Breakup of deep-water methane bubbles

During the Russian Academy of Sciences “MIRI na Baikale. 2008–2009” expedition, deep-water experiments on methane bubbles emerging from the lake bottom at depth of 1400 and 860 meters were carried out. Bubbles escaping the seabed were caught by a trap, which was an inverted glass. Entering in the trap, bubbles became covered by a gas hydrate envelope and then after a time period collapsed into a number of gas hydrate solid fragments. Due to positive buoyancy, fragments remained in the top part of a trap, exhibiting properties of a powder. The glass’s bottom was replaced with a 1 mm mesh grid, allowing the finest gas hydrate particles to sift through the grid, rising upwards. It is proposed that bubble collapse into fragments is related to the pressure drop in the bubble in the course of formation of the gas hydrate envelope. No visible changes in the gas hydrate powder were observed in the course of lifting it to a depth of 380 meters. Shallower than 380 meters, i.e., outside the zone of gas hydrate stability, decomposition of the gas hydrate powder into methane gas was observed.     

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.     

Experimental formation of massive hydrate deposits from accumulation of CH4 gas bubbles within synthetic and natural sediments

In order for methane to be economically produced from the seafloor, prediction and detection of massive hydrate deposits will be necessary. In many cases, hydrate samples recovered from seafloor sediments appear as veins or nodules, suggesting that there are strong geologic controls on where hydrate is likely to accumulate. Experiments have been conducted examining massive hydrate accumulation from methane gas bubbles within natural and synthetic sediments in a large volume pressure vessel through temperature and pressure data, as well as visual observations. Observations of hydrate growth suggest that accumulation of gas bubbles within void spaces and at sediment interfaces likely results in the formation of massive hydrate deposits. Methane hydrate was first observed as a thin film forming at the gas/water interface of methane bubbles trapped within sediment void spaces. As bubbles accumulated, massive hydrate growth occurred. These experiments suggest that in systems containing free methane gas, bubble pathways and accumulation points likely control the location and habit of massive hydrate deposits.     

The first experience the transportation of deep-water methane hydrates in a container

Deep-water experiments on the transportation of collected samples of methane hydrates from a lake’s bottom to a support container were carried out as part of the MIRY na Baikale (2008–2009) expedition run by the Russian Academy of Sciences. High pressures and low temperatures are necessary for gas hydrates stability. As a sample of the hydrate is lifted to the water’s surface, it intensively decomposes into water and methane gas. To reduce the decomposition, we used a container in which the hydrate’s sample occurs in a gas medium rather than in water, which results in a substantial reduction in the rate of the heat exchange. At that, the gas for the container’s filling was supplied by the hydrate itself due to its partial decomposition. To estimate the method’s efficiency, we observed the hydrate’s decomposition during lifting from a depth of 1400 m using different transportation techniques such as gas- or water-filled containers or fixing the sample in the manipulator’s arm of the submersible. The sample in the gaseous medium was the only one that was safely delivered on board the support container, while the two others completely decomposed during the transportation. It is remarkable that all the samples started to decompose simultaneously at a depth of 380 m but their decomposition occurred at different rates.     

硫酸盐-甲烷界面与甲烷通量及下伏天然气水合物赋存的关系

硫酸盐-甲烷界面在富甲烷和含天然气水合物的海洋沉积区已经成为一个重要的生物地球化学识别边界。在硫酸盐-甲烷界面之上,沉积物中的硫酸盐因参与分解有机质和甲烷厌氧氧化反应而被消耗,而其界面之下沉积物中的甲烷则不断生成,含量逐渐增加。根据该界面附近硫酸盐浓度和甲烷浓度的变化特征,可以判断该区甲烷流体通量的大小,从而指示下伏天然气水合物的可能赋存状况。南海北部陆坡的柱状沉积物孔隙水数据的分析显示,硫酸盐-甲烷界面埋深比较浅,表明该海域的甲烷通量较高。这种高甲烷通量很可能是由下伏的天然气水合物所引起的,并暗示着该区下伏海底可能有天然气水合物沉积层赋存。     

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.     

Microstructure characteristics during hydrate formation and dissociation revealed by X-ray tomographic microscopy

Despite much progress over the past years in fundamental gas hydrate research, frontiers to the unknown are the early beginning and early decomposition of gas hydrates in their natural, submarine environment: gas bubbles meeting ocean water and forming hydrate, and gas starting to escape from the surface of a hydrate grain. In this paper we report on both of these topics, and present three-dimensional microstructure results obtained by synchrotron radiation X-ray cryo-tomographic microscopy (SRXCTM). Hydrates can precipitate when hydrate-forming molecules such as methane exceed solubility, and combine with water within the gas hydrate stability zone. Here we show hydrate formation on surfaces of bubbles from different gas mixtures and seawater, based on underwater robotic in situ experiments in the deep Monterey Canyon, offshore California. Hydrate begins to form from the surrounding water on the bubble surfaces, and subsequently grows inward into the bubble, evidenced by distinct edges. Over time, the bubbles become smaller while gas is being incorporated into newly formed hydrate. In contrast, current understanding has been that hydrate decomposition starts on the outer surface of hydrate aggregates and grains. It is shown that in an early stage of decomposition, newly found tube structures connect well-preserved gas hydrate patches to areas that are dissociating, demonstrating how dissociating areas in a hydrate grain are linked through hydrate that is still intact and will likely decompose at a later stage.

