Raman spectroscopic measurements of synthetic gas hydrates in the ocean

A Raman spectrometer extensively modified for deep ocean use was used to measure synthetic hydrates formed in an ocean environment. This was the first time hydrates formed in the ocean have been measured in situ using Raman spectroscopy. Gas hydrates were formed in situ in the Monterey Bay by pressurizing a Pyrex cell with various gas mixtures. Raman spectra were obtained for sI methane hydrate and sII methane + ethane hydrate. Gas occlusion resulting from rapid gas growth of methane hydrate was measured immediately after formation. The Raman shift for methane free gas was coincident with that of methane in the small 5¹² hydrate cage. The methane Raman peak widths were used to discriminate between methane in the free gas and hydrate phase. Methane + ethane sII hydrate was formed for 43 days on the seafloor. In this case, gas occlusion was not measured when the gas hydrates were allowed to form over an extended time period. Equivalent Raman spectra were obtained for the in situ and laboratory-formed sII methane + ethane hydrates, under similar p, T, and x conditions. With the Raman spectrometer operating in the ocean, seawater contributes to the Raman spectra obtained. Both the Raman bands for the sulfate ion and water were used to qualitatively determine the distribution of water phases measured (hydrate, seawater) in the Raman spectra.     

Gas-hydrate promotion by smectite–bioproduct interactions

Gas hydrates accumulate on the Gulf of Mexico seafloor around hydrocarbon seeps in waters sufficiently deep to provide adequate pressure/temperature combinations. High microbial activities occur around the hydrate accumulations. To understand apparent catalytic effects of bioproducts on hydrate formation, the mechanism of sII hydrate nucleation in unconsolidated porous media was investigated in our laboratory. Because smectite clays interacting with biopolymers had been shown to promote laboratory hydrates by decreasing induction times, increasing formation rates and altering morphology, these materials commonly found in near-surface sediments were selected for study as possible nucleating agents. Dynamic light scattering (DLS) with a helium–neon laser was used to measure particle diameters down to about 2 nm. Scanning electron microscopy (SEM) was utilized to verify particle sizes and to give additional information on biopolymer–clay associations. This paper presents evidence that nanometer-sized particles of mineral–bioproduct associations of about 80 nm–450 nm diameter may act as nucleation sites for hydrate crystal initiations in sediments and then remain dispersed throughout the accumulated hydrate mass. Emulsan biopolymer was shown by SEM to apparently unfold and associate with the smectite (nontronite) in a backbone arrangement and to give multiple hydrate nucleation sites along a linear network. SEM and DLS measurements were in agreement on particle sizes and shapes. X-ray diffraction suggested that biopolymer intercalates the smectite interlayer, probably driven by clay associations with biopolymer hydrophilic groups. It is hypothesized that hydrocarbon gases attach to biopolymer hydrophobic fatty-acid branches protruding from clay interlayers and subsequently facilitate hydrate structure formation by interacting with nearby water associated with the hydrophilic segments of the biopolymer.     

High-resolution well-log derived dielectric properties of gas-hydrate-bearing sediments, Mount Elbert Gas Hydrate Stratigraphic Test Well, Alaska North Slope

A dielectric logging tool, electromagnetic propagation tool (EPT), was deployed in 2007 in the BPXA-DOE-USGS Mount Elbert Gas Hydrate Stratigraphic Test Well (Mount Elbert Well), North Slope, Alaska. The measured dielectric properties in the Mount Elbert well, combined with density log measurements, result in a vertical high-resolution (cm-scale) estimate of gas hydrate saturation. Two hydrate-bearing sand reservoirs about 20 m thick were identified using the EPT log and exhibited gas-hydrate saturation estimates ranging from 45% to 85%. In hydrate-bearing zones where variation of hole size and oil-based mud invasion are minimal, EPT-based gas hydrate saturation estimates on average agree well with lower vertical resolution estimates from the nuclear magnetic resonance logs; however, saturation and porosity estimates based on EPT logs are not reliable in intervals with substantial variations in borehole diameter and oil-based invasion.EPT log interpretation reveals many thin-bedded layers at various depths, both above and below the thick continuous hydrate occurrences, which range from 30-cm to about 1-m thick. Such thin layers are not indicated in other well logs, or from the visual observation of core, with the exception of the image log recorded by the oil-base microimager. We also observe that EPT dielectric measurements can be used to accurately detect fine-scale changes in lithology and pore fluid properties of hydrate-bearing sediments where variation of hole size is minimal. EPT measurements may thus provide high-resolution in-situ hydrate saturation estimates for comparison and calibration with laboratory analysis.     

