南海北部莺歌海岭头岬近岸烃类渗漏喷口分布及气体地球化学

Natural hydrocarbon seeps in a marine environment are one of the important contributors to greenhouse gases in the atmosphere,including methane,which is significant to the global carbon cycling and climate change.Four hydrocarbon seep areas,the Lingtou Promontory,the Yinggehai Rivulet mouth,the Yazhou Bay and the Nanshan Promontory,occurring in the Yinggehai Basin delineate a near-shore gas bubble zone.The gas composition and geochemistry of venting bubbles and the spatial distribution of hydrocarbon seeps are surveyed on the near-shore Lingtou Promontory.The gas composition of the venting bubbles is mainly composed of CO_2,CH_4,N_2 and O_2,with minor amounts of non-methane hydrocarbons.The difference in the bubbles' composition is a possible consequence of gas exchange during bubble ascent.The seepage gases from the seafloor are characterized by a high CO_2 content(67.35%) and relatively positive δ~(13)C_(V_PDB) values(-0.49×10~(-3)-0.86×10~(-3)),indicating that the CO_2 is of inorganic origin.The relatively low CH_4 content(23%) and their negative δ~(13)C_(V-PDB) values(-34.43×10~(-3)--37.53×10~(-3)) and high ratios of C_1 content to C_(1-5) one(0.98-0.99)as well point to thermogenic gases.The hydrocarbon seeps on the 3.5 Hz sub-bottom profile display a linear arrangement and are sub-parallel to the No.1 fault,suggesting that the hydrocarbon seeps may be associated with fracture activity or weak zones and that the seepage gases migrate laterally from the central depression of the Yinggehai Basin.     

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.     

Ongoing methane discharge at well site 22/4b (North Sea) and discovery of a spiral vortex bubble plume motion

First direct evidence for ongoing gas seepage activity on the abandoned well site 22/4b (Northern North Sea, 57°55′ N, 01°38′ E) and discovery of neighboring seepage activity is provided from observations since 2005. A manned submersible dive in 2006 discovered several extraordinary intense seepage sites within a 60 m wide and 20 m deep crater cut into the flat 96 m deep seafloor. Capture and (isotope) chemical analyses of the gas bubbles near the seafloor revealed in situ concentrations of methane between 88 and 90%Vol. with δ¹³C–CH₄ values around −74‰ VPDB, indicating a biogenic origin. Bulk methane concentrations throughout the water column were assessed by 120 Niskin water samples showing up to 400.000 nM CH₄ in the crater at depth. In contrast, concentrations above the thermocline were orders of magnitude lower, with a median value of 20 nM. A dye tracer injection into the gas seeps revealed upwelling bubble and water motion with gas plume rise velocities up to ∼1 ms⁻¹ (determined near the seabed). However, the dissolved dye did not pass the thermocline, but returned down to the seabed. Measurements of direct bubble-mediated atmospheric flux revealed low values of 0.7 ± 0.3 kty⁻¹, much less than current state-of-the-art bubble dissolution models would predict for such a strong and upwelling in situ gas bubble flux at shallow water depths (i.e. ∼100 m).Acoustic multibeam water column imaging data indicate a pronounced 200 m lateral intrusion at the thermocline together with high methane concentration at this layer. A partly downward-orientated bubble plume motion is also visible in the acoustic data with potential short-circuiting in accordance to the dye experiment. This observation could partly explain the observed trapping of most of the released gas below the well-established thermocline in the North Sea. Moreover, 3D analyses of the multibeam water column data reveal that the upwelling plume transforms into a spiral expanding vortex while rising through the water column. Such a spiral vortex motion has never been reported before for marine gas seepage and might represent an important process with strong implication on plume dynamics, dissolution behavior, gas escape to the atmosphere, and is considered very important for respective modeling approaches.     

