青海木里三露天天然气水合物土壤热释烃技术应用研究

吸附烃(酸解烃和热释烃)技术在常规油气地球化学勘查中已显示出良好的应用效果。选择青海木里三露天进行土壤热释烃地球化学方法试验,通过对土壤样品热释烃特征值和地球化学异常分布特征的分析,显示研究区已知矿藏区上方存在良好的土壤热释烃地球化学环状异常,异常的空间展布受到地下矿藏的控制,二者具有良好的对应关系 。通过对研究区烃类甲烷碳同位素分析,指示土壤热释烃地球化学异常为热解成因,与天然气水合物具有相似的成因类型。试验结果表明,土壤热释烃技术适用于天然气水合物地球化学勘查,能够圈出水合物矿藏范围,可与其他水合物化探技术互相补充。     

羌塘盆地泥火山发育区天然气水合物地球化学勘查

泥火山是天然气水合物赋存的标志之一,是天然气水合物存在的主要证据。羌塘盆地冻土区发育大量泥火山。对泥火山发育区进行了地球化学勘查,结果表明,泥火山周围具有酸解烃、荧光光谱、碳酸盐、蚀变碳酸盐、微量元素等地球化学指标显著异常,甲烷碳同位素和三维荧光结果显示地球化学烃类异常为原油伴生气和凝析油成因,表明泥火山外围烃类富集是由油气藏渗漏形成。该结论对羌塘盆地天然气水合物勘查突破具有重要意义。     

海底沉积物酸解烃脱气装置的改进

酸解烃方法过去主要用在常规油气地球化学勘查中。近几年通过对海底天然气水合物地球化学勘查试验研究,发现该方法也能应用其中。酸脱气过程是酸解烃方法的最重要组成部分,它直接影响到该方法的最后测试结果。为满足当前海洋地质调查中沉积物取样特点,笔者等在前人工作基础上对酸解烃方法中酸脱气装置进行了改进。通过一系列条件试验,确定了在改进后装置下酸脱气过程中最佳的样品粒度、盐酸浓度、反应时间等条件。通过平行性试验和准确性试验,证明该酸脱气装置所得到的数据基本可靠,结果符合部颁标准。     

陆域天然气水合物地球化学勘查技术试验研究

选择青海省木里地区天然气水合物已知区作为试验区,探索和研究了传统油气地球化学方法(酸解烃、顶空气、ΔC)对陆域天然气水合物勘查的适用性和有效性。试验结果表明,天然气水合物已知区浅表层土壤酸解烃、顶空气、ΔC等地球化学指标具有顶部异常特征,各指标按累积频率圈定了3处异常,异常范围基本吻合且与地下天然气水合物分布具有良好的相关性,初步提出了"酸解烃+顶空气+ΔC"异常是地下天然气水合物赋存的重要标志。     

青海省天峻县木里地区天然气水合物发现区 浅表地球化学特征

在青海木里天然气水合物发现区分别采集50件浅表土壤样品和顶空气样品,采用顶空间轻烃法、酸解烃法和蚀变碳酸盐法研究其浅表地球化学特征。结果表明,顶空气中可检测出C1—C3,土壤中检测出C1—C5,酸解烃各指标之间具有显著的相关性,碳酸盐指标与酸解烃也呈显著的正相关。地表烃类气体来源为原油伴生气、凝析油伴生气和煤型气,与水合物同源,显示出深部热解成因气的特征。     

祁连山天然气水合物地球化学勘查方法稳定性和异常重现性分析

根据祁连山木里地区已知天然气水合物上方不同期次近地表土壤地球化学勘查重复性试验,对土壤酸解烃、顶空气、荧光光谱、碳酸盐等指标方法的稳定性及异常重现性问题进行研究和探讨。结果表明,各项化探指标不同期次含量最大值等特征值虽然存在一定程度的差异,但是其数据波动特征和数据结构是相对一致的。顶空气甲烷、酸解烃、荧光光谱和碳酸盐方法指标前后两次测量结果均具有较高的相关性,配对T-检验显示顶空气轻烃、酸解烃和碳酸盐指标数据变化差异不显著,从统计学上看其指标数据具有较好的稳定性。顶空气甲烷、酸解烃、荧光光谱等指标地球化学异常在研究区已知天然气水合物矿区上方具有相似的空间分布特征,说明其化探指标异常空间上具有良好的稳定性和重现性;但是顶空气重烃异常模式、碳酸盐异常强度的变化,反映其具有重现性,但异常稳定性相对较差。这为地球化学勘查在陆域冻土区天然气水合物勘查中发挥作用提供了较好的基础。     

