations, the recurrence of fluid seeping structures is controlled by the lithology (coarse-grained versus fine-grained sediments) linked to glacial-interglacial fluctuations and a monsoon regime. Conditions favorable for fluid flow are related to the deposition of coarse-grained layers, glacial periods, sea-level lowstands, and low sedimentation rates. We hypothesize that cyclic gravity-driven sediment deformations controlled by glacial-interglacial and long-term variations in accommodation and sedimentation, have led to the cyclic evolution of the plumbing systems and associated seeping structures since the Plio-Pleistocene. • Diverse faults networks are associated with varied fluid flow structures. • The recurrence of fluid flow structures is coeval to glacial periods. • Gravity-driven deformations possibly control fluid flow during the Pleistocene. [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 and silicon cycles at the Earth surface are linked to long-term variations of atmospheric CO 2 and oceanic primary production. In these cycles, the river-sea interface is considered a biogeochemical hotspot, and deltas presently receive and preserve a major fraction of riverine particles in shallow water sediments. In contrast, periods of glacial maximum lowstand were characterized by massive exports of sediments to the deep-sea via submarine canyons and accumulation in deep-sea fans. Here, we calculate present-day mass balances for organic carbon (OC) and amorphous silica (aSi) in the terminal lobe complex of the Congo River deep-sea fan as an analogue for glacial periods. We show that this lobe complex constitutes a megasink with the current accumulation of 18 and 35% of the OC and aSi river input, respectively. This increases the estimates of organic carbon burial by 19% in the South Atlantic Ocean in a zone representing less than 0.01% of the basin. These megasinks might have played a role in carbon trapping in oceanic sediments during glacial times. • Sediments located at the termination of Congo Canyon are a megasink of organic carbon (0.35 TgC/yr) and aSi (0.11 TgSi/yr). • These sediments store in the deep-sea at 5 km depth 18 and 35% of Congo River OC and amorphous silica inputs, respectively. • OC burial in these sediments increases OC burial in the South Atlantic deep basin (>3000m) by 19% for a surface area <0.01%. • Burial efficiencies in this megasink are 85% for OC and 73% for aSi. [ABSTRACT FROM AUTHOR]