Terminal velocities of pure and hydrate coated CO2 droplets and CH4 bubbles rising in a simulated oceanic environment

Understanding the upward motion of CO₂ droplets or CH₄ bubbles in oceanic waters is prerequisite to predict the vertical distribution of the two most important greenhouse gases in the water column after these have been released from the seabed. One of the key parameters governing the fate of droplets or bubbles dissolving into the surrounding seawater as they rise, is the terminal velocity, u_T. The latter is strongly influenced by the ability of both compounds to form skins of gas hydrate, if pressure and temperature satisfy thermodynamic framework conditions. Experimental efforts aiming to elucidate the rise properties of CO₂ droplets and CH₄ bubbles and specifically the influence of hydrate skins open the possibility to obtain a parameterization of u_T applicable to both hydrate-coated and pure fluid particles of CH₄ and CO₂. With the present study, we report on experimentally determined terminal velocities of single CH₄ bubbles released to pressurized and temperature-regulated seawater. Hydrate skins were identified by high bubble sphericities and changed motion characteristics. Based on these experiments as well as published data on the rise of hydrate-coated and pure liquid CO₂ droplets and physical principles previously successfully used for clean bubbles near atmospheric pressures, a new parameterization of u_T is proposed. Model predictions show a good agreement with the data base established from the laboratory-based measurements.     

苏北滨海湿地互花米草潮滩CO2,CH4和N2O通量的日变化规律

The invasions of the alien species such as Spartina alterniflora along the northern Jiangsu coastlines have posed a threat to biodiversity and the ecosystem function.Yet,limited attention has been given to their potential influence on greenhouse gas(GHG) emissions,including the diurnal variations of GHG fluxes that are fundamental in estimating the carbon and nitrogen budget.In this study,we examined the diurnal variation in fluxes of carbon dioxide(CO_2),methane(CH_4),and nitrous oxide(N2O) from a S.alterniflora intertidal flat in June,October,and December of 2013 and April of 2014 representing the summer,autumn,winter,and spring seasons,respectively.We found that the average CH_4 fluxes on the diurnal scale were positive during the growing season while negative otherwise.The tidal flat of S.alterniflora acted as a source of CH_4 in summer(June) and a combination of source and sink in other seasons.We observed higher diurnal variations in the CO_2 and N_2O fluxes during the growing season(1 536.5 mg CO_2 m~(–2) h~(–1) and 25.6 μg N_2O m~(–2) h~(–1)) compared with those measured in the non-growing season(379.1 mg CO_2 m~(–2) h~(–1) and 16.5 μg N_2O m~(–2) h~(–1)).The mean fluxes of CH_4 were higher at night than that in the daytime during all the seasons but October.The diurnal variation in the fluxes of CO_2 in June and N_2O in December fluctuated more than that in October and April.However,two peak curves in October and April were observed for the diurnal changes in CO_2 and N_2O fluxes(prominent peaks were found in the morning of October and in the afternoon of April,respectively).The highest diurnal variation in the N_2O fluxes took place at 15:00(86.4 μg N_2O m~(–2) h~(–1)) in June with an unimodal distribution.Water logging in October increased the emission of CO_2(especially at nighttime),yet decreased N_2O and CH_4 emissions to a different degree on the daily scale because of the restrained diffusion rates of the gases.The seasonal and diurnal variations of CH_4 and CO_2 fluxes did not correlate to the air and soil temperatures,whereas the seasonal and diurnal variation of the fluxes of N_2O in June exhibited a significant correlation with air temperature.When N_2O and CH_4 fluxes were converted to CO_2-e equivalents,the emissions of N_2O had a remarkable potential to impact the global warming.The mean daily flux(MF) and total daily flux(TDF) were higher in the growing season,nevertheless,the MF and TDF of CO_2 were higher in October and those of CH_4 and N_2O were higher in June.In spite of the difference in the optimal sampling times throughout the observation period,our results obtained have implications for sampling and scaling strategies in estimating the GHG fluxes in coastal saline wetlands.     

