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.     

http://www.sciencedirect.com/science/article/pii/S1674987114000668

Microbial diversity in the hydrate-containing (sites SH3B and SH7B) and-free (sites SH1B, SH5B, SH5C) sediments collected from the Shenhu area of the South China Sea (SCS) was investigated using 16S rR...     

南海北部九龙甲烷礁邻区沉积物层中垂向细菌群落结构特征研究

本研究应用微生物16S rRNA-DGGE和T-RFLP技术,结合环境参数,对我国天然气水合物潜在区南海九龙甲烷礁附近973-4柱状样沉积物中3个层位12个不同深度(表层20 cm至382 cm,中层552 cm至796 cm,深层862 cm至1 196 cm)细菌群落结构及其分布进行了对比研究.其中T-RFLP实验表明,细菌丰度、香农指数和均匀度变化趋势相同,由深层到716 cm处先降后升,中层716 cm深度范围处微生物群落丰度、均匀度、香农指数相对较高,716 cm至表层先降后升.DGGE图谱和T-RFLP色谱峰聚类分析表明:表层20 cm至192 cm相似性较高,表层236 cm至382 cm与深层1 082 cm、1 196 cm群落结构相似性较高,但中层沉积物中微生物群落结构与表层及深层均有较大差异.环境参数表明中层甲烷含量较高,推测甲烷是影响微生物群落结构差异的主要因素之一.T-RFLP色谱峰与微生物数据库比对及DGGE条带测序也表明了:本区变形杆菌(Proteobacteria)为优势菌群,其中α-、γ-、δ-变形杆菌(Proteobacteria)为主要的细菌亚群,其他细菌包括放线菌(Actinobacteria)、厚壁菌门(Firmicutes)、绿弯菌门(Chloroflexi)为次优势菌群.甲烷含量较高的中层,甲烷氧化菌(Methanotrophs),硫还原菌(Sulfate-reducing bacteria)等与甲烷密切相关的细菌均有被检测到,表明该区域存在与天然气水合物的分解释放相关的微生物群落.     

祁连山冻土区天然气水合物DK一2钻孔微生物群落

对青海省祁连山永久冻土区天然气水合物DK一2钻孔的11件样品进行分析,通过微生物群落分析来探寻水合物层样品与非水合物层样品的差别。在11件样品中均发现了细菌16SrDNA,未检测到海洋天然气水合物地区常见的古菌16SrDNA、mc以（I,Ⅱ）、pmoA、mmoX和mxaF。分析得到的细菌16SrDNA分属5个门,包括变形杆菌门、放线菌门、拟杆菌门、厚壁菌门和异常球菌一栖热菌门,随着样品深度的增加,细菌多样性有降低的趋势。对非水合物层样品DK2—19和水合物层样品DK2—25进行细菌系统发育树分析,发现这2个样品群落结构相差较大。水合物层样品与非水合物层样品细菌群落对比后发现,水合物层样品中叫一变形杆菌的比例低于非水合物层样品中1一变形杆菌的比例,而Arthrobacter属多发现于非水合物层的样品中。     

南海北部海区海底沉积物中孔隙水的Cl~-和SO_4~(2-)浓度异常特征及其对天然气水合物的指示意义

报道了中国南海北部海区海底沉积物中孔隙水的Cl-和SO42-质量浓度的变化特征, 圈定了孔隙水中Cl-质量浓度的高值异常区。由于水合物形成过程中的排盐效应, 会使其上覆浅表层沉积物中孔隙水的盐度增高, 因此这些氯离子的高值异常区值得进一步的勘查。对孔隙水中SO42-的质量浓度分析表明, 研究区的一些站位表现出随深度增加SO42-的质量浓度梯度发生明显的变化, 计算的硫酸盐甲烷交接带SMI界面深度均在 10m左右, 与ODP164航次和ODP204航次有天然气水合物的钻孔的SMI界面深度基本吻合, 说明这些站位深部有天然气水合物存在的可能性。     

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.     

海洋天然气水合物钻井的硅酸盐钻井液研究

在海洋含天然气水合物地层中钻进时,遇到的问题有水合物在井底的分解和管线内的再生成,以及井壁稳定和井涌的问题。配制合适的钻井液是解决上述问题的关键。通过大量实验,得到一种加入无机盐和动力学抑制剂的稀硅酸盐钻井液,并通过实验对其性能进行评价。结果表明:配制的硅酸盐钻井液不仅能满足常规钻井液携带岩屑和清洁井眼的要求,还能有效抑制井壁岩层的水化,抑制水合物地层的分解,以及控制水合物在管线内的再生成;因此可以满足深水含水合物地层钻进的要求,确保水合物地层钻探安全高效地进行。     

