Gas hydrate systems at Hydrate Ridge offshore Oregon inferred from molecular and isotopic properties of hydrate-bound and void gases

We report and discuss molecular and isotopic properties of hydrate-bound gases from 55 samples and void gases from 494 samples collected during Ocean Drilling Program (ODP) Leg 204 at Hydrate Ridge offshore Oregon. Gas hydrates appear to crystallize in sediments from two end-member gas sources (deep allochthonous and in situ) as mixtures of different proportions. In an area of high gas flux at the Southern Summit of the ridge (Sites 1248-1250), shallow (0-40 m below the seafloor [mbsf]) gas hydrates are composed of mainly allochthonous mixed microbial and thermogenic methane and a small portion of thermogenic C₂₊ gases, which migrated vertically and laterally from as deep as 2- to 2.5-km depths. In contrast, deep (50-105 mbsf) gas hydrates at the Southern Summit (Sites 1248 and 1250) and on the flanks of the ridge (Sites 1244-1247) crystallize mainly from microbial methane and ethane generated dominantly in situ. A small contribution of allochthonous gas may also be present at sites where geologic and tectonic settings favor focused vertical gas migration from greater depth (e.g., Sites 1244 and 1245). Non-hydrocarbon gases such as CO₂ and H₂S are not abundant in sampled hydrates. The new gas geochemical data are inconsistent with earlier models suggesting that seafloor gas hydrates at Hydrate Ridge formed from gas derived from decomposition of deeper and older gas hydrates. Gas hydrate formation at the Southern Summit is explained by a model in which gas migrated from deep sediments, and perhaps was trapped by a gas hydrate seal at the base of the gas hydrate stability zone (GHSZ). Free gas migrated into the GHSZ when the overpressure in gas column exceeded sealing capacity of overlaying sediments, and precipitated as gas hydrate mainly within shallow sediments. The mushroom-like 3D shape of gas hydrate accumulation at the summit is possibly defined by the gas diffusion aureole surrounding the main migration conduit, the decrease of gas solubility in shallow sediment, and refocusing of gas by carbonate and gas hydrate seals near the seafloor to the crest of the local anticline structure.     

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。     

Velocity-porosity relationships in hydrate-bearing sediments measured from pressure cores,Shenhu Area,South China Sea

Evaluating velocity-porosity relationships of hydrate-bearing marine sediments is essential for characterizing natural gas hydrates below seafloor as either a potential energy resource or geohazards risks. Four sites had cored using pressure and non-pressure methods during the gas hydrates drilling project (GMGS4) expedition at Shenhu Area, north slope of the South China Sea. Sediments were cored above, below, and through the gas-hydrate-bearing zone guided with logging-while-drilling analysis results. Gamma density and P-wave velocity were measured in each pressure core before subsampling. Methane hydrates volumes in total 62 samples were calculated from the moles of excess methane collected during depressurization experiments. The concentration of methane hydrates ranged from 0.3% to 32.3%. The concentrations of pore fluid (25.44% to 68.82%) and sediments (23.63% to 54.28%) were calculated from the gamma density. The regression models of P-wave velocity were derived and compared with a global empirical equation derived from shallow, unconsolidated sediments data. The results were close to the global trend when the fluid concentration is larger than the critical porosity. It is concluded that the dominant factor of P-wave velocity in hydrate-bearing marine sediments is the presence of the hydrate. Methane hydrates can reduce the fluid concentration by discharging the pore fluid and occupying the original pore space of sediments after its formation.©2022 China Geology Editorial Office.     

