南海沉积物中烃类气体(酸解烃)特征及其成因与来源

烃类气体是形成天然气和天然气水合物的物质基础,可通过顶空气、吸附烃和酸解烃等方法来探测。南海473个站位767件沉积物样品的酸解烃分析结果表明,甲烷含量为0.8~22153.6μl/kg,平均为335.8μl/kg,并可分成台西南—东沙、笔架南、琼东南—西沙海槽、中建南—中业北、万安—南薇西和南沙海槽等6大异常区,其中南沙海槽是异常最强烈的地区,台西南盆地次之。154件甲烷样品的碳同位素分析结果表明,其δ13C1值为-101.7‰~-24.4‰(PDB标准,下同),平均为-44.5‰,其中南沙海槽的δ13C1值明显偏低,为-101.7‰~-71.4‰,应是微生物气或是以微生物气为主的混合气,而南海其他地区的δ13C1值相对较高,为-51.0‰~-24.4‰,明显属于热解气。     

综合大洋钻探计划311航次沉积物中自生碳酸盐岩碳、氧稳定同位素特征

为了探索水合物背景下沉积物中自生矿物响应,对采自综合大洋钻探计划（IODP）311航次沉积物中自生碳酸盐岩颗粒进行了矿物组成、形貌特征和碳、氧稳定同位素特征等研究。X光粉晶衍射（XRD）和扫描电镜（SEM）结果显示碳酸盐岩颗粒的主要矿物成分是铁白云石和方解石,呈多孔状结核和不规则状集合体产出。碳酸盐岩颗粒的碳稳定同位素δ¹³C_PDB低至-41.50‰,证实其碳源源自甲烷,其成因与甲烷厌氧氧化过程有关,印证了研究区存在海底甲烷渗漏现象,是甲烷水合物赋存区重要的识别标志之一。碳酸盐岩颗粒的氧稳定同位素δ¹⁸O_PDB总体上随着沉积物深度增加而减小,可能指示沉积物的背景温度由下而上（从早到晚）逐渐降低。研究结果提供了现代海洋天然气水合物背景下沉积物中自生碳酸盐岩的碳、氧稳定同位素记录,对于寻找我国海域天然气水合物资源,探索地史时期古海洋沉积物中类似的甲烷事件记录具有重要的理论和实践指导意义。     

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.     

含天然气水合物土水-力特性联合测试装置及应用

海底天然气水合物(以下简称水合物)的开采会劣化储层的力学性质,威胁钻井平台、破坏开采井甚至可能诱发地质灾害。为探究含水合物沉积物的力学特性及开采扰动下水合物储层的力学强度劣化机理,本文搭建了一套含天然气水合物土水-力特性联合测试装置,主要包括:压力室、压力控制系统,注/除气系统,温度控制系统,数据采集及人机交互管理系统。该装置可实现不同条件下含水合物沉积物试样的合成,并可开展渗透试验、等向压缩试验、以及不同应力路径下三轴压缩试验测试。以细砂作为赋存介质,采用富气法制备含天然气水合物沉积物试样,对其进行了一系列水-力特性试验测试,并对结果进行了简要地分析。这些试验结果证实了装置测试含水合物沉积物水-力学特性的功能和可靠性。     

Geochemical Process of Gas Hydrate Formation in the Nankai Trough Based on Chloride and Isotopic Anomalies in Interstitial Water

Abstract: Interstitial water expelled from gas hydrate-bearing and -free sediments in the Nankai Trough are analyzed in terms of Cl-, SO₄²-, δ¹⁸O and δD. The baselines for the Cl- concentration and δ¹⁸O value are close to seawater values (530 mM and 0%), indicating that the interstitial water is of seawater origin. The δD values decrease with depth, implying isotopic exchange of hydrogen between upwelling biogenic methane depleted in D and interstitial water. The Cl- concentrations in gas hydrate-bearing sediments are anomalously low, while the δ¹⁸O and δD values are both high, suggesting that the water forming these gas hydrates was poor in Cl- and enriched in ¹⁸O and D during gas hydrate formation. Calculation of the gas hydrate saturations using Cl "and δ¹⁸O anomalies gives results of up to 80 % in sand, and shows that the δ¹⁸O baseline is not consistent with the Cl" baseline. The δ¹⁸O baseline increases by +1% in gas hydrate-free clay and silt. This is considered to be caused by clustering of water molecules after gas hydrate dissociation in response to the upward migration of the base of gas hydrate stability, as indicated by the presence of a double bottom-simulating reflector at this site. The water clusters enriched in ¹⁸O are responsible for the increase in the δ¹⁸O baseline with normal Cl". The abrupt shallowing of the base of gas hydrate stability may induce the dissociation of gas hydrates and the accumulation of gases in the new stability zone, representing a geological process that increases gas hydrate saturation.     

