Diverse methane concentrations in anoxic brines and underlying sediments,eastern Mediterranean Sea

Elevated methane (CH₄) concentrations (128–2692×10³ nM) occur in the hypersaline anoxic brine pools of Bannock and Urania Basins, eastern Mediterranean Sea, compared to low concentrations (17–80×10³ nM) in the sediments below the anoxic brines. The CH₄ enrichment in the brines might be due to the long residence time of the brine in the Basin. An attempt is made to determine the sources for the enriched dissolved CH₄ by considering the influence of hydrothermal activity, the occurrence of sapropel layers (biogenic) and dissolution of gas hydrates. Furthermore, it is suggested that the enriched CH₄ in Bannock and Urania Basins is diffused and mixed with the overlying waters by local upward transport mechanisms that selectively move CH₄ upward in these Basins.     

The Norwegian–Barents–Svalbard (NBS) continental margin: Introducing a natural laboratory of mass wasting, hydrates, and ascent of sediment, pore water, and methane

Side-scan sonar mapping and ground-truthing of the Norwegian–Barents–Svalbard continental margin shed new light on shelf glaciation, mass wasting, hydrates, and features like the Håkon Mosby mud volcano (HMMV), reflecting upward mobility of gas, pore fluids, and sediments. Detailed HMMV examination revealed thermal gradients to 10°/m, bottom-water CH₄ and temperature anomalies, H₂S- and CH₄-based chemosynthetic ecosystems, and subbottom methane hydrate (to 25%). Seismic and chemical data suggest HMMV origins at 2–3?km depth within the 6-km-thick depocenter. The HMMV and mound fields bordering the Bjørnøyrenna slide valley and pockmarks bordering the Storegga slide may all have formed in response to sediment failure.     

Temporal variations in carbon dioxide and methane concentrations under urban conditions

Temporal variations in the surface concentrations of two greenhouse gases (carbon dioxide and methane) in the atmosphere over a large city are studied on the basis of the data obtained during the 2003–2005 observations at a Moscow station for environmental monitoring. This station is based on the TROICA mobile observatory and located at the meteorological station of the Faculty of Geography, Moscow State University, on Vorob’evy gory. The methods of isolating the background concentrations of greenhouse gases under urban conditions are proposed, and the excess concentrations of CO₂ and CH₄ over their background values are estimated for different seasons and times of day. The CO₂ and CH₄ concentrations are shown to have more pronounced diurnal cycles in summer than in winter. The main causes of temporal variations in the surface concentrations of CO₂ and CH₄ under urban conditions and the differences between the mean concentrations of these greenhouse gases in Moscow and other areas of Russia are analyzed. It is shown that variations in the surface concentrations of carbon dioxide and methane on different time scales are caused by different atmospheric processes (global circulation, mesoscale gravity waves, surface temperature inversions, etc.)     

In situ hydrocarbon concentrations from pressurized cores in surface sediments, Northern Gulf of Mexico

Two newly developed coring devices, the Multi-Autoclave-Corer and the Dynamic Autoclave Piston Corer were deployed in shallow gas hydrate-bearing sediments in the northern Gulf of Mexico during research cruise SO174 (Oct–Nov 2003). For the first time, they enable the retrieval of near-surface sediment cores under ambient pressure. This enables the determination of in situ methane concentrations and amounts of gas hydrate in sediment depths where bottom water temperature and pressure changes most strongly influence gas/hydrate relationships. At seep sites of GC185 (Bush Hill) and the newly discovered sites at GC415, we determined the volume of low-weight hydrocarbons (C₁ through C₅) from nine pressurized cores via controlled degassing. The resulting in situ methane concentrations vary by two orders of magnitudes between 0.031 and 0.985 mol kg^− 1 pore water below the zone of sulfate depletion. This includes dissolved, free, and hydrate-bound CH₄. Combined with results from conventional cores, this establishes a variability of methane concentrations in close proximity to seep sites of five orders of magnitude. In total four out of nine pressure cores had CH₄ concentrations above equilibrium with gas hydrates. Two of them contain gas hydrate volumes of 15% (GC185) and 18% (GC415) of pore space. The measurements prove that the highest methane concentrations are not necessarily related to the highest advection rates. Brine advection inhibits gas hydrate stability a few centimeters below the sediment surface at the depth of anaerobic oxidation of methane and thus inhibits the storage of enhanced methane volumes. Here, computerized tomography (CT) of the pressure cores detected small amounts of free gas. This finding has major implications for methane distribution, possible consumption, and escape into the bottom water in fluid flow systems related to halokinesis.     