ODP/IODP典型水合物站位稳定带界限和水合物分布的地球化学识别标志

本文采用ODP/IODP典型站位样品实测和相关数据搜集对比研究的方法,进行了多种游离烃甲烷及相关指标在水合物形成过程中的地质作用和地球化学特征研究,以及酸解烃甲烷与围岩组分和沉积中自生碳酸盐、浊积岩的关系及地球化学特征的研究,据此筛选出判识水合物稳定带(GHSZ)的地球化学标志。结果显示:(1)下伏地层中游离甲烷异常是天然气水合物稳定带孔隙中赋存动态甲烷的反映,由于指标测试方法和沉积物状态的差异,深部水合物稳定带上呈现出特定的两种游离烃甲烷指标HS和VAC正负拆离分隔的异常模式;(2)酸解烃与地层吸附甲烷能力和围岩组分性质密切相关,对应于水合物最佳赋存条件的自生碳酸盐和浊流岩,酸解烃甲烷具有显著的量化异常特征;(3)水合物形成过程中甲烷通量促进了甲烷厌氧氧化反应(AMO)和自生碳酸盐的生成。酸解烃甲烷与浅层自生碳酸盐具有显著的对应关系,弥补了浅部沉积中游离烃甲烷异常具多源和多解性的不足;(4)游离烃甲烷异常组合模式和酸解烃甲烷量化异常分布是GHSZ和有利水合物赋存条件的综合反映,能够为水合物稳定带和带内水合物聚集的判识提供依据。     

西沙海槽研究区天然气水合物地球化学勘探及成藏模式研究

依据ODP204航次1250C站位钻井样品酸解烃数据结果,以及作者在南海西沙海槽研究区天然气水合物地球化学现场勘查中得到的多种烃类指标数据、异常点上微量甲烷碳同位素数值等资料,对海洋水合物地球化学勘探的依据和研究区气态烃异常特征、气体成因、天然气水合物成藏模式等相关问题进行了研究探讨。结果表明:气态烃指标地球化学异常主要分布在工区北部斜坡地带,并与BSR等地震标志及深部断裂关系密切;西沙海槽研究区海底沉积物气态烃甲烷以热解成因为主,但也有混合成因;推测该区天然气水合物为断层渗滤综合成藏模式。研究成果比较合理地解释了BSR分布和海底沉积物甲烷局部异常并非完全一致的原因;评价预测了该区天然气水合物有利勘探目标。成果为该区天然气水合物勘探、天然气水合物成因机制研究和天然气水合物远景预测,提供了地球化学方面的证据。     

青海省天峻县木里地区天然气水合物发现区浅表地球化学特征

在青海木里天然气水合物发现区分别采集50件浅表土壤样品和顶空气样品,采用顶空间轻烃法、酸解烃法和蚀变碳酸盐法研究其浅表地球化学特征。结果表明,顶空气中可检测出C1-C3,土壤中检测出C1-C5,酸解烃各指标之间具有显著的相关性,碳酸盐指标与酸解烃也呈显著的正相关。地表烃类气体来源为原油伴生气、凝析油伴生气和煤型气,与水舍物同源,显示出深部热解成因气的特征。     

海底沉积物酸解烃分析方法

在SY/T 6009.1-2003方法的基础上,对海底沉积物酸解烃的分析测试方法进行了研究,重点考查了方法准确度、精密度、检出限、实验室间重现性及保存时间的影响,该方法实用、可靠,基本能满足海底沉积物酸解烃的测试要求。     

海底沉积物中不同形式烃类气体的地球化学意义

顶空气法和酸解烃法将东沙群岛海域海底浅表层沉积物中不同形式的烃类气体释放出来,通过分析两类气体在沉积物中的含量及其甲烷碳同位素,发现两类气体的成因和来源不同。笔者认为,相对而言,吸附气(包裹气)反映的是一种更为早期的信息,而游离气(溶解气)则更具有“现代性”。笔者进一步认为,两类气体的不同形成过程,对于天然气水合物调查具有不同的意义,其中游离气(溶解气)具有直接的指示意义,而吸附气(包裹气)可能指示成岩时沉积物中的空间信息。     

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。     

Geochemical Indications of Possible Gas Hydrates in the Northeastern South China Sea

