Identification of functionally active aerobic methanotrophs and their methane oxidation potential in sediments from the Shenhu Area,South China Sea

Large amounts of gas hydrate are distributed in the northern slope of the South China Sea, which is a potential threat of methane leakage. Aerobic methane oxidation by methanotrophs, significant methane biotransformation that occurs in sediment surface and water column, can effectively reduce atmospheric emission of hydrate-decomposed methane. To identify active aerobic methanotrophs and their methane oxidation potential in sediments from the Shenhu Area in the South China Sea, multi-day enrichm...     

The Geochemical Context of Gas Hydrate in the Eastern Nankai Trough

Abstract. Geochemical studies for gas hydrate, gas and organic matter collected from gas hydrate research wells drilled at the landward side of the eastern Nankai Trough, offshore Tokai, Japan, are reported. Organic matter in the 2355 m marine sediments drilled to Eocene is mainly composed of Type III kerogen with both marine and terrigenous organic input. The gas hydrate-bearing shallow sediments are immature for hydrocarbon generation, whereas the sediments below 2100 mbsf are thermally mature. The origins of gases change from microbial to thermogenic at around 1500 mbsf.
Carbon isotope compositions of CH₄ and CO₂, and hydrocarbon compositions consistently suggest that the CH₄ in the gas hydrate-bearing sediments is generated by microbial reduction of CO₂. The δ¹³C depth-profiles of CH₄ and CO₂ suggest that the microbial methanogenesis is less active in the Nankai Trough sediments compared with other gas hydrate-bearing sediments where solid gas hydrate samples of microbial origin were recovered. Since in situ generative-potential of microbial methane in the Nankai Trough sediments is interpreted to be low due to the low total organic carbon content (0.5 % on the average) in the gas hydrate-bearing shallow sediments, upward migration of microbial methane and selective accumulation into permeable sands should be necessary for the high concentration of gas hydrate in discrete sand layers.     

多孔介质中天然气水合物稳定性的实验研究进展

勘探表明天然气水合物多产出于细碎屑沉积物中,其分布和赋存形式受温度、压力、水化学条件等多种物理化学因素的影响。前人的实验研究表明不同孔径尺度中的甲烷水合物稳定性有别于块状、层状水合物,同时孔隙表面的润湿性也是影响因素之一。在综合分析前人研究成果的基础上,系统阐述了孔隙的孔径、孔隙内表面润湿性对所含天然气水合物稳定性的影响规律,总结了可能的内在机理;并指出了当前应当尽快建立包括空间效应、温度、压力和组分等因素的综合天然气水合物相图,查明含天然气水合物沉积物的孔隙结构和表界面特征,建立天然气水合物的稳定性模型,将有助于精确预测天然气水合物的分布和规模,对于水合物开发和甲烷存储技术的研发也有着重要的意义。     

Subsurface Occurrence of Natural Gas Hydrate in the Nankai Trough Area: Implication for Gas Hydrate Concentration

Abstract. The Nankai Trough runs along the Japanese Islands, where extensive BSRs have been recognized in its forearc basins. High resolution seismic surveys and site-survey wells undertaken by the MITI have revealed the gas hydrate distribution at a depth of about 290 mbsf. The MITI Nankai Trough wells were drilled in late 1999 and early 2000. The highlights were successful retrievals of abundant gas hydrate-bearing cores in a variety of sediments from the main hole and the post survey well-2, keeping the cored gas hydrate stable, and the obtaining of continuous well log data in the gas hydrate-dominant intervals from the main hole, the post survey well-1 and the post survey well-3. Gas-hydrate dominant layers were identified at the depth interval from 205 to 268 mbsf. Pore-space hydrate, very small in size, was recognized mostly filling intergranular pores of sandy sediments. Anomalous chloride contents in extracted pore water, core temperature depression, core observations as well as visible gas hydrates confirmed the presence of pore-space hydrates within moderate to thick sand layers. Gas hydrate-bearing sandy strata typically were 10 cm to a meter thick with porosities of about 40 %. Gas hydrate saturations in most hydrate-dominant layers were quite high, up to 90 % pore saturation.
All the gas hydrate-bearing cores were subjected to X-ray CT imagery measurements for observation of undisturbed sedimentary textures and gas-hydrate occurrences before being subjected to other analyses, such as (1) petrophysical properties, (2) biostratigraphy, (3) geochemistry, (4) microbiology and (5) gas hydrate characteristics.     