The characteristics of gas hydrates recovered from the Mount Elbert Gas Hydrate Stratigraphic Test Well, Alaska North Slope

Systematic analyses have been carried out on two gas hydrate-bearing sediment core samples, HYPV4, which was preserved by CH₄ gas pressurization, and HYLN7, which was preserved in liquid-nitrogen, recovered from the BPXA-DOE-USGS Mount Elbert Stratigraphic Test Well. Gas hydrate in the studied core samples was found by observation to have developed in sediment pores, and the distribution of hydrate saturation in the cores imply that gas hydrate had experienced stepwise dissociation before it was stabilized by either liquid nitrogen or pressurizing gas. The gas hydrates were determined to be structure Type I hydrate with hydration numbers of approximately 6.1 by instrumentation methods such as powder X-ray diffraction, Raman spectroscopy and solid state ¹³C NMR. The hydrate gas composition was predominantly methane, and isotopic analysis showed that the methane was of thermogenic origin (mean δ¹³C = −48.6‰ and δ_D = −248‰ for sample HYLN7). Isotopic analysis of methane from sample HYPV4 revealed secondary hydrate formation from the pressurizing methane gas during storage.     

Greenhouse gases generated from the anaerobic biodegradation of natural offshore asphalt seepages in southern California

Significant offshore asphaltic deposits with active seepage occur in the Santa Barbara Channel offshore southern California. The composition and isotopic signatures of gases sampled from the oil and gas seeps reveal that the coexisting oil in the shallow subsurface is anaerobically biodegraded, generating CO₂ with secondary CH₄ production. Biomineralization can result in the consumption of as much as 60% by weight of the original oil, with ¹³C enrichment of CO₂. Analyses of gas emitted from asphaltic accumulations or seeps on the seafloor indicate up to 11% CO₂ with ¹³C enrichment reaching +24.8‰. Methane concentrations range from less than 30% up to 98% with isotopic compositions of –34.9 to –66.1‰. Higher molecular weight hydrocarbon gases are present in strongly varying concentrations reflecting both oil-associated gas and biodegradation; propane is preferentially biodegraded, resulting in an enriched ¹³C isotopic composition as enriched as –19.5‰. Assuming the 132 million barrels of asphaltic residues on the seafloor represent ~40% of the original oil volume and mass, the estimated gas generated is 5.0×10¹⁰ kg (~76×10⁹ m³) CH₄ and/or 1.4×10¹¹ kg CO₂ over the lifetime of seepage needed to produce the volume of these deposits. Geologic relationships and oil weathering inferences suggest the deposits are of early Holocene age or even younger. Assuming an age of ~1,000 years, annual fluxes are on the order of 5.0×10⁷ kg (~76×10⁶ m³) and/or 1.4×10⁸ kg for CH₄ and CO₂, respectively. The daily volumetric emission rate (2.1×10⁵ m³) is comparable to current CH₄ emission from Coal Oil Point seeps (1.5×10⁵ m³/day), and may be a significant source of both CH₄ and CO₂ to the atmosphere provided that the gas can be transported through the water column.     