Gas hydrate, mainly composed of hydrocarbon gas and water, is considered to be a clean energy in the 21st century. Many indicators such as BSRs （Bottom-Simulating Reflections）, which are thought to be related to gas hydrate, are found in the South China Sea （SCS） in recent years. The northeastern part of the SCS is taken as one of the most potentials in the area by many scientists. It is situated in the conjunction of the northern divergent continental margin and the eastern convergent island margin, whose geological settings are much preferable for gas hydrate to occur. Through this study, brightness temperature anomalies recorded by satellite-based thermal infrared remotely sensed images before or within the imminent earthquake, the high content of hydrocarbon gas acid-degassed from subsurface sediment and the high radioactive thermoluminescence value of subsurface sediment were found in the region. Sometimes brightness temperature anomalies alone exist in the surrounding of the Dongsha Islands. The highest content of hydrocarbon gas amounts to 393 μL methane per kilogram sediment and the highest radioactive thermoluminescence value is 31752 unit; their geometric averages are 60.5 μL/kg and 2688.9 unit respectively. What is more inspiring is that there are three sites where the methane contents are up to 243, 268 and 359μL/kg and their radioactive thermoluminescence values are 8430, 9537 and 20826 unit respectively. These three locations are just in the vicinity of one of the highest confident BSRs identified by predecessors. Meanwhile, the anomalies are generally coincident with other results such as headspace gas anomaly in the sediment and chloride anomaly in the interstitial water in the site 1146 of Leg 184. The above-mentioned anomalies are most possibly to indicate the occurrence of gas hydrate in the northeastern SCS.     

The biogeochemistry of sorbed methane in marine sediments

Sorption of volatile hydrocarbon gases (VHCs) to marine sediments is a recognized phenomenon that has been investigated in the context of petroleum exploration. However, little is known about the biogeochemistry of sorbed methane and higher VHCs in environments that are not influenced by thermogenic processes. This study evaluated two different extraction protocols for sorbed VHCs, used high pressure equipment to investigate the sorption of methane to pure clay mineral phases, and conducted a geochemical and mineralogical survey of sediment samples from different oceanographic settings and geochemical regimes that are not significantly influenced by thermogenic gas. Extraction of sediments under alkaline conditions yielded higher concentrations of sorbed methane than the established protocol for acidic extraction. Application of alkaline extraction in the environmental survey revealed the presence of substantial amounts of sorbed methane in 374 out of 411 samples (91%). Particularly high amounts, up to 2.1 mmol kg⁻¹ dry sediment, were recovered from methanogenic sediments. Carbon isotopic compositions of sorbed methane suggested substantial contributions from biogenic sources, both in sulfate-depleted and sulfate-reducing sediments. Carbon isotopic relationships between sorbed and dissolved methane indicate a coupling of the two pools. While our sorption experiments and extraction conditions point to an important role for clay minerals as sorbents, mineralogical analyses of marine sediments suggest that variations in mineral composition are not controlling variations in quantities of sorbed methane. We conclude that the distribution of sorbed methane in sediments is strongly influenced by in situ production.     

海上气态烃快速测试与西沙海槽天然气水合物资源勘查

西沙海槽具有适合天然气水合物形成和赋存的地形地貌及地质条件 ,是中国海洋天然气水合物资源勘查的远景区。为配合中国首次天然气水合物资源的调查研究 ,在该区进行了海底表层沉积物甲烷、乙烷等气态烃快速现场测试。研究发现 ,海底沉积物随着埋深的增加气态烃含量具有增高的趋势 ;最佳取样深度应在埋深 1～ 4m处 ;海底沉积物甲烷高含量异常区域主要分布在B33周围、A0 9—A11周围、B17—A0 2周围和B0 1—B0 3周围等区域。西沙海槽北部陆坡比槽底及南部斜坡具有更好的甲烷异常显示。该研究成果为以后该区天然气水合物资源的重点勘查提供了科学依据     

Application of a Simulation Model for the Formation of Methane Hydrate to the Nankai Trough and the Blake Ridge: Natural Examples of Two End-member Cases

Abstract. Simulation experiments with a one-dimensional static model for formation of methane hydrate are used to demonstrate models of hydrate occurrence and its generation mechanism for two end-member cases. The simulation results compare well with experimental data for two natural examples (the Nankai Trough and the Blake Ridge).
At the MITI Nankai Trough wells, the hydrate occurrence is characterized by strongly hydrated sediments developing just above the BGHS. Such occurrence can be reproduced well by simulation in which the end-member case of upward advective fluid flow from below the BGHS is set. The strongly hydrated sediments is formed by oversaturated solution with free gas which directly enters the BGHS by the upward advective fluid flow. The recycling of dissociated methane of preexisting hydrate also contributes to the increase of hydrate saturation.
At the Site 997 in the Blake Ridge area, the hydrate occurrence is characterized by thick zone with poorly hydrated sediments and no hydrate zone developing above the hydrate zone. Such occurrence can be reproduced well by simulation in which the end-member case of in-situ biogenic production of methane in the sediment of methane hydrate zone is set. The distribution pattern of hydrate saturation is basically controlled by that of TOC. However, the hydrate concentration near the bottom of the hydrate zone is increased by the effect of recycling of dissociated methane of pre-existing hydrate. No hydrate zone expresses the geologic time needed until the local concentration of methane exceeds the solubility by gradual accumulation of in-situ biogenic methane with burial.     