南海神狐天然气水合物系统沉积物中自生黄铁矿的特征研究

南海神狐海域是中国最重要的天然气水合物调查研究区之一,为了解水合物存在对沉积物地球化学环境的影响,对采自神狐海域W19B井位的沉积物样品进行了矿物学和地球化学研究。X射线衍射分析和主量元素结果显示部分层位有异常高含量的硫化物（主要为黄铁矿）。扫描电镜结果表明随着样品深度的增加,黄铁矿的晶面、晶棱更加明显,且集合体形态呈现聚莓→单莓→细粒的变化趋势,扫描电镜还观察到草莓状黄铁矿向细粒自形黄铁矿转化的中间产物。在53.0 mbsf（meters below seafloor）和140.4 mbsf层位均发现异常高含量的黄铁矿。其中140.4 mbsf层位黄铁矿充填有孔虫壳体的现象普遍,并伴有大量柱状黄铁矿产出,可能与有机质和甲烷厌氧氧化相关,但主导作用应为甲烷厌氧氧化,该层位可能位于古硫酸根-甲烷界面（sulfate-methane interface,SMI）附近。根据所得结果,推测地质历史时期中甲烷异常渗漏事件的发生,致使向上的甲烷通量增加,推动SMI上移,导致53.0 mbsf和140.4 mbsf界面处因甲烷厌氧氧化而形成大量黄铁矿。多个黄铁矿富集层的存在可能表示沉积史中曾发生多期次的深部流体渗漏或者天然气水合物的分解活动。     

Acoustic investigations of gas “flares” in the Sea of Okhotsk

The results of acoustic investigations of over 250 gas “flares” (GFs) located in the depth range of 160–1400 m in the vicinity of the northeastern slope of Sakhalin Island are presented. Pronounced features in the GFs distribution by the seabed’s depth have been identified, which allowed dividing them into four groups corresponding to four depth intervals. The number of GFs per seabed unit area decreases, and the power of the individual GFs increases with depth. The average methane flux per seabed unit of area has been estimated for each depth interval. It has been demonstrated that the total quantity of methane emitted from the seabed in the form of bubbles in the studied area is ∼0.1 million tons per year.     

Heat and mass transfer effects during displacement of deepwater methane hydrate to the surface of Lake Baikal

The present paper focuses on heat and mass exchange processes in methane hydrate fragments during in situ displacement from the gas hydrate stability zone (GHSZ) to the water surface of Lake Baikal. After being extracted from the methane hydrate deposit at the lakebed, hydrate fragments were placed into a container with transparent walls and a bottom grid. There were no changes in the hydrate fragments during ascent within the GHSZ. The water temperature in the container remained the same as that of the ambient water (~3.5 °С). However, as soon as the container crossed the upper border of the GHSZ, first signs of hydrate decomposition and transformation into free methane gas were observed. The gas filled the container and displaced water from it. At 300 m depth, the upper and lower thermometers in the container simultaneously recorded noticeable decreases of temperature. The temperature in the upper part of the container decreased to –0.25 °С at about 200 m depth, after which the temperature remained constant until the water surface was reached. The temperature at the bottom of the container reached –0.25 °С at about 100 m depth, after which it did not vary during further ascent. These observed effects could be explained by the formation of a gas phase in the container and an ice layer on the hydrate surface caused by heat consumption during hydrate decomposition (self-preservation effect). However, steady-state simulations suggest that the forming ice layer is too thin to sustain the hydrate internal pressure required to protect the hydrate from decomposition. Thus, the mechanism of self-preservation remains unclear.     