海底水合物地球化学探测方法的试验研究

选择西沙海槽水合物潜在富集区作为已知区 ,利用陆上油气地球化学勘查方法 (酸解烃、热释烃、蚀变碳酸盐方法 )开展了试验性研究。通过对海底浅表层沉积物各项测试指标的分析 ,发现酸解烃方法效果好 ,而热释烃方法和蚀变碳酸盐方法的试验效果并不理想。同时还对海底浅表层沉积物酸解烃重新进行了释义 ,认为酸解烃方法适合于海底水合物的勘查 ,值得进一步推广     

祁连山冻土区天然气水合物现场识别方法

天然气水合物是一种赋存在低温、高压条件下,陆上永久冻土区和海底沉积物中的规模巨大的新型能源。在冻土区的天然气水合物研究过程中,钻探取样和天然气水合物岩芯研究仍是识别和推断天然气水合物最直接有效的方法。因此,如何在钻探现场快速有效地识别出天然气水合物及相关异常特征就显得极其重要。近几年在祁连山天然气水合物勘探过程中,探索性地总结出适用于冻土区的天然气水合物现场识别方法,主要包括肉眼观测、孔口气涌观测、岩芯红外测温、岩芯裂隙孔隙水盐度测定、岩芯气体解析与组分测定和岩芯次生构造与伴生矿物鉴别等方法。利用该套现场识别方法和随钻岩芯编录,有效地查明了祁连山冻土区天然气水合物在岩芯中的产状和分布特征,为该区天然气水合物资源评价和试开采试验提供了重要依据。     

Petroleum degradation and associated microbial signatures at the Chapopote asphalt volcano, Southern Gulf of Mexico

At the Chapopote Knoll in the Southern Gulf of Mexico, deposits of asphalt provide the substrate for a prolific cold seep ecosystem extensively colonized by chemosynthetic communities. This study investigates microbial life and associated biological processes within the asphalts and surrounding oil-impregnated sediments by analysis of intact polar membrane lipids (IPLs), petroleum hydrocarbons and stable carbon isotopic compositions (δ¹³C) of hydrocarbon gases. Asphalt samples are lightly to heavily biodegraded suggesting that petroleum-derived hydrocarbons serve as substrates for the chemosynthetic communities. Accordingly, detection of bacterial diester and diether phospholipids in asphalt samples containing finely dispersed gas hydrate suggests the presence of hydrocarbon-degrading bacteria. Biological methanogenesis contributes a substantial fraction to the methane captured as hydrate in the shallow asphalt deposits evidenced by significant depletion in ¹³C relative to background thermogenic methane. In sediments, petroleum migrating from the subsurface stimulates both methanogenesis and methanotrophy at a sulfate-methane transition zone 6-7 m below the seafloor. In this zone, microbial IPLs are dominated by archaeal phosphohydroxyarchaeols and archaeal diglycosidic diethers and tetraethers. Bacterial IPLs dominate surface sediments that are impregnated by severely biodegraded oil. In the sulfate-reduction zone, diagnostic IPLs indicate that sulfate-reducing bacteria (SRB) play an important role in petroleum degradation. A diverse mixture of phosphohydroxyarchaeols and mixed phospho- and diglycosidic archaeal tetraethers in shallow oil-impregnated sediments point to the presence of anaerobic methane-oxidizing ANME-2 and ANME-1 archaea, respectively, or methanogens. Archaeal IPLs increase in relative abundance with increasing sediment depth and decreasing sulfate concentrations, accompanied by a shift of archaeol-based to tetraether-based archaeal IPLs. The latter shift is suggested to be indicative of a community shift from ANME-2 and/or methanogenic archaea in shallower sediments to ANME-1/methanogenic archaea and possibly benthic archaea in deeper sediments.     

羌塘盆地沉积物热释光特征及潜在意义

热释光测量在探测陆地或海洋油气方面已显示出良好的应用效果,天然气水合物与常规油气在物源及运移机制上非常相似,可将热释光方法借鉴到天然气水合物的调查研究中。羌塘盆地147件沉积物样品的热释光测定结果表明,该区沉积物热释光具有近似对数正态分布的特征。结合前人研究结果及调查分析认为,该区热释光异常与深部油气或天然气水合物的对应模型为:矿藏上方出现热释光高值异常。研究区热释光高值异常出现2处集中分布区域,大致指示深部油气或天然气水合物藏的位置。研究结果对羌塘盆地油气或水合物的进一步调查研究有重要的参考价值。     

南海北部神狐海域地质环境综合调查及科学意义

在南海北部神狐海域水合物活跃区域开展了一次综合的海洋地质、物理海洋和生态环境调查,10个站位分布在水深1 000~4 000 m范围内的陆坡和深水盆地区域,是南海北部油气活跃的重要区域和天然气水合物试采区域.航次主要对10个海底站位进行了表层沉积物箱式和重力活塞柱状取样.针对天然气水合物试采区域,开展了一台"海燕"水下滑翔机的海洋物理环境连续走航剖面观测.利用海底地震仪在两个站位开展了连续海底地震和微振动观测.进行了站位的分层水体和沉积物样品中微生物学实验研究.初步航次结果展示了沉积物为黏土和软泥.站位和水下滑翔机走航观测提供了水体内海洋物理环境参数变化特征.海底地震仪观测展示了研究区天然地震活动和可能与水合物活动有关的微震动和短持续事件记录.微生物学实验揭示了沉积物中的微生物细菌群落特征.      