东太平洋水合物海岭BSR以上沉积物粒度变化与气体水合物分布

文中对国际大洋钻探204航次在太平洋水合物海岭8 个站位BSR深度以上气体水合物稳定带的沉积物进行了粒度分析和对比研究。结果表明,该稳定带内沉积物总体粒径变化特征为:粉砂质量分数在60%~75%之间,为气体水合物稳定带内沉积组分的主体组分。粘土质量分数一般小于35%,砂质量分数小于5%。该结果获得的粒径变化范围,与204 航次中沉积学研究所确定的粘土质粉砂、粉砂质粘土夹含砂质粉砂、含砂质粘土岩性特征一致。各站位沉积粒径变化和代表气体水合物存在的岩心红外照相IR异常低温记录之间的初步对比说明,气体水合物主要富集在沉积组分较粗,相当于粉砂或者砂级质量分数较高的粒度层。统计学的相关性研究结果定量地揭示了各个站位沉积物粒径变粗与气体水合物的存在有不同的相关关系。归纳起来发现,不同构造部位沉积物中气体水合物赋存层段的粒径范围不同。坡后盆地由于当地总体沉积物颗粒细,气体水合物赋存在极细粉砂粒级(8~26μm)的沉积物中。水合物海岭南峰顶部附近站位气体水合物主要赋存在粗粉砂和细砂(50~148μm)之间。     

Characteristic features of the occurrence of gas-fluid emanations on the northeastern slope of Sakhalin Island, Sea of Okhotsk

This paper summarizes the results of combined studies in the areas of the occurrence of gas-fluid emanations in the water column, on the seafloor, and in the upper part of the sedimentary section on the northeastern slope of Sakhalin Island (Sea of Okhotsk). The phenomena typical of methane seeps were characterized in detail: the presence of acoustic anomalies, high concentrations of methane in the water and sediments, and the specific features of the sedimentary section (the textural and structural features, the character of the mineral inclusions and gas hydrates, and the chemical composition). The component composition of the gases (including the accompanying gas hydrates), which is almost free of heavy hydrocarbon homologues of methane; the light carbon isotopic compositions of the methane and carbonate concretions; and the low temperatures of the near-bottom water and sediments suggest that the occurrence of numerous methane emanations is related to gas generation in the upper part of the sedimentary sequence. No evidence was found for the existence of a deep center of gas formation within the seafloor area considered. Typical submarine mud volcanic edifices were also not found.     

论河北丰宁牛圈银（金）矿床的成矿时限问题

南沙海槽的构造和沉积受控于南海的构造运动和加里曼丹西北大陆边缘的演化,具有适于天然气水合物形成的物源基础、温压条件、输导系统和储藏场所。似海底反射层(BSR)出现在水深650~2 800 m、海底下65~350 m深的晚中新世沉积物中,与褶皱、逆冲推覆构造及穹窿构造有关;沉积物中的甲烷含量和孔隙水的SO24-含量表现出异常变化特征,硫酸盐-甲烷界面(SMI)深度仅为8~11 m;表层沉积的自生石膏和黄铁矿的成岩环境与甲烷流体排溢引起的厌氧甲烷氧化(AOM)有关,这些地球物理和地球化学指标均指示南沙海槽发育天然气水合物。研究表明,南沙海槽沉积物的甲烷以二氧化碳还原型微生物成因为主,少量为混合气,海槽东南部可能是最有潜力的天然气水合物远景区。     

A natural hydrate dissolution experiment on complex multi-component hydrates on the sea floor

Dissolution of natural hydrate cores was measured using time-lapse photography on the seafloor at Barkley Canyon (850 m depth and 4.17 °C). Two types of hydrate fabrics in close contact with one another were studied: a “yellow” hydrate stained with condensate oil and a “white” hydrate. From thermogenic origins, both fabrics contained methane as well as heavier hydrocarbons. These multi-component hydrates were calculated to be well within p-T stability conditions (<200 m water depth needed at 4.17 °C). While stable in pressure and temperature, the hydrates were bathed in under-saturated seawater, which promoted dissolution. The flux of gas from the shrinking yellow hydrate core was 0.15 ± 0.01 mmol gas/m² s, while the white hydrate dissolved faster at 0.25 ± 0.02 mmol gas/m² s. To determine the controlling mechanism for the observed changes in the hydrate cores, experimental results were compared with an engineering correlation for convective mass transfer. Using water velocity as a fitting parameter, the correlation agreed well with results from a previous dissolution experiment on well-characterized synthetic hydrates. Even with a number of other unknowns, when applied to the natural hydrate, the mass transfer correlation predicted the dissolution rate within 20%. This seafloor-based experiment, along with visual observations of seafloor hydrate dissolution over a 3-day period, were used to further understand the fate of natural seafloor hydrates exposed on the seafloor. By showing that mass transfer is the rate-controlling mechanism for dissolution of these natural hydrate outcrops, proper hydrodynamic calculations can be employed to give a refined estimate on hydrate dissolution rates.     