天然气水合物研究中的几个重要问题

综述了当前关于天然气水合物研究中的几个重要问题，提出了今后的主要研究方向，全球大约有10^19g碳以天然气水合物的形式储存在沉积物中，大约是其它所有化石燃料沉积物形式储存量的2倍多，因此，天然气水合物被认为是21世纪具有商业开发无景的潜在的战略资源，天然气水合物是一种亚稳态物质，极易受到温度和压力条件的影响，海底天然气水合物的分解将会影响沉积物的物理化学性质（如剪切强度和流变性等），地球物理性质（如地震波速和电导性），以及地球化学性质（如孔隙流体成分）的明显变化，导致诸如海底滑塌等地质灾害的发生，天然气水合物的分解会产生导致“温室效应”的甲烷气体，该气体进入大气圈中会引起全球气候和环境的变化。     

Overview of the MITI Nankai Trough Wells: A Milestone in the Evaluation of Methane Hydrate Resources

Abstract. Bottom-simulating reflectors suggestive of the presence of methane hydrates are widely distributed below the ocean floor around Japan. In late 1999, drilling of the MITI Nankai Trough wells was conducted to explore this potential methane hydrate resource and a Tertiary conventional structure. The wells are located in the Northwest Pacific Ocean off Central Japan at a water depth of 945 m. A total of six wells were drilled, including the main well, two pilot wells, and three post survey wells at intervals of 10–100 m. All wells except the first confirmed the occurrence of hydrates based on logging-while-drilling, wire-line logging and/or coring using a pressure and temperature coring system in addition to conventional methods. Based on the various well profiles, four methane hydrate-bearing sand-rich intervals in turbidite fan deposits were recognized. Methane hydrates fill the pore spaces in these deposits, reaching saturation of up to 80 % in some layers. The methane hydrate-bearing turbiditic sand layers are less than 1 m thick, with a total thickness of 12–14 m. The bottom depth of high hydrate concentration correlates well with the depth of the bottom-simulating reflector. Based on these exploration results, the Japanese government inaugurated a 16-year methane hydrate exploitation program in 2001.     

Progress in Global Gas Hydrate Development and Production as a New Energy Resource

Natural gas hydrates have been hailed as a new and promising unconventional alternative energy, especially as fossil fuels approach depletion, energy consumption soars, and fossil fuel prices rise, owing to their extensive distribution, abundance, and high fuel efficiency. Gas hydrate reservoirs are similar to a storage cupboard in the global carbon cycle, containing most of the world’s methane and accounting for a third of Earth’s mobile organic carbon. We investigated gas hydrate stability zone burial depths from the viewpoint of conditions associated with stable existence of gas hydrates, such as temperature, pressure, and heat flow, based on related data collected by the global drilling programs. Hydrate-related areas are estimated using various biological, geochemical and geophysical tools. Based on a series of previous investigations, we cover the history and status of gas hydrate exploration in the USA, Japan, South Korea, India, Germany, the polar areas, and China. Then, we review the current techniques for hydrate exploration in a global scale. Additionally, we briefly review existing techniques for recovering methane from gas hydrates, including thermal stimulation, depressurization, chemical injection, and CH4–CO2 exchange, as well as corresponding global field trials in Russia, Japan, United States, Canada and China. In particular, unlike diagenetic gas hydrates in coarse sandy sediments in Japan and gravel sediments in the United States and Canada, most gas hydrates in the northern South China Sea are non-diagenetic and exist in fine-grained sediments with a vein-like morphology. Therefore, especially in terms of the offshore production test in gas hydrate reservoirs in the Shenhu area in the north slope of the South China Sea, Chinese scientists have proposed two unprecedented techniques that have been verified during the field trials: solid fluidization and formation fluid extraction. Herein, we introduce the two production techniques, as well as the so-called “four-in-one” environmental monitoring system employed during the Shenhu production test. Methane is not currently commercially produced from gas hydrates anywhere in the world; therefore, the objective of field trials is to prove whether existing techniques could be applied as feasible and economic production methods for gas hydrates in deep-water sediments and permafrost zones. Before achieving commercial methane recovery from gas hydrates, it should be necessary to measure the geologic properties of gas hydrate reservoirs to optimize and improve existing production techniques. Herein, we propose horizontal wells, multilateral wells, and cluster wells improved by the vertical and individual wells applied during existing field trials. It is noteworthy that relatively pure gas hydrates occur in seafloor mounds, within near-surface sediments, and in gas migration conduits. Their extensive distribution, high saturation, and easy access mean that these types of gas hydrate may attract considerable attention from academia and industry in the future. Herein, we also review the occurrence and development of concentrated shallow hydrate accumulations and briefly introduce exploration and production techniques. In the closing section, we discuss future research needs, key issues, and major challenges related to gas hydrate exploration and production. We believe this review article provides insight on past, present, and future gas hydrate exploration and production to provide guidelines and stimulate new work into the field of gas hydrates.     