Gas flux and carbonate occurrence at a shallow seep of thermogenic natural gas

The Coal Oil Point seep field located offshore Santa Barbara, CA, consists of dozens of named seeps, including a peripheral ～200 m² area known as Brian Seep, located in 10 m water depth. A single comprehensive survey of gas flux at Brian Seep yielded a methane release rate of ～450 moles of CH₄ per day, originating from 68 persistent gas vents and 23 intermittent vents, with gas flux among persistent vents displaying a log normal frequency distribution. A subsequent series of 33 repeat surveys conducted over a period of 6 months tracked eight persistent vents, and revealed substantial temporal variability in gas venting, with flux from each individual vent varying by more than a factor of 4. During wintertime surveys sediment was largely absent from the site, and carbonate concretions were exposed at the seafloor. The presence of the carbonates was unexpected, as the thermogenic seep gas contains 6.7% CO₂, which should act to dissolve carbonates. The average δ¹³C of the carbonates was ?29.2?±?2.8‰ VPDB, compared to a range of ?1.0 to +7.8‰ for CO₂ in the seep gas, indicating that CO₂ from the seep gas is quantitatively not as important as ¹³C-depleted bicarbonate derived from methane oxidation. Methane, with a δ¹³C of approximately ?43‰, is oxidized and the resulting inorganic carbon precipitates as high-magnesium calcite and other carbonate minerals. This finding is supported by ¹³C-depleted biomarkers typically associated with anaerobic methanotrophic archaea and their bacterial syntrophic partners in the carbonates (lipid biomarker δ¹³C ranged from ?84 to ?25‰). The inconsistency in δ¹³C between the carbonates and the seeping CO₂ was resolved by discovering pockets of gas trapped near the base of the sediment column with δ¹³C-CO₂ values ranging from ?26.9 to ?11.6‰. A mechanism of carbonate formation is proposed in which carbonates form near the sediment–bedrock interface during times of sufficient sediment coverage, in which anaerobic oxidation of methane is favored. Precipitation occurs at a sufficient distance from active venting for the molecular and isotopic composition of seep gas to be masked by the generation of carbonate alkalinity from anaerobic methane oxidation.

A geochemical traverse along the “Sperchios Basin – Evoikos Gulf” graben (Central Greece): Origin and evolution of the emitted fluids

The studied area is a 130 km long fast spreading graben in Central Greece. Its complex geodynamical setting includes both the presence of a subduction slab at depth responsible for the recent (Quaternary) volcanic activity in the area and the western termination of a tectonic lineament of regional importance (the North-Anatolian fault). A high geothermal gradient is made evident by the presence of many thermal springs with temperatures from 19 to 82 °C, that discharge along the normal faults bordering the graben.In the period 2004–2012, 58 gas and 69 water samples were collected and their chemical and isotopic analysis revealed a wide range of compositions.Two main groups of thermal waters can be distinguished on the basis of their chemical composition. The first, represented by dilute waters (E.C. <0.6 mS/cm) of the westernmost sites, is characterised by the presence of CH₄-rich and mixed N₂–CH₄ gases. The second displays higher salinities (E.C. from 12 to 56 mS/cm) due to mixing with a modified marine component. Reservoir temperatures of 150–160 °C were estimated with cationic geothermometers at the easternmost sites.Along the graben, from west to east, the gas composition changes from CH₄- to CO₂-dominated through mixed N₂–CH₄ and N₂–CO₂ compositions, while at the same time the He isotopic composition goes from typical crustal values (<0.1 R/R_A) up to 0.87 R/R_A, showing in the easternmost sites a small (3–11%) but significant mantle input. The δ¹³C values of the CO₂-rich samples suggest a mixed origin (mantle and marine carbonates).     

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.     