Gas hydrates in shallow deposits of the Amsterdam mud volcano, Anaximander Mountains, Northeastern Mediterranean Sea

We investigated gas hydrate in situ inventories as well as the composition and principal transport mechanisms of fluids expelled at the Amsterdam mud volcano (AMV; 2,025 m water depth) in the Eastern Mediterranean Sea. Pressure coring (the only technique preventing hydrates from decomposition during recovery) was used for the quantification of light hydrocarbons in near-surface deposits. The cores (up to 2.5 m in length) were retrieved with an autoclave piston corer, and served for analyses of gas quantities and compositions, and pore-water chemistry. For comparison, gravity cores from sites at the summit and beyond the AMV were analyzed. A prevalence of thermogenic light hydrocarbons was inferred from average C₁/C₂₊ ratios <35 and δ¹³C-CH₄ values of ?50.6‰. Gas venting from the seafloor indicated methane oversaturation, and volumetric gas–sediment ratios of up to 17.0 in pressure cores taken from the center demonstrated hydrate presence at the time of sampling. Relative enrichments in ethane, propane, and iso-butane in gas released from pressure cores, and from an intact hydrate piece compared to venting gas suggest incipient crystallization of hydrate structure II (sII). Nonetheless, the co-existence of sI hydrate can not be excluded from our dataset. Hydrates fill up to 16.7% of pore volume within the sediment interval between the base of the sulfate zone and the maximum sampling depth at the summit. The concave-down shapes of pore-water concentration profiles recorded in the center indicate the influence of upward-directed advection of low-salinity fluids/fluidized mud. Furthermore, the SO ₄ ^2? and Ba²⁺ pore-water profiles in the central part of the AMV demonstrate that sulfate reduction driven by the anaerobic oxidation of methane is complete at depths between 30 cm and 70 cm below seafloor. Our results indicate that methane oversaturation, high hydrostatic pressure, and elevated pore-water activity caused by low salinity promote fixing of considerable proportions of light hydrocarbons in shallow hydrates even at the summit of the AMV, and possibly also of other MVs in the region. Depending on their crystallographic structure, however, hydrates will already decompose and release hydrocarbon masses if sediment temperatures exceed ca. 19.3°C and 21.0°C, respectively. Based on observations from other mud volcanoes, the common occurrence of such temperatures induced by heat flux from below into the immediate subsurface appears likely for the AMV.     

Spatial variation in shallow sediment methane sources and cycling on the Alaskan Beaufort Sea Shelf/Slope

The MITAS (Methane in the Arctic Shelf/Slope) expedition was conducted during September, 2009 onboard the U.S. Coast Guard Cutter (USCGC) Polar Sea (WAGB-11), on the Alaskan Shelf/Slope of the Beaufort Sea. Expedition goals were to investigate spatial variations in methane source(s), vertical methane flux in shallow sediments (<10 mbsf), and methane contributions to shallow sediment carbon cycling. Three nearshore to offshore transects were conducted across the slope at locations approximately 200 km apart in water column depths from 20 to 2100 m. Shallow sediments were collected by piston cores and vibracores and samples were analyzed for sediment headspace methane (CH₄), porewater sulfate (SO₄²⁻), chloride (Cl⁻), and dissolved inorganic carbon (DIC) concentrations, and CH₄ and DIC stable carbon isotope ratios (δ¹³C). Downward SO₄²⁻ diffusion rates estimated from sediment porewater SO₄²⁻ profiles were between −15.4 and −154.8 mmol m⁻² a⁻¹ and imply a large spatial variation in vertical CH₄ flux between transects in the study region. Lowest inferred CH₄ fluxes were estimated along the easternmost transect. Higher inferred CH₄ flux rates were observed in the western transects. Sediment headspace ${\mathrm{\delta }}^{13}{\text{C}}_{{\text{CH}}_4}$ values ranged from −138 to −48‰, suggesting strong differences in shallow sediment CH₄ cycling within and among sample locations. Measured porewater DIC concentrations ranged from 2.53 mM to 79.39 mM with δ¹³C_DIC values ranging from −36.4‰ to 5.1‰. Higher down-core DIC concentrations were observed to occur with lower δ¹³C where an increase in ${\mathrm{\delta }}^{13}{\text{C}}_{{\text{CH}}_4}$ was measured, indicating locations with active anaerobic oxidation of methane. Shallow core CH₄ production was inferred at the two western most transects (i.e. Thetis Island and Halkett) through observations of low ${\mathrm{\delta }}^{13}{\text{C}}_{{\text{CH}}_4}$ coupled with elevated DIC concentrations. At the easternmost Hammerhead transect and offshore locations, ${\mathrm{\delta }}^{13}{\text{C}}_{{\text{CH}}_4}$ and DIC concentrations were not coupled suggesting less rapid methane cycling. Results from the MITAS expedition represent one of the most comprehensive studies of methane source(s) and vertical methane flux in shallow sediments of the U.S. Alaskan Beaufort Shelf to date and show geospatially variable sediment methane flux that is highly influenced by the local geophysical environment.     