天然气水合物的重要特征与评价及其在中国海域的勘探前景

从勘探技术和资源评价的角度综述了甲烷水合物生成和聚集的重要特征, 如地震反射剖面、测井曲线资料、地球化学特点等以及对未知区的地质勘探和选区评价 .甲烷水合物在地震剖面上主要表现为BSR(似海底反射)、振幅变形(空白反射)、速度倒置、速度-振幅结构(VAMPS)等,大规模的甲烷水合物聚集可以通过高电阻率(＞100欧姆.米)声波速度、低体积密度等号数进行直接判读.此项研究实例表明,沉积物中典型甲烷水合物具有低渗透性和高毛细管孔隙压力特点,地层孔隙水矿化度也呈异常值,并具有各自独特的地质特征.现场计算巨型甲烷水合物储层中甲烷资源量的方法可分为:测井资料计算法公式为:SW＝(abRw/φm.Rt)1/n;地震资料计算法公式为:ρp＝(1-φ)ρm+(1-s)φρw+sφρh、VH＝λ.φ.S.对全球甲烷水合物总资源量预测的统计达20×1015m3以上.甲烷水合物形成需满足高压、低温条件,要求海水深度＞300 m.因此,甲烷水合物的分布严格地局限于两极地区和陆坡以下的深水地区,并具有3种聚集类型:1.永久性冻土带;2.浅水环境;3.深水环境.深海钻探计划(DSDP)和大洋钻探计划(ODP)已在下述10个地区发现大规模的甲烷水合物聚集,他们是:秘鲁、哥斯达黎加、危地马拉、墨西哥、美国东南大西洋海域、美国西部太平洋海域、日本海域的两个地区、阿拉斯加和墨西哥湾地区.在较浅水沉积物岩心样中发现甲烷水合物的地区,包括黑海、里海、加拿大北部、美国加里福尼亚岸外、墨西哥湾北部、鄂霍茨克海的两个地区.在垂向上,甲烷水合物主要分布于海底以下2 000 m以浅的沉积层中.最新统计表明又主要分布于二个深度区间:200～450 m和700～920 m,前者是由ODP995～997站位发现的;后者在加拿大麦肯齐河三角洲马立克2L-38号井中897～922 m处发现.中国海域已发现多处甲烷水合物可能赋存地区,包括东沙群岛南部、西沙海槽北部、西沙群岛南部以及东海海域地区.姚伯初报道了南海地区9处地震剖面速度异常值的发现,海水深度为420～3 920 m,海洋地质研究所则在东海海域解释了典型BSR反射的剖面,具有速度异常、弱振幅、空白反射、与下伏反射波组具不整合接触关系(VAMPS)等,大致圈定了它们的分布范围,表明在中国海域寻找甲烷水合物具有光明的前景.     

Formation pressure testing at the Mount Elbert Gas Hydrate Stratigraphic Test Well, Alaska North Slope: Operational summary, history matching, and interpretations

In February 2007, the U.S. Department of Energy, BP Exploration (Alaska), and the U.S. Geological Survey, collected open-hole pressure-response data, as well as gas and water sample collection, in a gas hydrate reservoir (the BPXA-DOE-USGS Mount Elbert Gas Hydrate Stratigraphic Test Well) using Schlumberger's Modular Dynamics Formation Tester (MDT) wireline tool. Four such MDT tests, ranging from six to twelve hours duration, and including a series of flow, sampling, and shut-in periods of various durations, were conducted. Locations for the testing were selected based on NMR and other log data to assure sufficient isolation from reservoir boundaries and zones of excess free water. Test stages in which pressure was reduced sufficiently to mobilize free water in the formation (yet not cause gas hydrate dissociation) produced readily interpretable pressure build-up profiles. Build-ups following larger drawdowns consistently showed gas-hydrate dissociation and gas release (as confirmed by optical fluid analyzer data), as well as progressive dampening of reservoir pressure build-up during sequential tests at a given MDT test station.History matches of one multi-stage, 12-h test (the C2 test) were accomplished using five different reservoir simulators: CMG-STARS, HydrateResSim, MH21-HYDRES, STOMP-HYD, and TOUGH + HYDRATE. Simulations utilized detailed information collected across the reservoir either obtained or determined from geophysical well logs, including thickness (11.3 m, 37 ft.), porosity (35%), hydrate saturation (65%), both mobile and immobile water saturations, intrinsic permeability (1000 mD), pore water salinity (5 ppt), and formation temperature (3.3-3.9 °C). This paper will present the approach and preliminary results of the history-matching efforts, including estimates of initial formation permeability and analyses of the various unique features exhibited by the MDT results.     