水合物沉积物力学性质的三维离散元分析

水合物沉积物力学特性研究是天然气水合物开采领域中的热点问题。为深入了解水合物对沉积物力学特性的影响,在提出一个新的水合物沉积物离散元数值试样制备方法的基础上,模拟了不同水合物饱和度沉积物试样的三轴排水试验,并从其应力-应变关系、体变特性、弹性模量及峰值强度等方面对模拟结果及已有室内三轴试验结果进行了对比,然后利用该方法对具有不同微观胶结参数的水合物沉积物样进行了三轴离散元数值试验。研究结果表明：所提出的离散元模拟方法能较好地反映水合物沉积物的主要力学特性;天然气水合物与土颗粒间胶结性能的改变会对水合物沉积物的力学响应产生一定的影响;水合物沉积物强度和模量的增加是孔隙填充水合物和粒间胶结水合物共同作用的结果。     

羌塘盆地QK-1孔烃类气体分布特征与成因来源

青藏高原冻土区面积约150×104 km²,是中国最大的冻土区,具备良好的天然气水合物形成条件和找矿前景,而羌塘盆地是形成条件和找矿前景最好的地区。南羌塘盆地毕洛错地区QK-1科学钻探试验井顶空气样品的烃类气体组分和碳同位素分析测试结果表明,其烃类气体组分复杂,CH₄含量为3.0×10^-6~4 526.8×10^-6,平均为209.0×10^-6;δ¹³C₁值为-55.9‰~-37.8‰,平均为-43.2‰,C₁/(C₂+C₃)值小于10,显示出明显的热解气特征。结合钻探区的地质背景和岩性特征,推断QK-1孔烃类气体可能来源于深部迁移上来的热解气,浅部可能有生物成因气的混入。     

Worldwide distribution and significance of secondary microbial methane formed during petroleum biodegradation in conventional reservoirs

Around half of world’s endowment of in-place oil and bitumen experienced biodegradation, which is now believed to be largely an anaerobic methanogenic process. However, the distribution and scale of methanogenic biodegradation in the world’s petroleum accumulations and the significance of its terminal product, secondary microbial methane, in the global gas endowment and carbon cycle are largely unknown. Here, I present geological and geochemical criteria to recognize secondary microbial methane in conventional petroleum reservoirs. These include the presence of biodegraded oil (as pools, legs or shows) in the reservoir or down-dip, the relatively dry (methane dominated) gas containing methane with δ¹³C values between −55‰ and −35‰ and, most importantly, CO₂ with δ¹³C > +2‰. Based on these criteria, the presence of secondary microbial methane is apparent in 22 basins, probable in 12 basins and possible in six basins worldwide. Reservoirs apparently containing secondary microbial methane are mostly Cenozoic and clastic and occur at depths of 37-1834 m below surface/mudline and temperatures of 12-71 °C. Using the current global endowment of in-place oil and bitumen and reasonable assumptions about conversion of oil into methane during biodegradation, I estimated that ∼65,500 tcf of secondary microbial methane could have been generated in existing worldwide accumulations of oil and bitumen through their geological history. From 1461-2760 tcf in-place (845-1644 tcf recoverable) of secondary microbial methane may be accumulated as free and oil-dissolved gas in petroleum reservoirs. I also updated the inventory of primary microbial methane and estimated that the global primary microbial gas endowment (free and oil-dissolved) is from 676-797 tcf in-place (407-589 tcf recoverable). Secondary microbial methane may account for ∼5-11% of the global conventional recoverable gas endowment and appears more abundant than primary microbial gas (∼3-4% of the global gas endowment). Most of the generated secondary microbial methane probably is aerobically and anaerobically oxidized to CO₂ in the overburden above petroleum reservoirs. However, some secondary microbial methane may escape from shallow reservoirs into the atmosphere and affect present and past global climate.     