Molecular and isotopic partitioning of low-molecular-weight hydrocarbons during migration and gas hydrate precipitation in deposits of a high-flux seepage site

Detailed knowledge of the extent of post-genetic modifications affecting shallow submarine hydrocarbons fueled from the deep subsurface is fundamental for evaluating source and reservoir properties. We investigated gases from a submarine high-flux seepage site in the anoxic Eastern Black Sea in order to elucidate molecular and isotopic alterations of low-molecular-weight hydrocarbons (LMWHC) associated with upward migration through the sediment and precipitation of shallow gas hydrates. For this, near-surface sediment pressure cores and free gas venting from the seafloor were collected using autoclave technology at the Batumi seep area at 845 m water depth within the gas hydrate stability zone.Vent gas, gas from pressure core degassing, and from hydrate dissociation were strongly dominated by methane (> 99.85 mol.% of ∑[C₁–C₄, CO₂]). Molecular ratios of LMWHC (C₁/[C₂ + C₃] > 1000) and stable isotopic compositions of methane (δ¹³C = ? 53.5‰ V-PDB; D/H around ? 175‰ SMOW) indicated predominant microbial methane formation. C₁/C₂₊ ratios and stable isotopic compositions of LMWHC distinguished three gas types prevailing in the seepage area. Vent gas discharged into bottom waters was depleted in methane by > 0.03 mol.% (∑[C₁–C₄, CO₂]) relative to the other gas types and the virtual lack of ¹⁴C–CH₄ indicated a negligible input of methane from degradation of fresh organic matter. Of all gas types analyzed, vent gas was least affected by molecular fractionation, thus, its origin from the deep subsurface rather than from decomposing hydrates in near-surface sediments is likely.As a result of the anaerobic oxidation of methane, LMWHC in pressure cores in top sediments included smaller methane fractions [0.03 mol.% ∑(C₁–C₄, CO₂)] than gas released from pressure cores of more deeply buried sediments, where the fraction of methane was maximal due to its preferential incorporation in hydrate lattices. No indications for stable carbon isotopic fractionations of methane during hydrate crystallization from vent gas were found. Enrichments of ¹⁴C–CH₄ (1.4 pMC) in short cores relative to lower abundances (max. 0.6 pMC) in gas from long cores and gas hydrates substantiates recent methanogenesis utilizing modern organic matter deposited in top sediments of this high-flux hydrocarbon seep area.     

晚期泥底辟控制作用导致神狐海域SH5钻位未获水合物的分析

海底泥底辟构造与天然气水合物成藏关系密切,泥底辟既能为水合物提供充分的气源物质,同时又能促使地层温度场改变进而影响水合物成藏稳定性。南海北部神狐海域SH5站位虽然BSR明显,但钻探证实不存在天然气水合物。该钻位温度剖面异常高,温度场上移,同时在其下伏地层中发现泥底辟构造和裂隙通道。根据上述事实并结合泥底辟发育各个阶段中的特点,认为泥底辟构造对天然气水合物成藏具有控制作用。泥底辟发育早期和中期阶段,低热导率和低热量有机气体有利于天然气水合物生成;而在晚期阶段,高热量液体上侵稳定带底界,导致水合物分解迁移。SH5站位很可能由于受到处于晚期阶段的泥底辟上侵而未能获取天然气水合物。     

Distinct microbial communities thriving in gas hydrate-associated sediments from the eastern Japan Sea

Marine gas hydrate and cold-seep systems, which maintain a large amount of methane in the seabed, may critically impact the geochemical and ecological characteristics of the deep-sea sedimentary environment. However, it remains unclear whether marine sediments associated with gas hydrate harbor novel microbial communities that are distinct from those from typical marine sediments. In this study, microbial community structures thriving in sediments associated with and without gas hydrate in the eastern Japan Sea were characterized by 16S rRNA gene-based phylogenetic analyses. Uncultivated bacterial lineages of candidate division JS1 and a novel group NT-B2 were dominant in the sediments from gas hydrate-associated sites. Whereas, microbial populations from sites not associated with gas hydrate were mainly composed of Bacteroidetes, Nitrospirales, Chlamydiales, Chlorobiales, and yet-uncultured bacterial lineages of OD1 and TM06. The good correlation between the dominance of JS1 and NT-B2 and the association of gas hydrate could be attributed to the supply of more energetically favorable energy sources in gas-rich fluids from the deep subsurface than refractory organic matter of terrigenous and diatomaceous origin.     

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.