Geothermal modeling for the base of gas hydrate stability zone and saturation of gas hydrate in the Krishna-Godavari basin,eastern Indian margin

The passive eastern Indian margin is rich in gas hydrates, as inferred from the wide-spread occurrences of bottom-simulating reflectors (BSRs) and recovery of gas hydrate samples from various sites in the Krishna Godavari (KG) and Mahanadi (MN) basins drilled by the Expedition 01 of the Indian National Gas Hydrate Program (NGHP). The BSRs are often interpreted to mark the thermally controlled base of gas hydrate stability zone (BGHSZ). Most of the BSRs exhibit moderate to typically higher amplitudes than those from other seismic reflectors. We estimate the average geothermal gradient of ∼40°C/km and heat flow varying from 23 to 62 mW/m² in the study area utilizing the BSR’s observed on seismic sections. Further we provide the BGHSZ where the BSR is not continuous or disturbed by local tectonics or hidden by sedimentation patterns parallel to the seafloor with a view to understand the nature of BSR.     

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.     

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.     

国际天然气水合物勘查开发研究新进展——第七届爱丁堡国际天然气水合物大会特邀报告综述

简要介绍了2011年7月在英国爱丁堡召开的第七届国际天然气水合物大会概况。对会议中5个大会特邀主题报告给予介绍或评述。Thomas介绍了亨弗利·戴维对科学发现的追求和应用,后者在实验室发现了气水合物。Ripmeeste总结了实验模拟中对气水合物客体与载体相互作用、水合物形成和分解过程的认识和成果。Suess指出过去25年间人们对海洋天然气水合物的研究经历了从“避免策略到旨在获取”、“能源开发和二氧化碳储存兼顾”、“追求储量到记录环境变化”3个阶段。Kurihara总结了日本多年的研发结果,包括数字模拟研究、对甲烷储层的分类和产气能力的评估、天然气生产方法等,讨论了商业发展甲烷水合物的可行性和挑战。Sloan介绍了管道安全复杂体系的4种概念性端元类型,并指出风险管理策略比防治更为经济,是未来防止水合物堵塞的重要工具。     

Dissolution rates of pure methane hydrate and carbon-dioxide hydrate in undersaturated seawater at 1000-m depth

To help constrain models involving the chemical stability and lifetime of gas clathrate hydrates exposed at the seafloor, dissolution rates of pure methane and carbon-dioxide hydrates were measured directly on the seafloor within the nominal pressure-temperature (P/T) range of the gas hydrate stability zone. Other natural boundary conditions included variable flow velocity and undersaturation of seawater with respect to the hydrate-forming species. Four cylindrical test specimens of pure, polycrystalline CH₄ and CO₂ hydrate were grown and fully compacted in the laboratory, then transferred by pressure vessel to the seafloor (1028 m depth), exposed to the deep ocean environment, and monitored for 27 hours using time-lapse and HDTV cameras. Video analysis showed diameter reductions at rates between 0.94 and 1.20 μm/s and between 9.0 and 10.6 · 10⁻² μm/s for the CO₂ and CH₄ hydrates, respectively, corresponding to dissolution rates of 4.15 ± 0.5 mmol CO₂/m²s and 0.37 ± 0.03 mmol CH₄/m²s. The ratio of the dissolution rates fits a diffusive boundary layer model that incorporates relative gas solubilities appropriate to the field site, which implies that the kinetics of the dissolution of both hydrates is diffusion-controlled. The observed dissolution of several mm (CH₄) or tens of mm (CO₂) of hydrate from the sample surfaces per day has major implications for estimating the longevity of natural gas hydrate outcrops as well as for the possible roles of CO₂ hydrates in marine carbon sequestration strategies.     