Authigenic barite nodules and carbonate concretions in the Upper Devonian shale succession of western New York – A record of variable methane flux during burial

Authigenic barite nodules associated with modestly ¹³C-depleted calcium carbonate concretions and ³⁴S-enriched pyrite at the bottom of the Upper Devonian Hanover Shale of western New York provide evidence of sulfate reduction coupled with anaerobic oxidation of methane (AOM). The methane, much of it biogenic in origin, may have diffused upward from Middle Devonian Marcellus Shale and perhaps the Upper Ordovician Utica Shale. Strong ³⁴S enrichment and high δ³⁴S/δ¹⁸O values of the barite nodules reflect: (1) substantial kinetic fractionation induced by microbial sulfate reduction perhaps intensified by a low seawater sulfate recharge rate and (2) upward delivery of Ba²⁺- and CH₄- bearing pore fluid sourced within underlying sulfate-depleted deposits. However, the association of authigenic calcium carbonate and barite in the same stratigraphic interval, especially the presence of barite overgrowths on carbonate concretions, is not consistent with what is known of AOM-related mineralization of a sediment column passing downward through the sulfate–methane transition (SMT). The documented early formation of authigenic carbonate followed by barite observed relations may reflect a diminished rate of methanogenesis and/or CH₄ supply. The tempered methane flux would have induced the SMT to descend the sediment column enabling barite to form within the same stratigraphic horizon that ¹³C-depleted calcium carbonate had most recently precipitated. Diminished methane flux may have been caused by burial-related passage of the organic-rich Marcellus Shale below the depth of peak biogenic methane generation and its replacement at that depth interval by organic-lean deposits of the upper part of the Hamilton Group. Subsidence of the SMT would have increased the preservation potential of authigenic barite. However, continued survival of the labile barite as it eventually moved through the SMT suggests that the underlying sulfate-depleted zone was strongly enriched in Ba²⁺.     

Potential map of gas hydrate formation in Caspian Sea based on physicochemical stability evaluation of methane hydrate

Preliminary studies of Caspian Sea have shown the possibility of gas hydrate accumulations, because of suitable physicochemical conditions, existence of clayey deposits, and high concentrations of organic matter. Studies have indicated that gas hydrates are mainly composed of methane. Therefore, based on physicochemical equations for methane hydrate stability in different pressure, temperature, and salinity, this study was designed to calculate the potential of gas hydrate formation in the Caspian Sea basin. For this, data of more than 600 locations were analyzed and in each location, upper and lower limits of methane hydrate formation zone were calculated. Then, the zoning maps of upper and lower limits were prepared which can be useful for exploring the gas hydrate as an energy source or predicting gas hydrate hazards. According to the calculations and maps, methane hydrate formation in Caspian Sea, theoretically, can take place from near the seabed to 4000 and 2500 m beneath the sea surface when low and high geothermal gradient are supposed, respectively. By comparing the results with gas hydrate zones revealed in geophysical profiles, it has been shown that, in Caspian Sea, gas hydrates probably accumulate near the lower limit when a high geothermal gradient is assumed.     