南海北部东沙群岛HD196站位地球化学特征及其对水合物的指示

南海北部是中国海上油气的重要基地,也是中国天然气水合物调查的首选地区。对南海北部东沙群岛附近具有BSR特征的HD196站位沉积物样品的地球化学特征进行综合分析,得到以下结果:柱状样沉积物的常量元素的分布具有分段性,且与沉积物孔隙水中的离子浓度和甲烷含量的变化趋势相一致,可能对其下面是否存在天然气水合物有指示意义;同时柱状样沉积物孔隙水中离子浓度的变化与世界上发现天然气水合物地点的孔隙水离子浓度的变化一致。HD196站位的地质条件表明本站位具有天然气水合物形成的温压条件、气源条件和构造条件,因此在本站位的下面赋存天然气水合物的可能性比较大,在此进一步工作有可能取得天然气水合物勘查的突破。     

Petrophysical Properties of Natural Gas Hydrates-Bearing Sands and Their Sedimentology in the Nankai Trough

Abstract. The Nankai Trough parallels the Japanese Island, where extensive BSRs have been interpreted from seismic reflection records. High resolution seismic surveys and drilling site-survey wells conducted by the MTI in 1997, 2001 and 2002 have revealed subsurface gas hydrate at a depth of about 290 mbsf (1235 mbsl) in the easternmost part of Nankai Trough. The MITI Nankai Trough wells were drilled in late 1999 and early 2000 to provide physical evidence for the existence of gas hydrate. During field operations, continuous LWD and wire-line well log data were obtained and numerous gas hydrate-bearing cores were recovered. Subsequence sedimentologic and geochemical analyses performed on the cores revealed important geologic controls on the formation and preservation of natural gas hydrate. This knowledge is crucial to predicting the location of other hydrate deposits and their eventual energy resource. Pore-space gas hydrates reside in sandy sediments from 205 to 268 mbsf mostly filling intergranular porosity. Pore waters chloride anomalies, core temperature depression and core observations on visible gas hydrates confirm the presence of pore-space hydrates within moderate to thick sand layers. Gas hydrate-bearing sandy strata typically were 10 cm to a meter thick. Gas hydrate saturations are typically between 60 and 90 % throughout most of the hydrate-dominant sand layers, which are estimated by well log analyses as well as pore water chloride anomalies.
It is necessary for evaluating subfurface fluid dlow behavious to know both porosity and permeability of gas hydrate-bearing sand to evaluate subsurface fluid flow behaviors. Sediment porosities and pore-size distributions were obtained by mercury porosimetry, which indicate that porosities of gas hydrate-bearing sandy strata are approximately 40 %. According to grain size distribution curves, gas hydrate is dominant in fine- to very fine-grained sandy strata.     

Greenhouse gas deposits in the deep sea

Gas hydrates are the largest deposits of hydrocarbons in the world. They are distributed throughout marine sediments and their stability depends largely upon temperature and pressure. Typically, ～99 percent of these hydrocarbon deposits are composed of methane, which is a potent greenhouse gas. Methane release from gas hydrates has been implicated in mass extinction events. Present and future changes in ocean temperature have the potential to increase the rate of methane production from gas hydrates and thus to affect Earth's climate. Whilst the deep sea normally serves as a sink for greenhouse gases, the release of methane from gas hydrates could be a hugely significant source in the future and pose a real threat to our efforts to limit greenhouse gas emissions.     