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.     

水合物生成过程中碳同位素组成变化的实验研究

天然气水合物是一种新型的洁净能源。甲烷天然气水合物是储量最丰富的一种类型,常出现在深海中或极地大陆上,其生成的过程中会发生同位素的分馏效应。通过实验室模拟水合物生成的过程,利用天然海水与甲烷或二氧化碳气体反应,以及更接近实际生成环境的甲烷-海水-沉积物动态聚散实验,对甲烷水合物和二氧化碳水合物生成前后δ13C值进行测定,研究水合物生成过程中δ13C的变化情况。实验证明,水合物反应中碳同位素分馏是存在的,其变化程度明显小于氧同位素和氢同位素。甲烷水合物碳同位素的分馏系数αC的值为1000 3~1000 9。二氧化碳水合物生成反应后气相的碳、氧同位素变轻,重同位素趋向于进入水合物中,二氧化碳水合物碳同位素的分馏系数αC的值为1000 7~1001 2。海水中溶解的CO2气体在甲烷水合物形成过程中会被水合物捕获,从而使得δ13CDIC值变小,重的碳同位素趋于进入水合物中,而较轻的碳同位素留在海水中。但由于海水中含有的溶解CO2气体有限,经过多轮水合物动态聚散后δ13CDIC值的变化幅度会越来越小。     

南海东北部陆坡天然气水合物多期次分解的沉积地球化学响应

南海地区天然气水合物资源丰富,针对其分解方式的研究有助于资源的开采.对南海东北部天然气水合物钻探区GMGS08站位岩心沉积物开展沉积学、地球化学分析研究.结果表明:该站位自上而下分布11层含自生碳酸盐岩和双壳碎屑层(其中6层呈粥状沉积)以及2层自生碳酸盐岩灰岩层;各层自生碳酸盐岩除一个样品δ13C值稍高(-38.85×10-3)外,其他的δ13C值介于-41.36×10-3~-56.74×10-3,均低于-40.00×10-3,δ18O值介于2.94×10-3~5.37×10-3,明显偏重,表明其为天然气水合物分解的产物,形成于微生物对甲烷的缺氧氧化作用,甲烷主要源自生物成因;各层自生碳酸盐岩层中的有机质碳同位素负偏明显,最低达-82.44×10-3,可能与微生物活动有关;根据自生碳酸盐岩的分布推断该站位至少发生过6次天然气水合物分解释放,每期次自生碳酸盐岩的差异说明其甲烷通量强弱不同.      

南海北部天然气水合物钻探区烃类气体成因类型研究

南海北部天然气水合物钻探区水合物气、顶空气样品和沉积物样品烃类气体组分和甲烷同位素特征测试结果表明,气体样品中烃类气体以甲烷为主,含微量乙烷和丙烷,C1/(C2+C3)值均大于或接近1 000。甲烷的碳同位素值为-54.1‰~-62.2‰,氢同位素值为-180‰~-255‰,属于微生物气或是以微生物气为主的混合气,甲烷由CO2还原生成,由原地提供或侧向运移而来。沉积物样品酸解烃分析显示多数样品甲烷丰度大于90%,含一定量的乙烷、丙烷及少量的丁烷,C1/(C2+C3)值均小于50。甲烷的碳同位素值为-29.8‰~-48.2‰,呈现典型的热解气特征,显示由深部运移而来。     

