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.     

Integrated core-log facies analysis and depositional model of the gas hydrate-bearing sediments in the northeastern continental slope,South China Sea

Host sediments may exert a significant influence on the formation of gas hydrate reservoirs. However, this issue has been largely neglected in the literature. In this study, we investigated the types, characteristics and the depositional model of the fine-grained gas hydrate-bearing sediments in the northeastern margin of the South China Sea by integrating core visual observations and logging-while-drilling downhole logs. The gas hydrate-bearing sediments consist dominantly of muddy sediments formed in the inter-canyon ridges of the upper continental slope, including hemipelagites, debrites (mud with breccia) and fine-grained turbidites. Cold-seep carbonates and associated slumping talus, muddy breccia debrites, as well as coarse-grained turbidites, may locally occur. Four classes and six sub-classes of log facies were defined by cluster analysis. Core-log correlation indicates that gas hydrates are majorly distributed in fine-grained sediments with high resistivity and low acoustic transit time (AC) log responses, which are easily differentiated from the fine-grained background sediments of high gamma-ray (GR), high AC, and low resistivity log values, and the seep carbonates characterized by low GR, high resistivity, high density, low AC and low porosity log values. The primary host sediments consist of fine-grained hemipelagic sediments formed by deposition from the nepheloid layers of river material and from the microfossils in seawater column. Most of the hemipelagic sediments, however, might have been extensively modified by slumping and associated gravity flow processes and were re-deposited in the forms of debrites and turbidites. Locally developed seep carbonates associated with gas hydrate dissociation and leakage provided additional sources for the gravity flow sediments.     

南海天然气水合物的形成和分布

从物理海洋、古气候、沉积环境和构造环境分析入手，研究了南海天然气水合物的形成条件。研究结果表明，在整个南海海域，天然气水合物生成的条件是存在差别的。南海，东北部，在氧同位素2、4、6期，由于菲律宾海的高盐度海水的注入，使这里的生物生产率特别高，陆坡上沉积了丰富的有机物质，加上此期间该处的沉积速率高，为天然气水合物的生成提供了物质条件；另外，自中新世末以来，由于菲律宾海板块与欧亚板块在台湾地区发生碰撞，对南海北部产生北西向挤压，加快了流体在沉积物中的活动，为天然气水合物的生成提供了良好的构造环境。因此认为南海东北部陆坡应是南海天然气水合物最丰富的地区。     

南海北部大陆边缘天然气水合物稳定带厚度的地热学研究

The exploration of unconventional and/or new energy resources has become the focus of energy research worldwide,given the shortage of fossil fuels.As a potential energy resource,gas hydrate exists only in the environment of high pressure and low temperature,mainly distributing in the sediments of the seafloor in the continental margins and the permafrost zones in land.The accurate determination of the thickness of gas hydrate stability zone is essential yet challenging in the assessment of the exploitation potential.The majority of previous studies obtain this thickness by detecting the bottom simulating reflectors(BSRs) layer on the seismic profiles.The phase equilibrium between gas hydrate stable state with its temperature and pressure provides an opportunity to derive the thickness with the geothermal method.Based on the latest geothermal dataset,we calculated the thickness of the gas hydrate stability zone(GHSZ) in the north continental margin of the South China Sea.Our results indicate that the thicknesses of gas hydrate stability zone vary greatly in different areas of the northern margin of the South China Sea.The thickness mainly concentrates on 200–300 m and distributes in the southwestern and eastern areas with belt-like shape.We further confirmed a certain relationship between the GHSZ thickness and factors such as heat flow and water depth.The thickness of gas hydrate stability zone is found to be large where the heat flow is relatively low.The GHSZ thickness increases with the increase of the water depth,but it tends to stay steady when the water depth deeper than 3 000 m.The findings would improve the assessment of gas hydrate resource potential in the South China Sea.     