Gas Sources of Natural Gas Hydrates in the Shenhu Drilling Area, South China Sea: Geochemical Evidence and Geological Analysis

The Shenhu gas hydrate drilling area is located in the central Baiyun sag, Zhu Ⅱ depression, Pearl River Mouth basin, northern South China Sea. The gas compositions contained in the hydrate-bearing zones is dominated by methane with content up to 99.89% and 99.91%. The carbon isotope of the methane (δ13C1 ) are 56.7‰ and 60.9‰, and its hydrogen isotope (δD) are 199‰ and 180‰, respectively, indicating the methane from the microbial reduction of CO2 . Based on the data of measured seafloor temperature and geothermal gradient, the gas formed hydrate reservoirs are from depths 24-1699 m below the seafloor, and main gas-generation zone is present at the depth interval of 416-1165 m. Gas-bearing zones include the Hanjiang Formation, Yuehai Formation, Wanshan Formation and Quaternary sediments. We infer that the microbial gas migrated laterally or vertically along faults (especially interlayer faults), slump structures, small-scale diapiric structures, regional sand beds and sedimentary boundaries to the hydrate stability zone, and formed natural gas hydrates in the upper Yuehai Formation and lower Wanshan Formation, probably with contribution of a little thermogenic gas from the deep sedments during this process.     

水力输送法开采海底浅层天然气水合物技术研究

海洋天然气水合物占全球水合物总储量的99%,海洋天然气水合物大部分沉积在海底浅层没有良好的覆盖层,无法采用开采传统油气资源的方法进行开采.为了开采海底浅层天然气水合物,分析了海洋天然气水合物的存在类型及地质特征,探讨了目前开采海洋天然气水合物的理论方法及局限性.根据海底天然气水合物成矿的地质特点及水合物的物理特性,提出了以水力输送技术为主要理论的海洋浅层天然气水合物开采方法.该方法克服了其他方法开采海底天然气水合物面临的技术困难,为海洋天然气水合物的开采提供了技术基础及理论支撑.     

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.     

海底沉积物孔隙水钡循环对天然气渗漏的指示

冷泉流体的渗漏活动强烈地影响着海底沉积物孔隙水钡循环。冷泉流体中的Ba2+ 向上扩散与孔隙水硫酸盐反应,在硫酸盐—碳氢化合物转化带（SHT）之上沉淀重晶石。随着沉积物的埋藏,先前沉淀的重晶石被埋藏于SHT之下的硫酸盐亏损带,将发生溶解,溶解的钡向上扩散,在SHT之上再次沉淀重晶石。当体系中向上扩散的Ba2+超过埋藏的重晶石中的钡时,在剖面上形成“钡锋”。向上渗漏的碳氢化合物（甲烷为主）通量控制了SHT的深度,二者之间存在很好的地球化学耦合关系,从而,可以用“钡锋”来评价天然气渗漏活动的特征。在总结和分析国际海底冷泉渗漏活动区沉积物孔隙水的甲烷和钡循环的研究进展基础上,综述了海底沉积物孔隙水钡循环对现在和过去天然气渗漏的指示,总结了渗漏成因重晶石的地质和地球化学特征。     