Acoustic monitoring of gas emissions from the seafloor. Part I: quantifying the volumetric flow of bubbles

Three decades of continuous ocean exploration have led us to identify subsurface fluid related processes as a key phenomenon in marine earth science research. The number of seep areas located on the seafloor has been constantly increasing with the use of multi-scale imagery techniques. Due to recent advances in transducer technology and computer processing, multibeam echosounders are now commonly used to detect submarine gas seeps escaping from the seafloor into the water column. A growing number of en-route surveys shows that sites of gas emissions escaping from the seafloor are much more numerous than previously thought. Estimating the temporal variability of the gas flow rate and volumes escaping from the seafloor has thus become a challenge of relevant interest which could be addressed by sea-floor continuous acoustic monitoring. Here, we investigate the feasibility of estimating the volumetric flow rates of gas emissions from horizontal backscattered acoustic signals. Different models based on the acoustic backscattering theory of bubbles are presented. The forward volume backscattering strength and the inversion volumetric flow rate solutions were validated with acoustic measurements from artificial gas flow rates generated in controlled sea-water tank experiments. A sensitivity analysis was carried out to investigate the behavior of the 120-kHz forward solution with respect to model input parameters (horizontal distance between transducer and bubble stream, bubble size distribution and ascent rate). The most sensitive parameter was found to be the distance of the bubble stream which can affect the volume backscattering strength by 20 dB within the horizontal range of 0–200 m. Results were used to derive the detection probability of a bubble stream for a given volume backscattering strength threshold according to different bubble flow rates and horizontal distance.     

Time series video analysis of bubble release processes at natural hydrocarbon seeps in the Northern Gulf of Mexico

This research quantifies the rate and volume of oil and gas released from two natural seep sites in the Gulf of Mexico: lease blocks GC600 (1200 m depth) and MC118 (850 m depth). Our objectives were to determine variability in release rates and bubble size at five individual vents and to investigate the effects of tidal fluctuations on bubble release. Observations with autonomous video cameras captured the formation of individual bubbles as they were released through partially exposed deposits of gas hydrate. Image processing techniques determined bubble type (oily, gaseous, and mixed: oily and gaseous), size distribution, release rate, and temporal variations (observation intervals ranged from 3 h to 26 d). A semi-automatic bubble counting algorithm was developed to analyze bubble count and release rates from video data. This method is suitable for discrete vents with small bubble streams commonly seen at seeps and is adaptable to multiple in situ set-ups. Two vents at GC600 (Birthday Candles 1 and Birthday Candles 2) were analyzed. They released oily bubbles with an average diameter of 5.0 mm at a rate of 4.7 bubbles s⁻¹, and 1.3 bubbles s⁻¹, respectively. Approximately 1 km away, within the GC600 seep site, two more vents (Mega Plume 1 and Mega Plume 2) were analyzed. These vents released a mixture of oily and gaseous bubbles with an average diameter of 3.9 mm at a rate of 49 bubbles s⁻¹, and 81 bubbles s⁻¹, respectively. The fifth vent at MC118 (Rudyville) released gaseous bubbles with an average diameter of 3.0 mm at a rate of 127 bubbles s⁻¹. Pressure records at Mega Plume and Rudyville showed a diurnal tidal cycle (24.5 h). Rudyville was the only vent that demonstrated any positive correlation (ρ = 0.60) to the 24.5 h diurnal tidal cycle. However, these observations were not conclusive regarding tidal effects on bubble release.     

Methane in the Sevastopol coastal area, Black Sea

Concentrations of dissolved methane in seawater and bottom sediments, as well as of methane emanating from gas seeps were measured at 18 stations including several small bays in the Sevastopol coastal area (Black Sea) during 2007–2008. Methane concentrations in surface waters ranged from 10 to 2,970 nmol l^?1, and correlated well with values recorded for sediments. Methane concentrations in the water column were influenced by water depth, as well as by air and water temperatures. In the spring and summer of 2008, in situ CH₄ saturation relative to air was in the range of 970–71,900%. Maximum saturation was in summer. CH₄ fluxes to the atmosphere from the Sevastopol coastal area were estimated to vary from 190 to 1,550 μmol m^?2 day^?1. Gas bubbles escaping from the seepages contained about 57 vol% methane. Radiocarbon dating of the methane revealed an age not exceeding 150 years, implying a biogenic origin.     