天然气水合物的聚集和形成及南海地质条件分析

天然气水合物目前已经成为世界范围的一个研究热点，而我国的天然气水合物研究起步则相对较晚，通过阅读国内外有关文献，总结了天然气水合物在海底的分布特征，聚集和形成机制，产状及其形成机理，甲烷羽的形成过程，天然气水合物在沉积物中的聚集位置通常有两种情况：一是较浅的沉积物（海底以下几米）中，受控于泥底辟，泥火山，断层等；二是较深的沉积物（海底以下几十米，甚至更深）中，受控于流体，当断层延伸至海底时，通常在水合物聚集处的上部发现甲烷羽，天然气以溶解气，游离气或分子扩散的形式运移，在温，压适宜的沉积物中，即水合物稳定带内聚集并形成水合物，水合物的形成过程是：最初形成晶体，呈分散状分布于沉积物中，之后逐渐聚集，生长成结核状，层状，最后形成块状，在细粒的浅层沉积物中，通常以较慢的速度生长，形成分散状的水合物；而在粗粒沉积物中，水合物通常呈填隙状，并且这种产状可能位于较深层位中，我国南海在温度，压力，构造条件，天然气来源等方面都能满足天然气水合物的形成条件，并且在南海也发现了一些水合物存在的标志，如似海底反射层（BSR）以及孔隙水中氯离子浓度的降低。因此，天然气水合物在我国南海海域可能有很好的前景。     

南海北部天然气水合物研究进展

天然气水合物是一种新型的储量巨大的绿色能源,是目前世界各国研究界的研究热点之一。我国以及美国、日本、印度、韩国等国家都采集到了天然气水合物的实物样品。虽然我国对天然气水合物的研究起步较晚,但近年来的研究已经取得了飞速的进步,而且也于2007年5月在南海北部陆坡的神狐海域成功采集到天然气水合物的实物样品,这是在南海海域首次获取天然气水合物实物样品,证实了南海北部蕴藏着丰富的天然气水合物资源,标志着我国天然气水合物调查研究水平又上了一个新的台阶。目前,南海北部陆坡已经作为我国天然气水合物未来开发的战略选区之一。在总结我国天然气水合物以往十几年研究工作的基础上,综述了我国天然气水合物近年来在南海北部的地质、地球物理、地球化学3个方面的研究进展,提出了未来天然气水合物勘探和研究的方向和建议。     

浅剖资料在南海北部东沙西南海域水合物调查中的应用

南海北部东沙海域陆坡已经被证实为天然气水合物前景分布区,浅地层剖面数据以其高效率采集过程和浅表层高分辨率的特点被国内外学者应用到天然气水合物调查中并取得了很多成果。以南海北部东沙西南海域的两条浅剖测线为例,分析了该区浅表层沉积物的声学特征,并在浅剖剖面上发现了浅层含气带以及气体泄露现象,初步推测为深部的天然气水合物分解后通过断层运移到浅层中形成了浅层含气带,部分浅层气体还通过泄露点喷射到海水中从而形成了剖面中的气体泄露现象。最后,进一步通过对研究区域的沉积及气源条件、温压条件、地质及生物证据的讨论,证实该区具有天然气水合物发育的基本条件,因此,可以证实上述浅剖资料解释中关于天然气水合物的推测。     

Depositional characteristics and accumulation model of gas hydrates in northern South China Sea

The South China Sea (SCS) shows favorable conditions for gas hydrate accumulation and exploration prospects. Bottom simulating reflectors (BSRs) are widely distributed in the SCS. Using seismic and sequence stratigraphy, the spatial distribution of BSRs has been determined in three sequences deposited since the Late Miocene. The features of gas hydrate accumulations in northern SCS were systematically analyzed by an integrated analysis of gas source conditions, migration pathways, heat flow values, occurrence characteristics, and depositional conditions (including depositional facies, rates of deposition, sand content, and lithological features) as well as some depositional bodies (structural slopes, slump blocks, and sediment waves). This research shows that particular geological controls are important for the presence of BSRs in the SCS, not so much the basic thermodynamic controls such as temperature, pressure and a gas source. Based on this, a typical depositional accumulation model has been established. This model summarizes the distribution of each depositional system in the continental shelf, continental slope, and continental rise, and also shows the typical elements of gas hydrate accumulations. BSRs appear to commonly occur more in slope-break zones, deep-water gravity flows, and contourites. The gas hydrate-bearing sediments in the Shenhu drilling area mostly contain silt or clay, with a silt content of about 70%. In the continental shelf, BSRs are laterally continuous, and the key to gas hydrate formation and accumulation lies in gas transportation and migration conditions. In the continental slope, a majority of the BSRs are associated with zones of steep and rough relief with long-term alternation of uplift and subsidence. Rapid sediment unloading can provide a favorable sedimentary reservoir for gas hydrates. In the continental rise, BSRs occur in the sediments of submarine fans, turbidity currents.     