中国滨海湿地互花米草群落甲烷通量研究的综述

互花米草(Spartina alterniflora)具有较强的固碳作用,了解互花米草群落的甲烷通量可为评估互花米草的净碳汇功能提供重要参数。本文分析了我国滨海湿地互花米草群落CH₄通量的总体特点和机制,结果表明：①不同地区互花米草群落CH₄通量无明显规律且差异较大。不同生长环境下的环境因子对CH₄排放有综合调控作用,其中很大部分是通过影响土壤中与CH₄产生有关的微生物影响CH₄通量。②互花米草群落CH₄通量夏季最高、冬春较低;日通量则处于不规则的波动中,但总体白天通量高于夜晚。CH₄通量季节差异与温度、生物量和光照呈正相关,温度影响参与CH₄生成的微生物的活性,生物量为CH₄产生提供有机质原料,光照则通过光合作用影响有机质的合成;日通量差异除与温度和光照有关外,最主要还受到潮汐变化的影响。③无潮水覆盖时CH₄通量远大于有潮水覆盖时。有潮水覆盖时互花米草下部作为CH₄排向大气的重要通道受阻,同时CH₄被储存于土壤或排放到潮水中,落潮后才进入大气,因此CH₄通量更低。④刈割会降低CH₄通量。互花米草植株为CH₄的产生提供了重要原料,同时利用通气组织将CH₄排放到大气,刈割切断了CH₄传输途径并减少了地上生物量,因此降低了CH₄通量。     

天然气水合物赋存区麻坑地貌特征及其地质灾害意义

文章通过对天然气水合物资源及其赋存区典型地貌体特征的分析,梳理了天然气水合物赋存区和麻坑地貌体的地质灾害类型,阐述了由于天然气水合物分解释放造成海底滑坡、滑塌和甲烷气体大规模逸散,继而引起海底输电或通信电缆毁坏、海洋石油钻井平台垮塌,甚至海啸和全球气候变暖等严重灾害。为天然气水合物勘探和开采提供有益参考。     

Continuous inline mapping of a dissolved methane plume at a blowout site in the Central North Sea UK using a membrane inlet mass spectrometer – Water column stratification impedes immediate methane release into the atmosphere

The dissolved methane (CH₄) plume rising from the crater of the blowout well 22/4b in the Central North Sea was mapped during stratified water column conditions. Geochemical surveys were conducted close to the seafloor at 80.3 m water depth, below the thermocline (61.1 m), and in the mixed surface layer (13.2 m) using membrane inlet mass spectrometry (MIMS) in combination with a towed CTD. Seawater was continuously transferred from the respective depth levels of the CTD to the MIMS by using an inline submersible pump. Close to the seafloor a well-defined CH₄ plume extended from the bubble release site ∼460 m towards the southwest. Along this distance CH₄ concentrations decreased from a maximum of 7872 nmol l⁻¹ to less than 250 nmol l⁻¹. Below the thermocline the well-defined CH₄ plume shape encountered at the seafloor was distorted and filaments were observed that extended towards the west and southwest in relation to current direction. Where the core of the bubble plume intersected this depth layer, footprints of high CH₄ concentrations of up to 17,900 nmol l⁻¹ were observed. In the mixed surface layer the CH₄ distribution with a maximum of up to 3654 nmol l⁻¹ was confined to a small patch of ∼60 m in diameter. The determination of the water column CH₄ inventories revealed that CH₄ transfer across the thermocline was strongly impeded as only ∼3% of the total water column inventory was located in the mixed surface layer. Best estimate of the CH₄ seabed release from the blowout was 1751 tons yr⁻¹. The fate of the trapped CH₄ (∼97%) that does not immediately reach the atmosphere remains speculative. In wintertime, when the water column becomes well mixed as well as during storm events newly released CH₄ and the trapped CH₄ pool can be transported rapidly to the sea surface and emitted into the atmosphere.     

Estimates of methane output from mud extrusions at the erosive convergent margin off Costa Rica