Phase stability and kinetics of methane hydrate formation in presence of calcium and magnesium carbonate

The huge amount of methane hydrate deposits identified in deep marine sediments is considered as the new resource for future energy. Since carbonates are one of the major components of marine sediments, in the present study, an investigation has been made to study methane hydrate stability and kinetics in the presence of CaCO₃ and MgCO₃. Effect of the presence of carbonates on the solubility of methane in the system has also been examined as it directly affects the hydrate formation process. It has been observed that in presence of CaCO₃ and MgCO₃, the hydrate formation is inhibited. Comparative studies have also been done in the presence of artificial seawater to consider the effect of presence of different salts. Mole consumption of methane gas during hydrate formation in different carbonate samples was measured using real gas equation and found to be minimum in CaCO₃ in seawater sample due to the combined effect of the presence of CaCO₃ and different salts of seawater. An increase in nucleation and induction time was also observed demonstrating the inhibition of hydrate formation in the presence of these components. Further, the decrease in hydrate formation rate also confirmed the inhibition effect of CaCO₃ and MgCO₃ on hydrate formation.     

The mechanism and verification analysis of permafrost-associated gas hydrate formation in the Qilian Mountain,Northwest China

Muri Basin in the Qilian Mountain is the only permafrost area in China where gas hydrate samples have been obtained through scientific drilling. Fracture-filling hydrate is the main type of gas hydrate found in the Qilian Mountain permafrost. Most of gas hydrate samples had been found in a thin-layer-like, flake and block group in a fracture of Jurassic mudstone and oil shale, although some pore-filling hydrate was found in porous sandstone. The mechanism for gas hydrate formation in the Qilian Mountain permafrost is as follows: gas generation from source rock was controlled by tectonic subsidence and uplift--gas migration and accumulation was controlled by fault and tight formation--gas hydrate formation and accumulation was controlled by permafrost. Some control factors for gas hydrate formation in the Qilian Mountain permafrost were analyzed and validated through numerical analysis and laboratory experiments. CSMGem was used to estimate the gas hydrate stability zone in the Qilian permafrost at a depth of 100–400 m. This method was used to analyze the gas composition of gas hydrate to determine the gas composition before gas hydrate formation. When the overlying formation of gas accumulation zone had a permeability of 0.05 × 10⁻¹⁵ m² and water saturation of more than 0.8, gas from deep source rocks was sealed up to form the gas accumulation zone. Fracture-filling hydrate was formed in the overlap area of gas hydrate stability zone and gas accumulation zone. The experimental results showed that the lithology of reservoir played a key role in controlling the occurrence and distribution of gas hydrate in the Qilian Mountain permafrost.     

Numerical modeling of gas hydrate emplacements in oceanic sediments

We have implemented a 2-dimensional numerical model for simulating gas hydrate and free gas accumulation in marine sediments. The starting equations are those of the conservation of the transport of momentum, energy, and mass, as well as those of the thermodynamics of methane hydrate stability and methane solubility in the pore-fluid. These constitutive equations are then integrated into a finite element in space, finite-difference in time scheme. We are then able to examine the formation and distribution of methane hydrate and free gas in a simple geologic framework, with respect to the geothermal heat flow, fluid flow, the methane in-situ production and basal flux. Three simulations are performed, leading to the build up of hydrate emplacements largely linear through time. Models act primarily as free gas accumulators and are relatively inefficient with respect to hydrate emplacements: 26–33% of formed methane are converted to hydrate. Seepage of methane across the sea-floor is negligible for fluid flow below 2. 10⁻¹¹ kg/m²/s. At 5.625 10⁻¹¹ kg/m²/s however, 9.7% of the formed methane seeps out of the model. Moreover, along strike variation arising in the 2-dimensional model are outlined. In the absence of focused flow, the thermodynamics of hydrate accumulation are primarily one-dimensional. However, changes in free methane compressibility (density) and methane solubility (the intrinsic dissolved methane flux) subtlety impact on the formation of a free gas zone and the distribution of the hydrate emplacements in our 2-dimensional simulations.     