The importance of shale composition and pore structure upon gas storage potential of shale gas reservoirs

The effect of shale composition and fabric upon pore structure and CH₄ sorption is investigated for potential shale gas reservoirs in the Western Canadian Sedimentary Basin (WCSB). Devonian–Mississippian (D–M) and Jurassic shales have complex, heterogeneous pore volume distributions as identified by low pressure CO₂ and N₂ sorption, and high pressure Hg porosimetry. Thermally mature D–M shales (1.6–2.5% VRo) have Dubinin–Radushkevich (D–R) CO₂ micropore volumes ranging between 0.3 and 1.2 cc/100 g and N₂ BET surface areas of 5–31 m²/g. Jurassic shales, which are invariably of lower thermal maturity ranging from 0.9 to 1.3% VRo, than D–M shales have smaller D–R CO₂ micropore volumes and N₂ BET surface areas, typically in the range of 0.23–0.63 cc/100 g (CO₂) and 1–9 m²/g (N₂).     

Paragenesis of fluids under evaporates in the Volga-Ural Basin

To unravel the mystery of the relationship between evaporates, Ca–Cl brines and accumulations of oil and N₂ in the basins of ancient cratons, their N₂, CH₄ and He concentration ratios, as well as the isotopic composition (δ¹⁵N, δ¹³C and ³He/⁴He) were compared within the Volga-Ural basin. The study allowed subsalt fluids from Volga-Ural Basin to divide into two genetic groups. The first one is found within the basin's platform area. It includes Ca–Cl brines, high-viscosity heavy oil, bitumen and N₂, which has concentrations higher than that of CH₄ and positive values of δ¹⁵N. The second one is tied to the edge of the platform, the Ural Foredeep and Peri-Caspian Depression. In this group, only the oil and gas reservoirs, which have more CH₄ than N₂, and possibly negative values of δ¹⁵N, were discovered. Interaction of gas components in compared fluids indicates great role of degassing in the formation of their composition. It is suggested that the fluids of the first group (N₂ > CH₄) is what remains, and the second group (N₂ < CH₄) is what is disappears from the rocks during their metamorphism and degassing.     

Air-sea carbon-dioxide flux estimated by eddy covariance method from a buoy observation

Precise measurements of the CO2 gas transfer across the air-sea interface provide a better understanding of the global carbon cycle.The air-sea CO2 fluxes are obtained by the eddy covariance method and the bulk method from a buoy observation in the northern Huanghai sea.The effects of buoy motion on flux calculated by the eddy covariance method are demonstrated.The research shows that a motion correction can improve the correlation coefficient between the CO2 fluxes estimated from two different levels.Without the CO2-H2 O cross-correlation correction which is termed as PKT correction,the air-sea CO2 fluxes estimated by eddy covariance method using the motion corrected data are nearly an order of magnitude larger than those estimated by the bulk method.After the CO2-H2 O cross-correlation correction,some eddy covariance CO2 fluxes indeed become closer to the bulk CO2 flux,whereas some are overcorrected which are in response to small water vapor flux.     

Determination of gas bubble fractionation rates in the deep ocean by laser Raman spectroscopy