Growth behavior and resource potential evaluation of gas hydrate in core fractures in Qilian Mountain permafrost area,Qinghai-Tibet Plateau

The Qilian Mountain permafrost area located in the northern of Qinghai-Tibet Plateau is a favorable place for natural gas hydrate formation and enrichment, due to its well-developed fractures and abundant gas sources. Understanding the formation and distribution of multi-component gas hydrates in fractures is crucial in accurately evaluating the hydrate reservoir resources in this area. The hydrate formation experiments were carried out using the core samples drilled from hydrate-bearing sediments in Qilian Mountain permafrost area and the multi-component gas with similar composition to natural gas hydrates in Qilian Mountain permafrost area. The formation and distribution characteristics of multi-component gas hydrates in core samples were observed in situ by X-ray Computed Tomography (X-CT) under high pressure and low temperature conditions. Results show that hydrates are mainly formed and distributed in the fractures with good connectivity. The ratios of volume of hydrates formed in fractures to the volume of fractures are about 96.8% and 60.67% in two different core samples. This indicates that the fracture surface may act as a favorable reaction site for hydrate formation in core samples. Based on the field geological data and the experimental results, it is preliminarily estimated that the inventory of methane stored in the fractured gas hydrate in Qilian Mountain permafrost area is about 8.67×10¹³ m³, with a resource abundance of 8.67×10⁸ m³/km². This study demonstrates the great resource potential of fractured gas hydrate and also provides a new way to further understand the prospect of natural gas hydrate and other oil and gas resources in Qilian Mountain permafrost area.©2023 China Geology Editorial Office.     

Chemo‐thermo‐mechanically coupled seismic analysis of methane hydrate‐bearing sediments during a predicted Nankai Trough Earthquake

In the present study, we have developed a numerical method which can simulate the dynamic behaviour of a seabed ground during gas production from methane hydrate‐bearing sediments. The proposed method can describe the chemo‐thermo‐mechanical‐seismic coupled behaviours, such as phase changes from hydrates to water and gas, temperature changes and ground deformation related to the flow of pore fluids during earthquakes. In the first part of the present study, the governing equations for the proposed method and its discretization are presented. Then, numerical analyses are performed for hydrate‐bearing sediments in order to investigate the dynamic behaviour during gas production. The geological conditions and the material parameters are determined using the data of the seabed ground at Daini‐Atsumi knoll, Eastern Nankai Trough, Japan, where the first offshore production test of methane hydrates was conducted. A predicted earthquake at the site is used in the analyses. Regarding the seismic response to the earthquake which occur during gas production process, the wave profiles of horizontal acceleration and horizontal velocity were not extensively affected by the gas production. Hydrate dissociation behaviour is sensitive to changes in the pore pressure during earthquakes. Methane hydrate dissociation temporarily became active in some areas because of the main motion of the earthquake, then methane hydrate dissociation brought about an increase in the average pressure of the fluids during the earthquake. And, it was this increase in average pore pressure that finally caused the methane hydrate dissociation to cease during the earthquake. Copyright © 2016 John Wiley & Sons, Ltd.     

松散沉积物中天然气水合物生成、分解过程与声学特性的实验研究

为了解松散沉积物中天然气水合物的生成和分解规律以及水合物对沉积物声学特性的影响,在粒径为0.18~0.28mm天然沙中进行了甲烷水合物的生成和分解实验,并利用超声波探测技术和时域反射技术实时测量了反应体系的声学参数与含水量。结果表明:根据水合物的生成和分解速率,可将水合物的生成过程分为初始生长期、快速生长期和稳定期3个阶段,分解过程可分为初始分解期和样品表层水合物快速分解期以及样品内、外层水合物均快速分解期3个阶段;由温度和压力数据的分析,得出水合物先在沉积物表层生长,然后在沉积物内、外层迅速生成;由水合物分解过程3个阶段的平均分解率,得出水合物的分解是一个由慢到快的过程。对声学参数的研究表明:水合物在松散沉积物中先胶结骨架颗粒而生成,使纵波速度和声波衰减在饱和度0~1%之间陡然增大;随后水合物开始在沉积物孔隙中形成悬浮粒子,造成超声波信号在饱和度1%~90%间淬熄,声波速度无法获取。研究结果在揭示沉积物中水合物与颗粒间接触机制的同时,为海上地球物理勘探中地震信号的解释提供了新的思路。     