Four mud extrusions were investigated along the erosive subduction zone off Costa Rica. Active fluid seepage from these structures is indicated by chemosynthetic communities, authigenic carbonates and methane plumes in the water column. We estimate the methane output from the individual mud extrusions using two independent approaches. The first is based on the amount of CH₄ that becomes anaerobically oxidized in the sediment beneath areas covered by chemosynthetic communities, which ranges from 10⁴ to 10⁵ mol yr^− 1. The remaining portion of CH₄, which is released into the ocean, has been estimated to be 10²–10⁴ mol yr^− 1 per mud extrusion. The second approach estimates the amount of CH₄ discharging into the water column based on measurements of the near-bottom methane distribution and current velocities. This approach yields estimates between 10⁴–10⁵ mol yr⁻¹. The discrepancy of the amount of CH₄ emitted into the bottom water derived from the two approaches hints to methane seepage that cannot be accounted for by faunal growth, e.g. focused fluid emission through channels in sediments and fractures in carbonates. Extrapolated over the 48 mud extrusions discovered off Costa Rica, we estimate a CH₄ output of 20·10⁶ mol yr^− 1 from mud extrusions along this 350 km long section of the continental margin. These estimates of methane emissions at an erosional continental margin are considerably lower than those reported from mud extrusion at accretionary and passive margins. Almost half of the continental margins are described as non-accretionary. Assuming that the moderate emission of methane at the mud extrusions off Costa Rica are typical for this kind of setting, then global estimates of methane emissions from submarine mud extrusions, which are based on data of mud extrusions located at accretionary and passive continental margins, appear to be significantly too high.     

Methane, carbon monoxide, and carbon dioxide concentrations measured in the atmospheric surface layer over continental Russia in the TROICA experiments

The principal statistical regularities typical of the behaviors of the CH₄, CO, and CO₂ concentrations in the atmospheric surface layer over the continental Russian territory are revealed from the measurements performed in 1997–2004 along the Trans-Siberian Railroad from Moscow to Khabarovsk with a mobile laboratory. The data obtained under the conditions of the atmosphere free of anthropogenic pollutants are analyzed. For near-background conditions, the typical continental methane, carbon monoxide, and carbon dioxide concentrations and characteristic features of their large-scale spatial distributions and daily variations, including those caused by surface inversions, are determined. Variations in the concentrations of these trace gases over industrial regions are analyzed. Our results are compared to the data obtained at background stations of the world network of atmospheric monitoring and to the data of a numerical simulation.     

Comparison of marine gas hydrates in sediments of an active and passive continental margin

Two sites of the Deep Sea Drilling Project in contrasting geologic settings provide a basis for comparison of the geochemical conditions associated with marine gas hydrates in continental margin sediments. Site 533 is located at 3191 m water depth on a spit-like extension of the continental rise on a passive margin in the Atlantic Ocean. Site 568, at 2031 m water depth, is in upper slope sediment of an active accretionary margin in the Pacific Ocean. Both sites are characterized by high rates of sedimentation, and the organic carbon contents of these sediments generally exceed 0.5%. Anomalous seismic reflections that transgress sedimentary structures and parallel the seafloor, suggested the presence of gas hydrates at both sites, and, during coring, small samples of gas hydrate were recovered at subbottom depths of 238m (Site 533) and 404 m (Site 568). The principal gaseous components of the gas hydrates wer methane, ethane, and CO₂. Residual methane in sediments at both sites usually exceeded 10 mll^?1 of wet sediment. Carbon isotopic compositions of methane, CO₂, and ΣCO₂ followed parallel trends with depth, suggesting that methane formed mainly as a result of biological reduction of oxidized carbon. Salinity of pore waters decreased with depth, a likely result of gas hydrate formation. These geochemical characteristics define some of the conditions associated with the occurrence of gas hydrates formed by in situ processes in continental margin sediments.     

An experiment demonstrating that marine slumping is a mechanism to transfer methane from seafloor gas-hydrate deposits into the upper ocean and atmosphere

The scientific community is engaged in a lively debate over whether and how venting from the gas-hydrate reservoir and the Earth’s climate is connected. The various scenarios which have been proposed are based on the following assumptions: the inventory of methane gas-hydrate deposits is locally enormous, the stability of marine gas-hydrate deposits can easily be perturbed by temperature and pressure changes, enough methane can be released from these deposits to contribute adequate volumes of this isotopically distinct greenhouse gas to alter the composition of oceanic or atmospheric methane reservoirs, and the mechanisms exist for the transfer of methane from deeper geologic reservoirs to the ocean and/or atmosphere. However, some potential transfer mechanisms have been difficult to evaluate. Here, we consider the possibility of marine slumping as a mechanism to transfer methane carbon from gas hydrates within the seafloor into the ocean and atmosphere. Our analyses and field experiments indicate that large slumps could release volumetrically significant quantities of solid gas hydrates which would float upwards in the water column. Large pieces of gas hydrate would reach the upper layers of the ocean before decomposing, and some of the methane would be directly injected into the atmosphere.     