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.     

Seismic facies and specific character of the bottom simulating reflector on the western margin of Paramushir Island,Sea of Okhotsk

Seismic profiles from a venting area on the western margin of Paramushir Island (Sea of Okhotsk) reveal a local complex structure and an interesting, unusual pattern of the bottom simulating reflector (BSR). The BSR is gradual rising towards the venting area. The geothermal gradient and the bottom temperature confirmed the methane hydrate. The temperature appears to be the most important factor controlling the hydrate stability. A locally higher heat flow caused the upward migration of the hydrate stability field and the subsequent degradation of the hydrated sediments, causing gas vent formation and the flux of methane gas into the water column.     

东海天然气水合物的地球化学标志与找矿远景

利用大量的海底沉积物样品，开展了东海天然气水合物卫星热红外遥感和沉积物酸脱气地球化学找矿研究。根据卫星热红外增温异常和海底浅表层沉积烃类异常及其他各种异常标志，可以预测冲绳海槽中南部海域为最可能的水合物赋存区。     

Scale-dependent gas hydrate saturation estimates in sand reservoirs in the Ulleung Basin,East Sea of Korea

Through the use of 2-D and 3-D seismic data, several gas hydrate prospects were identified in the Ulleung Basin, East Sea of Korea and thirteen drill sites were established and logging-while-drilling (LWD) data were acquired from each site in 2010. Sites UBGH2–6 and UBGH2–10 were selected to test a series of high amplitude seismic reflections, possibly from sand reservoirs. LWD logs from the UBGH2–6 well indicate that there are three significant sand reservoirs with varying thickness. Two upper sand reservoirs are water saturated and the lower thinly bedded sand reservoir contains gas hydrate with an average saturation of 13%, as estimated from the P-wave velocity. The well logs at the UBGH2–6 well clearly demonstrated the effect of scale-dependency on gas hydrate saturation estimates. Gas hydrate saturations estimated from the high resolution LWD acquired ring resistivity (vertical resolution of about 5–8 cm) reaches about 90% with an average saturation of 28%, whereas gas hydrate saturations estimated from the low resolution A40L resistivity (vertical resolution of about 120 cm) reaches about 25% with an average saturation of 11%. However, in the UBGH2–10 well, gas hydrate occupies a 5-m thick sand reservoir near 135 mbsf with a maximum saturation of about 60%. In the UBGH2–10 well, the average and a maximum saturation estimated from various well logging tools are comparable, because the bed thickness is larger than the vertical resolution of the various logging tools. High resolution wireline log data further document the role of scale-dependency on gas hydrate calculations.     

南海北部神狐海域天然气水合物分布的主控因素

针对天然气水合物沉积成矿因素不明确等问题,通过利用南海北部神狐海域的高分辨率三维地震、测井和岩心等资料,对晚中新世以来的地层进行了高分辨率层序划分和精细的沉积解释。从温压、沉积、构造等方面探讨了神狐海域天然气水合物分布的主控因素,认为：BSR上部附近处于水合物稳定温压范围内;粗粒沉积物有利于天然气水合物的富集;在含水合物层段内,孔隙度与天然气水合物饱合度成正比关系;滑塌体是天然气水合物赋存的有利相带;气烟囱形成过程中产生的断裂系统可为富含甲烷流体向上运移提供通道,并在其上部滑塌体富集成矿。因此,神狐海域具备天然气水合物成藏的优越条件,是天然气水合物勘探开发的有利区块。     

用地球化学方法勘查中国南海的天然气水合物

天然气水合物是一种未来新型能源,赋存于低温高压环境下的海洋沉积物中,但也可形成于大陆永久冻土带中。天然气水合物资源量巨大,具有经济和环境上的研究意义。近年来,国际上己对天然气水合物的产况、分布和形成机理开展了大量研究,但国内这方面的工作还刚刚开展。对中国南海的调查表明该区存在天然气水合物赋存的有利地质条件、温压条件和富含有机质的沉积条件。在南海的许多海区还发现了指示天然气水合物存在的地震标志(BSR)。介绍了在南海天然气水合物勘查中的地球化学异常标志。这些地球化学异常的产生可能与天然气水合物的形成或分解过程有关。研究内容包括沉积物中气体含量(主要为甲烷和乙烷),甲烷的碳同位素,孔隙水中阴离子(Cl^-、SO4^2-等)、阳离子(Ca^2 、Mg^2 、Ba^2 、Sr^2 ,B^3 和NH4^ 等)浓度和δ^18,δD,δ^11B,及^87Sr／^86Sr等同位素组成,此外还对海底沉积物的热释光特征和紫外、可见、近红外反射光谱特征开展了探索性研究。通过进一步加强理论和实验研究,结合地球物理和地球化学资料,在不远的将来将会在南海发现和圈定天然气水合物矿藏。     