A new deep-sea laser Raman spectrometer (DORISS—Deep Ocean Raman In Situ Spectrometer) is used to observe the preferential dissolution of CO₂ into seawater from a 50%–50% CO₂–N₂ gas mixture in a set of experiments that test a proposed method of CO₂ sequestration in the deep ocean. In a first set of experiments performed at 300 m depth, an open-bottomed 1000 cm³ cube was used to contain the gas mixture; and in a second set of experiments a 2.5 cm³ funnel was used to hold a bubble of the gas mixture in front of the sampling optic. By observing the changing ratios of the CO₂ and N₂ Raman bands we were able to determine the gas flux and the mass transfer coefficient at 300 m depth and compare them to theoretical calculations for air–sea gas exchange. Although each experiment had a different configuration, comparable results were obtained. As expected, the ratio of CO₂ to N₂ drops off at an exponential rate as CO₂ is preferentially dissolved in seawater. In fitting the data with theoretical gas flux calculations, the boundary layer thickness was determined to be  42 μm for the gas cube, and  165 μm for the gas funnel reflecting different boundary layer turbulence. The mass transfer coefficients for CO₂ are k_L = 2.82 × 10^− 5 m/s for the gas cube experiment, and k_L = 7.98 × 10^− 6 m/s for the gas funnel experiment.     

Stable carbon isotopic ratios of CH4-CO2-bearing fluid inclusions in fracture-fill mineralization from the Lower Saxony Basin (Germany) - A tool for tracing gas sources and maturity

The stable carbon isotopic ratios (δ¹³C) of methane (CH₄) and carbon dioxide (CO₂) of gas-rich fluid inclusions hosted in fracture-fill mineralization from the southern part of the Lower Saxony Basin, Germany have been measured online using a crushing device interfaced to an isotopic ratio mass spectrometer (IRMS). The data reveal that CH₄ trapped in inclusions seems to be derived from different source rocks with different organic matter types. The δ¹³C values of CH₄ in inclusions in quartz hosted by Carboniferous rocks range between −25 and −19‰, suggesting high-maturity coals as the source of methane. Methane in fluid inclusions in minerals hosted by Mesozoic strata has more negative carbon isotope ratios (−45 to −31‰) and appears to represent primary cracking products from type II kerogens, i.e., marine shales. There is a positive correlation between increasing homogenization temperatures of aqueous fluid inclusions and less negative δ¹³C(CH₄) values of in co-genetic gas inclusions probably indicating different mtaturity of the potential source rocks at the time the fluids were released. The CO₂ isotopic composition of CH₄-CO₂-bearing inclusions shows slight negative or even positive δ¹³C values indicating an inorganic source (e.g., water-rock interaction and dissolution of detrital, marine calcite) for CO₂ in inclusions. We conclude that the δ¹³C isotopic ratios of CH₄-CO₂-bearing fluid inclusions can be used to trace migration pathways, sources of gases, and alteration processes. Furthermore, the δ¹³C values of methane can be used to estimate the maturity of the rocks from which it was sourced. Results presented here are further supported by organic geochemical analysis of surface bitumens which coexist with the gas inclusion-rich fracture-fill mineralization and confirm the isotopic interpretations with respect to fluid source, type and maturity.     

High-resolution mapping of shallow gas accumulations and gas seeps in San Simón Bay (Ría de Vigo, NW Spain). Some quantitative data

San Simón Bay in the innermost part of the Ría de Vigo is characterized by an abundance of very shallow gas accumulations and methane seeps. During the expeditions of April–June–September 2004 within the Spanish-funded Gs2G project, detailed very high-resolution seismic and field investigations were carried out to study the shallow gas and the seeps. Direct gas fluxes also were measured from bubble streams. For the first time, the surface area and gas front depth of a shallow gas field has been mapped and quantified in the inner bay of Ría de Vigo. This field overlaps spatially with the distribution of Holocene mud within the bay. Seismic data show 3.6 km² affected by acoustic turbidity but this surface can be extended up to 9.5 km² of San Simón’s muddy subtidal area. Mounded turbidity superimposed on the main gas field has been mapped and characterized as anthropogenically (mussel rafts) mediated gas accumulations. Different acoustic anomalies have been identified and interpreted as being due to gas escapes from the present seabed sediment. The very high resolution of the seismic data makes it possible to identify a new type of seep, here named ‘acoustic smoke.’ A direct relationship can be observed between the gas front of accumulations and escape features, both acoustic seeps and pockmarks. The methane flux has been estimated from the subtidal environment in San Simón based on detected acoustic targets and direct measurements of current bubble flow. The total estimated methane flux from the seabed into the water column ranges from 10.1 to 48.8 t/year, and into the atmosphere from 7.0 to 34.2 t/year. The intertidal San Simón environment is also actively venting methane, as indicated by the presence of bubbling during high tide and white patches of Beggiatoa sp.     