Modeling of rising methane bubbles during production leaks from the gas hydrate sites of India

Natural gas hydrates is considered as a strategic unconventional clean hydrocarbon resource in the energy sector. Understanding the behavior of the rising methane gas bubbles during production leaks from the deep marine gas hydrate reservoirs well head is essential for environmental impact studies and to design environmental monitoring systems. Numerical model for quantitatively characterizing the vertical dissolution pattern of the wellhead released methane gas bubbles is analyzed for three potential gas hydrate locations in India. Simulation results indicate that the methane bubbles with diameter of 10?mm can transport methane gas till 650, 800, and 750?m from the seabed in the Krishna–Godavari(KG), Mahanadi and Andaman basins respectively. Results brought out that potential well head damage during methane hydrate production at 1050?m water depth could release up to 28?m³ of methane gas, in which 50% of the molar mass shall get dissolved within 40?m of water column from the seafloor.     

Isotopic composition of gas hydrates in subsurface sediments from offshore Sakhalin Island, Sea of Okhotsk

Hydrate-bearing sediment cores were retrieved from recently discovered seepage sites located offshore Sakhalin Island in the Sea of Okhotsk. We obtained samples of natural gas hydrates and dissolved gas in pore water using a headspace gas method for determining their molecular and isotopic compositions. Molecular composition ratios C₁/_C2+ from all the seepage sites were in the range of 1,500–50,000, while δ¹³C and δD values of methane ranged from ?66.0 to ?63.2‰ VPDB and ?204.6 to ?196.7‰ VSMOW, respectively. These results indicate that the methane was produced by microbial reduction of CO₂. δ¹³C values of ethane and propane (i.e., ?40.8 to ?27.4‰ VPDB and ?41.3 to ?30.6‰ VPDB, respectively) showed that small amounts of thermogenic gas were mixed with microbial methane. We also analyzed the isotopic difference between hydrate-bound and dissolved gases, and discovered that the magnitude by which the δD hydrate gas was smaller than that of dissolved gas was in the range 4.3–16.6‰, while there were no differences in δ¹³C values. Based on isotopic fractionation of guest gas during the formation of gas hydrate, we conclude that the current gas in the pore water is the source of the gas hydrate at the VNIIOkeangeologia and Giselle Flare sites, but not the source of the gas hydrate at the Hieroglyph and KOPRI sites.     

Microbial processes of the carbon and sulfur cycles in the Kara Sea

The results of microbiological, biogeochemical, and isotope geochemical studies in the Kara Sea are described. The samples for these studies were obtained during the 54th voyage of the research vessel Akademik Mstislav Keldysh in September 2007. The studied area covered the northern, central, and southwestern parts of the Kara Sea and the Gulf of Ob. The quantitative characteristics of the total bacterial population and the activity of the microbial processes in the water column and bottom sediments were obtained. The total population of the bacterioplankton (BP) varied from 250000 cells/ml in the northern water area to 3000000 cells/ml in the Gulf of Ob. The BP population depended on the content of the water suspension. The net BP production was minimal in the central water area, amounting to 0.15–0.2 μg C/(l day), and maximal (0.5–0.75 μg C/(l day)) in the Gulf of Ob. The organic material at the majority of the stations in the Ob transect predominantly contained light carbon isotopes (−28.0 to −30.18‰) of terrigenous origin. The methane content in the surface water layer varied from 0.18 to 2.0 μl CH₄/l, and the methane oxidation rate changed in the range of 0.1–100 nl CH₄/(l day). The methane concentration in the upper sediment layer varied from 30 to 300 μl CH₄/dm³; the rate of the methanogenesis was 44 to 500 nl CH₄/(dm³ day) and that of the methane oxidation, 30 to 2000 nl CH₄/(dm³ day). The rate of the sulfate reduction varied from 4 to 184 μg S/(dm³ day).