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     

南海神狐海域天然气水合物饱和度的数值模拟分析

珠江口盆地神狐海域是天然气水合物钻探和试验开采的重点区域,大量钻探取心、测井与地震等综合分析表明不同站位水合物的饱和度、厚度与气源条件存在差异。本文利用天然气水合物调查及深水油气勘探所采集的测井和地震资料建立地质模型,利用PetroMod软件模拟地层的温度场、有机质成熟度、烃源岩生烃量、流体运移路径以及不同烃源岩影响下的水合物饱和度,结果表明:生物成因气分布在海底以下1500 m范围内的有机质未成熟地层,而热成因气分布在深度超过2300 m的成熟、过成熟地层。水合物稳定带内生烃量难以形成水合物,形成水合物气源主要来自于稳定带下方向上运移的生物与热成因气。模拟结果与测井结果对比分析表明,稳定带下部生物成因气能形成的水合物饱和度约为10%,在峡谷脊部的局部区域饱和度较高;相对高饱和度(>40%)水合物形成与文昌组、恩平组的热成因气沿断裂、气烟囱等流体运移通道幕式释放密切相关,W19井形成较高饱和度水合物的甲烷气体中热成因气占比达80%,W17井热成因气占比为73%,而SH2井主要以生物成因为主,因此,不同站位甲烷气体来源占比不同。     

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 decomposition recorded by authigenic barite at pockmark sites of the northern Congo Fan

The geochemical cycling of barium was investigated in sediments of pockmarks of the northern Congo Fan, characterized by surface and subsurface gas hydrates, chemosynthetic fauna, and authigenic carbonates. Two gravity cores retrieved from the so-called Hydrate Hole and Worm Hole pockmarks were examined using high-resolution pore-water and solid-phase analyses. The results indicate that, although gas hydrates in the study area are stable with respect to pressure and temperature, they are and have been subject to dissolution due to methane-undersaturated pore waters. The process significantly driving dissolution is the anaerobic oxidation of methane (AOM) above the shallowest hydrate-bearing sediment layer. It is suggested that episodic seep events temporarily increase the upward flux of methane, and induce hydrate formation close to the sediment surface. AOM establishes at a sediment depth where the upward flux of methane from the uppermost hydrate layer counterbalances the downward flux of seawater sulfate. After seepage ceases, AOM continues to consume methane at the sulfate/methane transition (SMT) above the hydrates, thereby driving the progressive dissolution of the hydrates “from above”. As a result the SMT migrates downward, leaving behind enrichments of authigenic barite and carbonates that typically precipitate at this biogeochemical reaction front. Calculation of the time needed to produce the observed solid-phase barium enrichments above the present-day depths of the SMT served to track the net downward migration of the SMT and to estimate the total time of hydrate dissolution in the recovered sediments. Methane fluxes were higher, and the SMT was located closer to the sediment surface in the past at both sites. Active seepage and hydrate formation are inferred to have occurred only a few thousands of years ago at the Hydrate Hole site. By contrast, AOM-driven hydrate dissolution as a consequence of an overall net decrease in upward methane flux seems to have persisted for a considerably longer time at the Worm Hole site, amounting to a few tens of thousands of years.     

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.     

Characterizing lipid biomarkers in methanotrophic communities of gas hydrate-bearing sediments in the Sea of Okhotsk

We studied specific lipid biomarkers of archaea and bacteria, that are associated with the anaerobic oxidation of methane (AOM) in a cold seep environment as well as the origin of sedimentary organic matter on the continental slope off NE Sakhalin in the Sea of Okhotsk. The organic geochemical parameters demonstrated that most of the sedimentary organic matter containing hydrate layers could be derived from marine phytoplankton and bacteria, except for a station (LV39-29H) which was remarkably affected by terrestrial vascular plant. Specific methanotrophic archaea biomarkers was vertically detected in hydrate-bearing cores (LV39-40H), coinciding with the negative excursion of the δ¹³C_org at core depths of 90–100 cm below the seafloor. These results suggest that methane provided from gas hydrates are already available substrates for microbes thriving in this sediment depth. In addition, the stable isotope mass balance method revealed that approximately 2.77–3.41% of the total organic carbon (or 0.036–0.044% dry weight sediment) was generated by the activity of the AOM consortium in the corresponding depth of core LV39-40H. On the other hand, the heavier δ¹³C values of archaeol in the gas hydrate stability zone may allow ongoing methanogenesis in deeper sediment depth.     

Geothermal modeling of the gas hydrate stability zone along the Krishna Godavari Basin

A wide-spread bottom simulating reflector (BSR), interpreted to mark the thermally controlled base of the gas hydrate stability zone, is observed over a close grid of multichannel seismic profiles in the Krishna Godavari Basin of the eastern continental margin of India. The seismic data reveal that gas hydrate occurs in the Krishna Godavari Basin at places where water depths exceed 850 m. The thickness of the gas hydrate stability zone inferred from the BSR ranges up to 250 m. A conductive model was used to determine geothermal gradients and heat flow. Ground truth for the assessment and constraints on the model were provided by downhole measurements obtained during the National Gas Hydrate Program Expedition 01 of India at various sites in the Krishna Godavari Basin. Measured downhole temperature gradients and seafloor-temperatures, sediment thermal conductivities, and seismic velocity are utilized to generate regression functions for these parameters as function of overall water depth. In the first approach the base of gas hydrate stability is predicted from seafloor bathymetry using these regression functions and heat flow and geothermal gradient are calculated. In a second approach the observed BSR depth from the seismic profiles (measured in two-way travel time) is converted into heat flow and geothermal gradient using the same ground-truth data. The geothermal gradient estimated from the BSR varies from 27 to 67°C/km. Corresponding heat flow values range from 24 to 60 mW/m². The geothermal modeling shows a close match of the predicted base of the gas hydrate stability zone with the observed BSR depths.     