Gas hydrate saturation in the Krishna–Godavari basin from P-wave velocity and electrical resistivity logs

During the Indian National Gas Hydrate Program (NGHP) Expedition 01, a series of well logs were acquired at several sites across the Krishna–Godavari (KG) Basin. Electrical resistivity logs were used for gas hydrate saturation estimates using Archie’s method. The measured in situ pore-water salinity, seafloor temperature and geothermal gradients were used to determine the baseline pore-water resistivity. In the absence of core data, Arp’s law was used to estimate in situ pore-water resistivity. Uncertainties in the Archie’s approach are related to the calibration of Archie coefficient (a), cementation factor (m) and saturation exponent (n) values. We also have estimated gas hydrate saturation from sonic P-wave velocity logs considering the gas hydrate in-frame effective medium rock-physics model. Uncertainties in the effective medium modeling stem from the choice of mineral assemblage used in the model. In both methods we assume that gas hydrate forms in sediment pore space. Combined observations from these analyses show that gas hydrate saturations are relatively low (<5% of the pore space) at the sites of the KG Basin. However, several intervals of increased saturations were observed e.g. at Site NGHP-01-03 (S_h = 15–20%, in two zones between 168 and 198 mbsf), Site NGHP-01-05 (S_h = 35–38% in two discrete zone between 70 and 90 mbsf), and Site NGHP-01-07 shows the gas hydrate saturation more than 25% in two zones between 75 and 155 mbsf. A total of 10 drill sites and associated log data, regional occurrences of bottom-simulating reflectors from 2D and 3D seismic data, and thermal modeling of the gas hydrate stability zone, were used to estimate the total amount of gas hydrate within the KG Basin. Average gas hydrate saturations for the entire gas hydrate stability zone (seafloor to base of gas hydrate stability), sediment porosities, and statistically derived extreme values for these parameters were defined from the logs. The total area considered based on the BSR seismic data covers ∼720 km². Using the statistical ranges in all parameters involved in the calculation, the total amount of gas from gas hydrate in the KG Basin study area varies from a minimum of ∼5.7 trillion-cubic feet (TCF) to ∼32.1 TCF.     

Methane hydrate dissolution rates in undersaturated seawater under controlled hydrodynamic forcing

The dissolution of in-situ generated methane hydrate in undersaturated, synthetic seawater (S = 35) was investigated in a series of laboratory-based experiments at P-/T-conditions within the hydrate stability field. A controlled flow field was generated across the smooth hydrate surface to test if, in addition to thermodynamic variables, the dissolution rate is influenced by changing hydrodynamic conditions. The dissolution rate was found to be strongly dependent on the friction velocity, showing that hydrate dissolution in undersaturated seawater is a diffusion-controlled process. The experimental data was used to obtain diffusional mass transfer coefficients k_d, which were found to correlate linearly with the friction velocity, u. The resulting k_d/u-correlation allows predicting the flux of methane from natural gas hydrate exposures at the sediment/seawater interface into the bulk water for a variety of natural P, T and flow conditions. It also is a tool for estimating the rate of hydrate regrowth at locations where natural hydrate outcrops at the seafloor persist in contact with undersaturated seawater.     

Appraisal of gas-hydrate/free-gas from VP/VS ratio in the Makran accretionary prism

Existence of gas-hydrate in the marine sediments elevates both the P- and S-wave seismic velocities, whereas even a small amount of underlying free-gas decreases the P-wave velocity considerably and the S-wave velocity remains almost unaffected. Study of both P- and S-wave seismic velocities or their ratio (V_P/V_S) for the hydrate-bearing sediment provides more information than that obtained by the P- or S-wave velocity alone for the quantitative assessment of gas-hydrate. We estimate the P- and S-wave seismic velocities across a BSR (interface between gas-hydrate and free-gas bearing sediments) using the travel time inversion followed by a constrained AVA modeling of multi channel seismic (MCS) data at two locations in the Makran accretionary prism. Using this V_P/V_S ratio, we then quantify the amount of gas-hydrate and free-gas based on two rock-physics models. The result shows an estimate of 12–14.5% gas-hydrate and 4.5–5.5% free-gas of the pore volume based on first model, and 13–20% gas-hydrate and 3–3.5% free-gas of the pore volume based on the second model, respectively.     