Dissociation of gas hydrates by hydrocarbon migration and accumulation-derived slope failures: An example from the South China Sea

The mechanism of slope failure associated with overpressure that is caused by hydrocarbon migration and accumulation remains unclear. High-resolution seismic data and gas hydrate drilling data collected from the Shenhu gas hydrate field (site SH5) offer a valuable opportunity to study the relations between submarine slope failure and hydrocarbon accumulation and flow that is associated with a ～2 km-diameter gas chimney developed beneath site SH5 where none gas hydrates had been recovered by drilling and sampling despite the presence of distinct bottom simulating reflectors (BSRs) and favorable gas hydrate indication. The mechanism of submarine slope failure resulted from buoyancy extrusion and seepage-derived deformation which were caused by overpressure from a ～1100 m-high gas column in a gas chimney was studied via numerical simulation. The ～9.55 MPa overpressure caused by hydrocarbons that migrated through the gas chimney and then accumulated beneath subsurface gas hydrate-bearing impermeable sediments. This may have resulted in a submarine slope failure, which disequilibrated the gas hydrate-bearing zone and completely decomposed the gas hydrate once precipitated at site SH5. Before the gas hydrate decomposition, the largely impermeable sediments overlying the gas chimney may have undergone a major upward deformation due to the buoyancy extrusion of the overpressure in the gas chimney, and slope failure was initiated from plastic strain of the sediments and reduced internal strength. Slope failure subsequently resulted in partial gas hydrate decomposition and sediment permeability increase. The pressurized gas in the gas chimney may have diffused into the overlying sediments controlled by seepage-derived deformation, causing an effective stress reduction at the base of the sediments and significant plastic deformation. This may have formed a new cycle of submarine slope failure and finally the total gas hydrate dissociation. The modeling results of buoyancy extrusion and seepage-derived deformation of the overpressure in the gas chimney would provide new understanding in the development of submarine slope failure and the link between slope failure and gas hydrate accumulation and dissociation.     

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。     

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.     

孔隙水中NH_4~+和HPO_4~(2-)浓度异常:一种潜在的天然气水合物地球化学勘查新指标

在海洋天然气水合物的勘查与研究中地球化学方法发挥了重大作用。利用海洋沉积物孔隙水中各种离子含量和同位素异常可以有效示踪天然气水合物的存在, 其中Cl-浓度异常、SO42-浓度梯度和氧同位素组成异常已成为指示天然气水合物存在的灵敏示踪剂。通过对比有和没有天然气水合物存在的海域浅表层沉积物中孔隙水的NH4+和HPO42-含量, 发现有天然气水合物区的孔隙水中NH4+和HPO42-浓度明显偏高, 且存在与SO42-类似的浓度梯度曲线, 认为孔隙水中NH4+和HPO42-浓度异常有可能成为一种新的地球化学示踪剂, 指示天然气水合物的存在; 探讨了引起孔隙水中NH +和HPO 2-浓度异常的可能机理及精确测定这些离子含量的方法。     

深水海底天然气水合物浅覆盖层钻井井壁稳定预测研究

以南海北部神狐海域天然气水合物浅覆盖层钻井井壁稳定为背景,对深水浅覆盖层钻井井壁稳定预测模型,南海沉积物物理、力学参数,以及神狐海域天然气水合物储集地层井壁稳定的研究现状进行分析和总结,探讨深水海底天然气水合物浅覆盖层钻井井壁稳定预测的难点和拟解决的方法,为深水海底天然气水合物浅覆盖层钻井井壁稳定预测提供支持。     

Effect of Agents on Hydrate Formation and Low-Temperature Rheology of Polyalcohol Drilling Fluid

In order to ensure safe drilling in deep water and marine gas hydrate bearing sediments,the needed characteristics of drilling fluid system were analyzed.Moreover,the effect of different agents on hydrate formation and the low-temperature rheology of designed polyalcohol drilling fluid were tested,respectively.The results show that clay can promote gas hydrate growth,while modified starch and polyalcohol can inhibit hydrate formation to some extent,and PVP K90 has a good performance on hydrate inhibition.Th...     

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。