Mass-transport deposits and gas hydrate occurrences in the Ulleung Basin,East Sea – Part 2: Gas hydrate content and fracture-induced anisotropy

Mass-transport-deposits (MTDs) and hemipelagic mud interbedded with sandy turbidites are the main sedimentary facies in the Ulleung Basin, East Sea, offshore Korea. The MTDs show similar seismic reflection characteristics to gas-hydrate-bearing sediments such as regional seismic blanking (absence of internal reflectivity) and a polarity reversed base-reflection identical to the bottom-simulating reflector (BSR). Drilling in 2007 in the Ulleung Basin recovered sediments within the MTDs that exhibit elevated electrical resistivity and P-wave velocity, similar to gas hydrate-bearing sediments. In contrast, hemipelagic mud intercalated with sandy turbidites has much higher porosity and correspondingly lower electrical resistivity and P-wave velocity.At drill-site UBGH1-4 the bottom half of one prominent MTD unit shows two bands of parallel fractures on the resistivity log-images indicating a common dip-azimuth direction of about ∼230° (strike of ∼140°). This strike-direction is perpendicular to the seismically defined flow-path of the MTD to the north-east. At Site UBGH1-14, the log-data suggest two zones with preferred fracture orientations (top: ∼250°, bottom: ∼130°), indicating flow-directions to the north-east for the top zone, and north-west for the bottom zone. The fracture patterns may indicate post-depositional sedimentation that gave rise to a preferred fracturing possibly linked to dewatering pathways. Alternatively, fractures may be related to the formation of pressure-ridges common within MTD units.For the interval of observed MTD units, the resistivity and P-wave velocity log-data yield gas hydrate concentrations up to ∼10% at Site UBGH1-4 and ∼25% at Site UBGH1-14 calculated using traditional isotropic theories such as Archie's law or effective medium modeling. However, accounting for anisotropic effects in the calculation to honor observed fracture patterns, the gas hydrate concentration is overall reduced to less than 5%. In contrast, gas hydrate was recovered at Site UBGH1-4 near the base of gas hydrate stability zone (GHSZ). Log-data predict gas hydrate concentrations of 10–15% over an interval of 25 m above the base of GHSZ. The sediments of this interval are comprised of the hemipelagic mud and interbedded thin sandy turbidites, which did contain pore-filling gas hydrate as identified from pore-water freshening and core infra-red imaging. Seismically, this unit reveals a coherent parallel bedding character but has overall faint reflection amplitude. This gas-hydrate-bearing interval can be best mapped using a combination of regular seismic amplitude and seismic attributes such as Shale indicator, Parallel-bedding indicator, and Thin-bed indicator.     

Effects of fine grain size on distribution of Mn in shallow and deep water Black Sea sediments: A comparison between oxic and anoxic depositional environments

The uppermost 5–6 cm of the sediments (between 8 and 2248 m water depths) were studied to understand the effects of varying redox conditions on the Mn distribution in the recent sediments of the Black Sea. It was found that most Mn concentrations are consistent with the average abundance in crustal and/or sedimentary rocks. There exist no important differences between Mn concentrations in oxic (shallower water; <70 m) and anoxic (deeper water; 120 m) sediments. Previously reported Mn-enrichment above the Black Sea oxic/anoxic interface, due to the peculiar redox cycling, shows no significant contribution of Mn to the bottom sediments. A marked relationship between total Mn concentrations and clay/mud contents at shelf depth along the southern Black Sea margin indicates increased accumulation of Mn in association with the fine-grained particles and eastward water circulation.     