The thermal structure of the Dvurechenskii mud volcano and its implications for gas hydrate stability and eruption dynamics

The sediment temperature distribution at mud volcanoes provides insights into their activity and into the occurrence of gas hydrates. If ambient pressure and temperature conditions are close to the limits of the gas hydrate stability field, the sediment temperature distribution not only limits the occurrence of gas hydrates, but is itself influenced by heat production and consumption related to the formation and dissociation of gas hydrates. Located in the Sorokin Trough in the northern Black Sea, the Dvurechenskii mud volcano (DMV) was in the focus of detailed investigations during the M72/2 and M73/3a cruises of the German R/V Meteor and the ROV Quest 4000 m in February and March 2007. A large number of in-situ sediment temperature measurements were conducted from the ROV and with a sensor-equipped gravity corer. Gas hydrates were sampled in pressurized cores using a dynamic autoclave piston corer (DAPC). The thermal structure of the DMV suggests a regime of fluid flow at rates decreasing from the summit towards the edges of the mud volcano, accompanied by intermittent mud expulsion at the summit. Modeled gas hydrate dissociation temperatures reveal that the gas hydrates at the DMV are very close to the stability limits. Changes in heat flow due to variable seepage rates probably do not result in changes in sediment temperature but are compensated by gas hydrate dissociation and formation.     

海洋天然气水合物生成机制的实验研究

天然气水合物在海洋环境中与在纯水溶液中的生成条件有很大的不同。海洋天然气水合物的生成除了受温度和压力的影响外,还要受到孔隙水的化学组成、流体中气体的浓度及沉积物类型的影响。本文综述了国外海洋天然气水合物的实验研究成果及其进展,重点介绍了海洋天然气水合物生成与分解的热力学条件及各种影响因素,并探讨了今后该领域的研究方向和问题。     

Gas and fluid venting at the Makran accretionary wedge off Pakistan

The Makran accretionary complex shows a distinct bottom-simulating reflector, indicating a thick gas-hydrate-bearing horizon between the deformational front and about 1350 m water depth which seals off the upward flow of gas-charged fluids. A field of presently inactive mud diapirs with elevations up to 65 m was discovered in the abyssal plain seawards of the deformation front, suggesting that in the past conditions were favorable for periodic but localized vigorous mud diapirism. Regional destabilization of the gas hydrate leading to focused flow was observed where deep-penetrating, active faults reach the base of the gas-hydrate layer, as in a deeply incised submarine canyon (2100–2500 m water depth). At this location we discovered seeps of methane and H₂S-rich fluids associated with chemoautotrophic vent faunas (e.g., Calyptogena sp.). Driven by the accretionary wedge dynamics, the landward part of the gas-hydrate layer below the Makran margin is being progressively uplifted. Due to reduced hydrostatic pressure and rising ocean bottom-water temperatures, gas hydrates are progressively destabilized and dissociated into hydrate water, methane and H₂S. Sediment temperatures lie outside the methane stability field wherever water depth is less than 800 m. Above this depth, upward migration of fluids to the seafloor is unimpeded, thus explaining the abundance of randomly distributed gas seeps observed at water depths of 350 to 800 m. Received: 14 June 1999 / Revision accepted: 6 February 2000     

沉积物中天然气水合物超声检测技术

海洋天然气水合物主要分布在海底沉积物的孔隙中.而海底沉积物可以看作是一种紧密的湿颗粒双相多孔介质.基于双相多孔介质理论,分析和研究在孔隙中天然气水合物发生相变过程引起的多孔介质物性的变化而导致的声波传播的改变,可以找出其中的变化规律,对于研究沉积物中的天然气水合物具有重要的理论意义和实际价值.     

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.     

Seismic imaging of a fractured gas hydrate system in the Krishna–Godavari Basin offshore India

Gas hydrate was discovered in the Krishna–Godavari (KG) Basin during the India National Gas Hydrate Program (NGHP) Expedition 1 at Site NGHP-01-10 within a fractured clay-dominated sedimentary system. Logging-while-drilling (LWD), coring, and wire-line logging confirmed gas hydrate dominantly in fractures at four borehole sites spanning a 500 m transect. Three-dimensional (3D) seismic data were subsequently used to image the fractured system and explain the occurrence of gas hydrate associated with the fractures. A system of two fault-sets was identified, part of a typical passive margin tectonic setting. The LWD-derived fracture network at Hole NGHP-01-10A is to some extent seen in the seismic data and was mapped using seismic coherency attributes. The fractured system around Site NGHP-01-10 extends over a triangular-shaped area of ∼2.5 km² defined using seismic attributes of the seafloor reflection, as well as “seismic sweetness” at the base of the gas hydrate occurrence zone. The triangular shaped area is also showing a polygonal (nearly hexagonal) fault pattern, distinct from other more rectangular fault patterns observed in the study area. The occurrence of gas hydrate at Site NGHP-01-10 is the result of a specific combination of tectonic fault orientations and the abundance of free gas migration from a deeper gas source. The triangular-shaped area of enriched gas hydrate occurrence is bound by two faults acting as migration conduits. Additionally, the fault-associated sediment deformation provides a possible migration pathway for the free gas from the deeper gas source into the gas hydrate stability zone. It is proposed that there are additional locations in the KG Basin with possible gas hydrate accumulation of similar tectonic conditions, and one such location was identified from the 3D seismic data ˜6 km NW of Site NGHP-01-10.     