川东北飞仙关组甲烷为主的TSR及其同位素分馏作用

川东北开江-梁平陆棚东北侧飞仙关组多孔鲕粒白云岩中发生了以甲烷为主的热化学硫酸盐还原作用(TSR),产生高达20%的H₂S;而西南侧鲕粒灰岩以低孔、低H₂S天然气为特征。东北侧白云岩主要发育白云石粒间溶孔或粒间扩大溶孔,这些溶孔可与方解石(δ¹³C=-10‰~-19‰)、储层沥青、元素硫、黄铁矿和石英紧密共生,可分布于片状储层沥青与白云石晶体之间,说明白云石溶解作用发生在沥青形成以后。白云石的溶解作用导致现今天然气以无机CO₂为主,δ¹³C_CO2主要介于-2‰~+2‰之间。这种溶解作用是在酸性条件下,硬石膏或天青石参与下发生的,可能先产生MgSO₄配对离子,而后MgSO₄又与甲烷反应产生H₂S,净增大了孔隙。研究还发现,普光气田及以东天然气的来源不同于河坝和元坝天然气;对普光气田及以东天然气分析显示,甲烷δ¹³C值与残余烃含量 之间存在对数相关关系。这表明TSR过程中,甲烷同位素分馏作用遵从封闭体系下瑞利分馏原理。据此计算显示,渡4井约有15%甲烷被氧化了。     

天然气水合物发现区和潜在区气源成因

为探讨天然气水合物发现区的气源成因,对ODP 204航次4个站位58个沉积物样品进行5个温度点的生气量模拟实验,对各温度点产生的气体进行同位素测定。测试结果显示,在低温阶段（25 ℃、35 ℃、45 ℃）,甲烷的δ¹³C明显偏大,一般大于-40‰,显示出热解成因气的特征;而高温阶段（55 ℃）甲烷的δ¹³C为-75.5‰,显示出明显的生物成因气的特征。结合东沙海域天然气水合物潜在区气源成因的讨论,可以得出如下结论：天然气水合物的气源成因受控因素多,需要综合多种指标进行判别。     

层状赋存含水合物沉积物的本构模型研究

推进天然气水合物资源开采是我国能源战略的重要任务。层状赋存形态的含水合物沉积物在目标开采储层中普遍存在,水合物开采引起的沉积物层扰动会直接诱发剪切变形影响储层的稳定性,严重制约水合物资源的安全开采。现有水合物沉积物的本构表征主要基于空间均匀分布、各向同性的材料特征假设,缺少考虑水合物沉积物的强非线性力学特性受层状赋存形态影响的本构表征方法,无法准确预测目标开采储层的应力-应变规律。本文采用均匀化理论,基于每层沉积物的弹塑性刚度矩阵构建层状形态代表体积单元的宏细观控制方程,建立了层状赋存含水合物沉积物的本构表征方法。代表体积单元内每层的沉积物模型参数可基于均质含水合物沉积物试样的三轴试验标定获取。通过将层状本构模型预测和层状沉积物三轴试验以及数值试验的应力-应变关系对比验证,本研究提出的层状本构模型可准确描述原位储层中层状赋存含水合沉积物的力学行为。     

祁连山冻土区含天然气水合物层段岩心热模拟实验研究

以热模拟实验为手段,对祁连山冻土区DK-2和DK-3孔含天然气水合物层段岩心(泥岩、油页岩和煤)热模拟烃类气体的组分、碳同位素组成与天然气水合物进行对比,以探寻这些气源岩与天然气水合物气源之间的可能联系。实验结果显示：低温(300 ℃以下)条件下,产生的气体以非烃CO₂为主,烃类气体含量少,且泥岩产生烃类气体量<油页岩产生烃类气体量<煤产生烃类气体量,表现出不同岩石吸附气体的差异性特征;随着热模拟温度增加,产生的烃类气体量明显增加,至500 ℃时达到最高,相反CO₂产气量变化不大;随热模拟温度增加,泥岩、油页岩、煤所产生烃类气体的碳同位素值呈现先变轻后变重的演化趋势和δ¹³C₁ ＜δ¹³C₂＜δ¹³C₃的正碳同位素序列特征;泥岩在350~400 ℃条件下或油页岩在380~400 ℃条件下所产生的烃类气体在组成和同位素特征上与天然气水合物中烃类气体较为相似,推测天然气水合物气源与深部泥岩或油页岩具有地球化学成生联系,相反煤产生的烃类气体虽然在组成上与天然气水合物中烃类气体较为相近,但两者同位素值相差较远,推测煤与天然气水合物气源关系不大。     