Structural-stratigraphic control on the Umitaka Spur gas hydrates of Joetsu Basin in the eastern margin of Japan Sea

Integrated geological, geochemical, and geophysical exploration since 2004 has identified massive accumulation of gas hydrate associated with active methane seeps on the Umitaka Spur, located in the Joetsu Basin on the eastern margin of Japan Sea. Umitaka Spur is an asymmetric anticline formed along an incipient subduction zone that extends throughout the western side of the Japanese island-arc system. Seismic surveys recognized chimney structures that seem strongly controlled by a complex anticlinal axial fault system, and exhibit high seismic amplitudes with apparent pull-up structures, probably due to massive and dense accumulation of gas hydrate. Bottom simulating reflectors are widely developed, in particular within gas chimneys and in the gently dipping eastern flank of the anticline, where debris can store gas hydrates that may represent a potential natural gas resource. The axial fault system, the shape of the anticline, and the carrier beds induce thermogenic gas migration to the top of the structure, and supply gas to the gas hydrate stability zone. Gas reaching the seafloor produces strong seepages and giant plumes in the sea water column.     

Sulfate reduction below the sulfate-methane transition in Black Sea sediments

A sudden increase in salinity about 7000 years ago caused a shift in the deposited sediments of the Black Sea from limnic to brackish-marine. Due to the development of an anoxic deep water basin and a relatively high sulfate concentration, organic matter is mineralized primarily through sulfate reduction in modern Black Sea sediments. Earlier studies showed that sulfate-reducing bacteria are abundant within the limnic sub-surface sediment in spite of extremely low concentrations of sulfate and organic carbon. A main objective of the present study was therefore to understand the depth distribution of sulfate reduction across the different sediment units, even deep below the sulfate-methane transition. Our study combined experimental measurements of sulfate reduction using ³⁵S radiotracer with analyses of sulfur and iron geochemistry in pore water and sediment. Potential sulfate reduction rates were measured with ³⁵S in sediment samples that were amended with sulfate and organic substrates and incubated in time-series up to 48 h. Sulfate reduction could thereby be detected and quantified at depths where concentrations of sulfate were otherwise too low to enable calculation of the rates. The results demonstrate that sulfate-reducing bacteria are active several meters below the sulfate-methane transition in Black Sea sediments. The cryptic sulfate reduction below the sulfate-methane transition may be driven by sulfate produced from re-oxidation of reduced sulfur species with oxidized iron minerals buried in the deep limnic sediment.     

Structural-stratigraphic control on the Umitaka Spur gas hydrates of Joetsu Basin in the eastern margin of Japan Sea

Integrated geological, geochemical, and geophysical exploration since 2004 has identified massive accumulation of gas hydrate associated with active methane seeps on the Umitaka Spur, located in the Joetsu Basin on the eastern margin of Japan Sea. Umitaka Spur is an asymmetric anticline formed along an incipient subduction zone that extends throughout the western side of the Japanese island-arc system. Seismic surveys recognized chimney structures that seem strongly controlled by a complex anticlinal axial fault system, and exhibit high seismic amplitudes with apparent pull-up structures, probably due to massive and dense accumulation of gas hydrate. Bottom simulating reflectors are widely developed, in particular within gas chimneys and in the gently dipping eastern flank of the anticline, where debris can store gas hydrates that may represent a potential natural gas resource. The axial fault system, the shape of the anticline, and the carrier beds induce thermogenic gas migration to the top of the structure, and supply gas to the gas hydrate stability zone. Gas reaching the seafloor produces strong seepages and giant plumes in the sea water column.     

Gas hydrate stability zone modelling in areas of salt tectonics and pockmarks of the Barents Sea suggests an active hydrocarbon venting system

The Barents Sea seabed exhibits an area of major glacial erosion exposing parts of the old hydrocarbon basins. In this region, we modelled the gas hydrate stability field in a 3D perspective, including the effects of higher order hydrocarbon gases. We used 3D seismic data to analyse the linkage between fluid-flow expressions and hydrate occurrences above old sedimentary basin systems and vertical faults. Pockmarks showed a relation to fault systems where some of them are directly connected to hydrocarbon bearing sedimentary formations. The influence of bottom water temperature, pore water salinity and geothermal gradient variation on gas hydrate stability zone (GHSZ) thickness is critically analysed in relation to both geological formations and salt tectonics. Our analysis suggests a highly variable GHSZ in the Barents Sea region controlled by local variations in the parameters of stability conditions. Recovery of gas-hydrate sample from the region and presence of gas-enhanced reflections below estimated BSR depths may indicate a prevalent gas-hydrate stable condition.