Dynamic processes observed at a gas hydrate outcropping on the continental slope of the Gulf of Mexico

A deep-sea time-lapse camera and several temperature probes were deployed on the Gulf of Mexico continental shelf at a biological community associated with a gas hydrate outcropping to study topographic and hydrologic changes over time. The deployment site, Bush Hill (GC-185), is located at 27°47.5′ N and 91°15.0′ W at depths of ∼540 m. The digital camera recorded one still image every 6 h for July-October in 2001, every 2 h for the month of June 2002, and every 6 h for the month of July 2002. Temperature probes were in place at the site for the entire experimental period. The data recovered provide a record of processes that occur at gas hydrate mounds. Sediment resuspension over the mound causes significant variation in luminosity of the time-lapse photographs. A marked diurnal pattern can be seen in the temperature and luminosity records. No major change in shape or size of the gas hydrate outcrop at this site was observed during this study. Stable topography of the gas hydrate mound, combined with high bacterial activity and sediment turnover, appears to focus biological activity in the mound area. Frequency and recurrence of sediment resuspension indicate that short-term change in the depth and distribution of surface sediments is a feature of the benthos at the site. Because the sediment interface is a critical environment for hydrocarbon oxidation and chemosynthesis, short-term variability and heterogeneity may be important characteristics of these settings.     

Fluid flow and methane occurrences in the Disko Bugt area offshore West Greenland: indications for gas hydrates?

The present study is the first to directly address the issue of gas hydrates offshore West Greenland, where numerous occurrences of shallow hydrocarbons have been documented in the vicinity of Disko Bugt (Bay). Furthermore, decomposing gas hydrate has been implied to explain seabed features in this climate-sensitive area. The study is based on archive data and new (2011, 2012) shallow seismic and sediment core data. Archive seismic records crossing an elongated depression (20×35 km large, 575 m deep) on the inner shelf west of Disko Bugt (Bay) show a bottom simulating reflector (BSR) within faulted Mesozoic strata, consistent with the occurrence of gas hydrates. Moreover, the more recently acquired shallow seismic data reveal gas/fluid-related features in the overlying sediments, and geochemical data point to methane migration from a deeper-lying petroleum system. By contrast, hydrocarbon signatures within faulted Mesozoic strata below the strait known as the Vaigat can be inferred on archive seismics, but no BSR was visible. New seismic data provide evidence of various gas/fluid-releasing features in the overlying sediments. Flares were detected by the echo-sounder in July 2012, and cores contained ikaite and showed gas-releasing cracks and bubbles, all pointing to ongoing methane seepage in the strait. Observed seabed mounds also sustain gas seepages. For areas where crystalline bedrock is covered only by Pleistocene–Holocene deposits, methane was found only in the Egedesminde Dyb (Trough). There was a strong increase in methane concentration with depth, but no free gas. This is likely due to the formation of gas hydrate and the limited thickness of the sediment infill. Seabed depressions off Ilulissat Isfjord (Icefjord) previously inferred to express ongoing gas release from decomposing gas hydrate show no evidence of gas seepage, and are more likely a result of neo-tectonism.     

Association among active seafloor deformation, mound formation, and gas hydrate growth and accumulation within the seafloor of the Santa Monica Basin, offshore California

Seafloor blister-like mounds, methane migration and gas hydrate formation were investigated through detailed seafloor surveys in Santa Monica Basin, offshore of Los Angeles, California. Two distinct deep-water (≥ 800 m water depth) topographic mounds were surveyed using an autonomous underwater vehicle (carrying a multibeam sonar and a chirp sub-bottom profiler) and one of these was explored with the remotely operated vehicle Tiburon. The mounds are > 10 m high and > 100 m wide dome-shaped bathymetric features. These mounds protrude from crests of broad anticlines (~ 20 m high and 1 to 3 km long) formed within latest Quaternary-aged seafloor sediment associated with compression between lateral offsets in regional faults. No allochthonous sediments were observed on the mounds, except slumped material off the steep slopes of the mounds. Continuous streams of methane gas bubbles emanate from the crest of the northeastern mound, and extensive methane-derived authigenic carbonate pavements and chemosynthetic communities mantle the mound surface. The large local vertical displacements needed to produce these mounds suggests a corresponding net mass accumulation has occurred within the immediate subsurface. Formation and accumulation of pure gas hydrate lenses in the subsurface is proposed as a mechanism to blister the seafloor and form these mounds.