不同类型天然气水合物真空分解过程实验研究

在放置于恒温室内的真空装置内,对合成的冰粉-气体水合物(包括甲烷、乙烷、丙烷、正丁烷-氮气、异丁烷、混合气水合物)、冰粉-不同粒度多孔介质甲烷水合物和祁连山冻土区及南海神狐海域天然气水合物进行了分解实验研究,初步探讨了不同气体水合物分解动力学特征和分解规律。实验结果表明,合成的冰粉-气体水合物的分解过程相似,除丙烷水合物和异丁烷水合物外,分解压力基本呈单调增长,均未出现明显的自保护效应;不同粒度多孔介质中甲烷水合物分解过程,压力增长呈现“快→慢→快”的特点,主要原因可能是多孔介质中的水合物尺寸较大,分解时更易产生自保护效应;祁连山冻土区天然气水合物的分解压力曲线与不同粒度多孔介质中甲烷水合物的相似,总体呈现“快→慢→快”的特点,水合物自保护效应明显;南海神狐海域天然气水合物分解气体压力变化虽然总体与祁连山冻土区天然气水合物压力增长过程相似,但同时呈现“阶梯状”增长,这可能与两种不同水合物岩心的岩性和水合物在岩心中的分布模式和赋存状态有关。     

与海洋天然气水合物微纳米尺度赋存和开采储存技术有关的研究进展

天然气水合物是一类潜在的储量巨大的清洁能源.近年来,水合物的研究已经逐渐拓展至纳米、介观层面.纳米科学贯穿了水合物研究的全过程,包括上游天然气水合物成藏、开采和下游的储运、分离等水合物应用技术,其核心在于研究水合物在纳米材料表面、内部、间隙中生长和分解的传质传热过程.将以第九届国际水合物大会（ICGH9）为切入点,从水合物成藏、开采和下游技术应用几个方面综述近年来水合物研究中的纳米研究进展.目前对水合物的研究尺度并未做到全覆盖,水合物在纳米材料间隙中的传质传热过程研究较少,纳米材料的累积放大效应研究也存在空白.这正是水合物成藏、开采研究中的瓶颈问题.未来的研究应该着眼于水合物在纳米材料中生成和分解的传质传热作用,以此为主线将水合物技术和水合物成藏、开采研究中的核心问题进行统一协同研究.      

基于天然气水合物地震数据计算南海北部陆坡海底热流

天然气水合物是一种由水的冰晶格架及其间吸附的气体分子（以甲烷为主）组成的固态化合物,地震剖面上的似海底反射BSR是天然气水合物赋存的重要地球物理标志。相同气体成分水合物的相对稳定的温压关系是根据BSR的赋存深度计算海底热流的理论基础。选择南海北部陆坡有典型BSR反射的地震剖面,计算了南海北部陆坡天然气水合物发育区的压力、温度、地温梯度、热导率及热流等地热参数。通过计算热流值与实测热流值的对比可以大致推测,在南海北部陆坡海底运用该方法计算的热流值误差可能在12％以内。本研究不仅可以为海底热流等理论研究提供一定信度的数据资料,而且通过实测热流值校正后的热流数据以及经验公式,可以反过来用于BSR深度的计算以及天然气水合物稳定域的预测,具有重要的实践意义。     

天然气水合物成因探讨

天然气水合物是未来的能源资源。其分布于极地地区、深海地区及深水湖泊中。在海洋里,天然气水合物主要分布于外大陆边缘和洋岛的周围,其分布与近代火山的分布范围具有一致性。同位素组成表明天然气水合物甲烷主要是由自养产甲烷菌还原CO₂形成的。典型的大陆边缘沉积物有机碳含量低（＜0．5％～1．0％）,不足以产生天然气水合物带高含量的甲烷。赋存天然气水合物的沉积物时代主要为晚中新世-晚上新世,具有一定的时限性,并且天然气水合物与火山灰或火山砂共存,表明其形成与火山-热液体系有一定联系。火山与天然气水合物空间上的一致性表明,天然气水合物甲烷的底物可能主要是由洋底火山喷发带来的CO2。由前人研究结果推断 HCO^－₃在脱去两个O原子的同时,可能发生了亲核重排,羟基 H原子迁移到 C原子上,形成了甲酰基（HCO^－）,使甲烷的第一个 H原子来源于水。探讨了甲烷及其水合物的形成机制,提出了天然气水合物成因模型。