Effects of natural organic matter from sediments on the growth of marine gas hydrates

Sediments recovered from 0 to 27 + meters below the seafloor (mbsf) of a gas-hydrate and gas-venting active area in the Gulf of Mexico were added to a hydrate growth test cell to determine the influence of the organic and inorganic sedimentary components on hydrate induction times and formation rates. Induction times were sixteen times shorter in the presence of sediment from approximately 18 mbsf (relative to sediment from 1 mbsf), and remained stable in the presence of sediment from 18 to 27 mbsf. Formation rates increased by a factor of 2.5 in the presence of sediments from approximately 18 mbsf and decreased somewhat in the presence of sediment from 18 to 27 mbsf. Selected samples (surface, 18 and 27 mbsf) were density fractionated and subjected to bulk elemental and X-ray photoelectron spectroscopy (XPS) analysis. XPS revealed the presence of iron in various chemical environments at depths of 18 and 27 mbsf. High Resolution Magic Angle Spinning Nuclear Magnetic Resonance (HR-MAS NMR) was used to characterize the organic component of sediments from selected depths. The discovery of intact proteinaceous material in the surface sediment was surprising due to the labile nature of these biopolymers, and potentially reflects microbial activity in these surface layers. This material was less abundant in sediment from increasing depths, where more lipid-like compounds were prominent. The results suggest that hydrate growth is inhibited by the presence of proteinaceous material but enhanced by lipid-like compounds associated with iron-bearing mineral surfaces.     

Contribution of thermogenic organic matter to the formation of biogenic gas hydrate: Evidence from geochemical and microbial characteristics of hydrate-containing sediments in the Taixinan Basin,South China Sea

High-saturation (40–100%), microbial gas hydrates have been acquired by expedition GMGS2 from the Taixinan Basin. In this study, geochemical and microbial features of hydrate-containing sediments from the drilling cores (GMGS2-09 and GMGS2-16) were characterized to explore their relationships with gas hydrate formation. Results showed that the average TOC content of GMGS2-09 and GMGS2-16 were 0.45% and 0.63%, respectively. They could meet the threshold for in situ gas hydrate formation, but were not available for the formation of high-saturation gas hydrates. The dominant members of Bacteria at the class taxonomic level were Alphaproteobacteria, Bacilli, Bacteroidia, Epsilonproteobacteria and Gammaproteobacteria, and those in Archaea were Marine_Benthic_Group_B (MBGB), Miscellaneous_Crenarchaeotic_Group (MCG), Group C3, Methanomicrobia and Methanobacteria. Indicators of microbes associated with thermogenic organic matter were measured. These include: (1) most of the dominant microbes had been found dominant in other gas hydrates bearing sediments, mud volcanos as well as oil/coal deposits; (2) hydrogenotrophic methanogens and an oilfield-origin thermophilic, methylotrophic methanogen were found dominant the methanogen community; (3) hydrocarbon-assimilating bacteria and other hyperthermophiles were frequently detected. Therefore, thermogenic signatures were inferred existed in the sediments. This deduction is consistent with the interpretation from the seismic reflection profiles. Owing to the inconsistency between low TOC content and gas hydrates with high saturation, secondary microbial methane generated from the bioconversion of thermogenic organic matters (oil or coal) was speculated to serve as enhanced gas flux for the formation of high-saturation gas hydrates. A preliminary formation model of high-saturation biogenic gas hydrates was proposed, in which diagenesis processes, tectonic movements and microbial activities were all emphasized regarding to their contribution to gas hydrates formation. In short, this research helps explain how microbial act and what kind of organic matter they use in forming biogenic gas hydrates with high saturations.