Application of AVO Analysis to Seismic Data for Detection of Gas below Methane Hydrate Stability Zone in Nankai Trough Area

Abstract. For the purpose of development of methane hydrate, occurring in the deep marine subsurface, as a resource, the most important issue is to understand the methane hydrate system (generation, migration and accumulation) as well as to delineate the methane hydrate reservoir properties. We have applied the Amplitude Versus Offset (AVO) analysis to the seismic data acquired in the Nankai Trough, offshore Japan, in order to confirm the occurrence of gas just below the methane hydrate-bearing zone, assuming that gas will show a so-called Class-3 AVO response. Knowledge of the amount and occurrence of gas in the sediment below methane hydrate-bearing zone is one of the keys to understand the methane hydrate system.
We have utilized the qualitative analysis of AVO methodology to delineate how gas is located below the BSR, which is thought to be the reflection event from the interface between the methane hydrate-bearing zone and the underlying gas-bearing zone. In the region of MITI Nankai Trough Well PSW-3, we observe two BSRs separated by 25 ms. After AVO modeling using well data, we applied AVO attribute analysis and attribute crossplot analysis to the seismic data. Finally we applied an offset-amplitude analysis to CMP gather data at specific locations to confirm the results of AVO attribute analysis. The AVO analysis shows that there is very little gas located in the underlying sediment below methane hydrate-bearing zone. This result supports the fact that we could not obtain any clear evidence of gas occurrence just below the methane hydrate-bearing zone in the Nankai Trough well drilling.     

海底天然气水合物分解与甲烷归宿研究进展

综述了近年来天然气水合物分解与甲烷归宿等方面的研究成果。天然气水合物的汇聚与地质构造或地层圈闭有关,其溶解受物质转换控制,分解则受热转换控制。水合物释放甲烷的运移方式包括分散式、中心式和大规模排放式。缺氧氧化和耗氧氧化是甲烷在海洋环境中的2种主要转化方式。天然气水合物释放甲烷的最终归宿主要为：①重新形成天然气水合物;②形成化能自养生物群落和沉淀出碳酸盐沉积;③与氧发生氧化后转变为CO2;④直接排放进入到大气中。沉积物中的微构造、化能自养生物群落、自生碳酸盐矿物及其碳氧同位素组成是水合物释放事件的指纹记录。     

Application of frequency division inversion in the prediction of heterogeneous natural gas hydrates reservoirs in the Shenhu Area,South China Sea

Drilling results suggest that the thickness of natural gas hydrates (NGHs) in the Shenhu Area, South China Sea (SCS) are spatially heterogenous, making it difficult to accurately assess the NGHs resources in this area. In the case that free gas exists beneath hydrate deposits, the frequency of the hydrate deposits will be noticeably attenuated, with the attenuation degree mainly affected by pore development and free gas content. Therefore, the frequency can be used as an important attribute to identify hydrate reservoirs. Based on the time-frequency characteristics of deposits, this study predicted the spatial distribution of hydrates in this area using the frequency division inversion method as follows. Firstly, the support vector machine (SVM) method was employed to study the amplitude versus frequency (AVF) response based on seismic and well logging data. Afterward, the AVF response was introduced as independent information to establish the nonlinear relationship between logging data and seismic waveform. Then, the full frequency band information of the seismic data was fully utilized to obtain the results of frequency division inversion. The inversion results can effectively broaden the frequency band, reflect the NGHs distribution, and reveal the NGHs reservoirs of two types, namely the fluid migration pathway type and the in situ self-generation self-storage diffusion type. Moreover, the inversion results well coincide with the drilling results. Therefore, it is feasible to use the frequency division inversion to predict the spatial distribution of heterogeneous NGHs reservoirs, which facilitates the optimization of favorable drilling targets and is crucial to the resource potential assessment of NGHs.©2022 China Geology Editorial Office.     