In-reservoir mixing of mantle-derived CO2 and metasedimentary CH4–N2 fluids – Noble gas and stable isotope study of two multistacked fields (Pannonian Basin System,W-Hungary)

Several multistacked gas fields, located in very different parts of Hungary, display a large variation in their gas composition. The shallow position of the mantle beneath the basement of the PBS is responsible for the high heat flux. It facilitates that the CO₂ – intensely released from the ascending upper-mantle derived melts – could reach the basin system. In this work the results of a geochemical study of the main components and noble gases of the multistacked Répcelak (CO₂–HC–N₂) and Mihályi (CO₂) fields are presented and discussed. The vertical variations of gas composition in the Répcelak and Mihályi fields fit well with in-reservoir mixing of two end-members, a mantle-related magmatic CO₂ fluid and a N₂-rich HC-gas fluid of crustal origin. However, it is very likely that other processes modified to some extent the gas composition of the two fields. Carbon isotopic composition of the CO₂ of the samples studied agrees with both the carbonate decomposition and mantle degassing origins. It is very likely that the marked difference in helium isotopic composition between the neighbouring Répcelak and Mihályi fields also reflects this heterogeneity.     

Carbon cycling within the upper methanogenic zone of continental rise sediments; An example from the methane-rich sediments overlying the Blake Ridge gas hydrate deposits

Data from piston cores collected from Carolina Rise and Blake Ridge, and from many DSDP/ODP sites indicate that extreme ¹³C-depletion of methane and ΣCO₂ occurs within the uppermost methanogenic zone of continental rise sediments. We infer that ¹³C-depleted methane is generated near the top of the methanogenic zone when carbon of ¹³C-depleted ΣCO₂, produced by microbially-mediated anaerobic methane oxidation, is recycled back to methane through CO₂ reduction. Interstitial water and gas samples were collected in 27 piston cores, 16 of which penetrated through the sulfate reduction zone into methane-bearing sediments of the Carolina Rise and Blake Ridge. Isotopic measurements (δ¹³C_CH4, δ¹³C_CO2, δD_CH4, and δD_H2O) indicate that this methane is microbial in origin, produced by microbially-mediated CO₂ reduction. Methane samples form two distinct isotopic pools. (1) Methane from a seafloor seep site shows a mean δ¹³C_CH4 value of − 69 ± 2%., mirroring values found at ≥ 160 mbsf from a nearby DSDP site. (2) Twenty, areally-separated sites (sample depth, 10 to 25 mbsf) have δ¹³C_CH4 values ranging from −85 to −103%., and δ¹³C_CO2 as negative as −48%.. The very low δ¹³C values from the methane and CO₂ pools highlight the importance of carbon cycling within continental rise sediments at and near the sulfate-methane boundary.     

Hydroacoustic experiments to establish a method for the determination of methane bubble fluxes at cold seeps

Hydroacoustic methods are particularly suitable for investigations of the occurrence, cyclicity and amount of bubbles released at cold seeps without disturbing them. Experiments with a horizontally looking single beam transducer (40 and 300 kHz) directed towards artificially produced bubbles show that the backscattering strength of the bubbles increases with the gas flux rate independently of the bubble radii distribution. It is demonstrated that an acoustic system can be calibrated in such a way that gas flux rates of bubble-size spectra, as observed at natural seeps, can be directly related to the echo level of a known, acoustically insonified volume. No system-specific parameters have to be known except the beam width.