三维离散元单轴试验模拟甲烷水合物宏观三轴强度特性

填充型水合物的砂性能源土试样可视为特殊的散粒体材料,即砂粒和水合物颗粒混合物,具有明显的非连续特征。为研究填充型水合物的能源土力学特性,初步探索了甲烷水合物在不同温度、反压条件下加荷模式的离散元模拟方法。离散元模拟中,将水合物块体视为由大量颗粒通过强胶结作用凝聚而成的整体,室内试验中的内部孔隙水压作用转化为水合物颗粒间的胶结力,故需要合理确定颗粒间胶结模型参数来实现反压的影响作用。通过参数反演建立了宏观强度、刚度参数与平行胶结模型的微观胶结参数间的宏、微观关系,基于已有室内甲烷水合物三轴试验资料,确定了给定温度和反压条件下的微观胶结参数取值,随后进行离散元单轴压缩试验。离散元单轴压缩试验模拟获得的水合物强度特性,与室内三轴试验结果符合较好;通过建立的宏、微观参数间的关系,实现了不同温度、反压下的水合物加荷模式的模拟。为进一步提出深海能源土离散元数值试验成样方法--孔隙填充水合物生成技术,形成含填充型水合物的能源土试样,研究其力学和变形特性奠定基础。     

祁连山冻土区天然气水合物分解气碳氢同位素组成特征

开展祁连山冻土区天然气水合物气体同位素研究,是解决其气体成因、来源等科学问题的一个重要手段。本研究采集祁连山南麓多年冻土区水合物科学钻探DK2和DK3孔共8个含水合物的岩芯样品,采用真空顶空法收集样品中水合物的分解气,分别用气相色谱(GC)、气相色谱同位素比值质谱(GC-IRMS)测定其气体成分和同位素组成,测试结果表明:祁连山冻土区天然气水合物样品的气体碳氢同位素变化较大,甲烷、乙烷和丙烷的碳同位素(δ13C)变化范围分别为-52.6‰～-48.1‰、-38.6‰～-30.7‰和-34.7‰～-21.2‰,而二氧化碳的碳同位素(δ13C)最低为-27.9‰,最高为16.7‰;甲烷、乙烷和丙烷的氢同位素(δD)变化范围分别为-285‰～-227‰、-276‰～-236‰和-247‰～-198‰。通过对这些碳氢同位素进行综合研究,包括气体分子组成与同位素的关系分析、甲烷的碳氢同位素之间的关系判断等,结果表明研究区天然气水合物的气体主要来源于热解气,而且是在淡水环境中形成的有机成因气。     

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。     

Carbon Geochemistry of Gas Hydrate‐associated Sediments in the Southwestern Taiwan Basin

Marine gas hydrates, one of the largest methane reservoirs on Earth, may greatly affect the deep sea sedimentary environment and biogeochemistry; however, the carbon geochemistry in gas hydrate-bearing sediments is poorly understood. In this study, we investigated the carbon variables in sediment core 973-3 from the southwestern Taiwan Basin in the South China Sea to understand the effect of environmental factors and archaeal communities on carbon geochemistry. The carbon profiles suggest the methanogenesis with the incerase of dissolved inorganic carbon(DIC) and high total organic carbon(TOC)(mean = 0.46%) originated from terrigenous organic matter(mean δ~(13)C_(TOC) value of-23.6‰) driven by the abundant methanogen ‘Methanosaeta and Methanomicrobiales'. The active anaerobic oxidation of methane is characterized by the increase of DIC and inorganic carbon(IC), and the depleted δ~(13)C_(IC), coupled with the increase of TOC and the decrease of δ~(13)C_(TOC) values owing to the methanotroph ‘Methanosarcinales/ANME' in 430–840 cm. Environmental factors and archaeal communities in core 973-3 are significantly correlated to carbon variables owing to methane production and oxidation. Our results indicate that the carbon geochemical characteristics are obviously responding to the formation and decomposition of gas hydrates. Furthermore, pH, Eh and grain size, and Methanosaeta greatly affect the carbon geochemistry in gas hydrate-associated sediments.