Experimental study on characteristics of pore water conversion during methane hydrates formation in unsaturated sand

Understanding the pore water conversion characteristics during hydrate formation in porous media is important to study the accumulation mechanism of marine gas hydrate. In this study, low-field NMR was used to study the pore water conversion characteristics during methane hydrate formation in unsaturated sand samples. Results show that the signal intensity of T₂ distribution isn’t affected by sediment type and pore pressure, but is affected by temperature. The increase in the pressure of hydrogen-containing gas can cause the increase in the signal intensity of T₂ distribution. The heterogeneity of pore structure is aggravated due to the hydrate formation in porous media. The water conversion rate fluctuates during the hydrate formation. The sand size affects the water conversion ratio and rate by affecting the specific surface of sand in unsaturated porous media. For the fine sand sample, the large specific surface causes a large gas-water contact area resulting in a higher water conversion rate, but causes a large water-sand contact area resulting in a low water conversion ratio (C_w=96.2%). The clay can reduce the water conversion rate and ratio, especially montmorillonite (C_w=95.8%). The crystal layer of montmorillonite affects the pore water conversion characteristics by hindering the conversion of interlayer water.©2022 China Geology Editorial Office.     

Correlations between the in situ acoustic properties and geotechnical parameters of sediments in the Yellow Sea,China

Knowledge about the marine sediment acoustic properties is a key to understanding wave propagation in sediments and is very important for military oceanography and ocean engineering. We developed a hydraulic-drived self-contained in situ sediment acoustic measurement system, and measured for the first time the in situ acoustic properties of sediments on 78 stations in the Yellow Sea, China, by employing this system. The relationships between the in situ measured acoustic properties and the onboard or laboratory determined geotechnical parameters were analyzed. Porosity was found to be the dominant factor in reducing velocity in a quadratic fashion; velocity showed an increment with bulk density and a decrement with mean grain size and clay content both with a nonlinear dependence; acoustic attenuation showed a bell-shaped correlation with porosity and mean grain size but reduced with clay content of the sediments. The attenuation results indicate that intergrain friction rather than viscous interactions between pore fluid and solid grains is the dominant loss mechanism in our marine sediments. The relationships established would be used to predict the geotechnical parameters from in situ measured acoustic properties and vice versa, as well as being an indicator of the seafloor processes, potential gas bubbles hazard and gas hydrates resources or other suitable targets of acoustic surveys.     

海底天然气水合物地球化学勘探新技术

天然气水合物是目前寻找新型替代能源的热点之一，其勘探、开发和利用的科学与技术是当前面临的重大课题。除地球物理方法可对天然气水合物定位外，地球化学勘探也是寻找它的重要手段。天然气水合物的几种地球化学勘探方法分别利用其直接标志和间接标志。直接标志包括烃类气体含量测定等；间接标志包括孔隙水离子浓度异常、同位素地球化学异常、标志性矿物(标型矿物)及沉积物热释光分析等方法。     

The methane hydrate formation and the resource estimate resulting from free gas migration in seeping seafloor hydrate stability zone

It is a typical multiphase flow process for hydrate formation in seeping seafloor sediments. Free gas can not only be present but also take part in formation of hydrate. The volume fraction of free gas in local pore of hydrate stable zone (HSZ) influences the formation of hydrate in seeping seafloor area, and methane flux determines the abundance and resource of hydrate-bearing reservoirs. In this paper, a multiphase flow model including water (dissolved methane and salt)-free gas hydrate has been established to describe this kind of flow-transfer-reaction process where there exists a large scale of free gas migration and transform in seafloor pore. In the order of three different scenarios, the conversions among permeability, capillary pressure, phase saturations and salinity along with the formation of hydrate have been deducted. Furthermore, the influence of four sorts of free gas saturations and three classes of methane fluxes on hydrate formation and the resource has also been analyzed and compared. Based on the rules drawn from the simulation, and combined information gotten from drills in field, the methane hydrate(MH) formation in Shenhu area of South China Sea has been forecasted. It has been speculated that there may breed a moderate methane flux below this seafloor HSZ. If the flux is about 0.5 kg m⁻² a⁻¹, then it will go on to evolve about 2700 ka until the hydrate saturation in pore will arrive its peak (about 75%). Approximately 1.47 × 10⁹ m³ MH has been reckoned in this marine basin finally, is about 13 times over preliminary estimate.