四川盆地高含H2S天然气的分布与TSR成因证据

四川盆地是中国高含硫化氢天然气分布最集中的地区,目前已在震旦系(威远气田)、下三叠统飞仙关组(罗家寨、普光、渡口河、铁山坡、七里北)、嘉陵江组(卧龙河)和中三叠统雷口坡组(磨溪、中坝)发现了近10个高含硫化氢的大中型气田(藏),探明储量5000×108 m3.这些高含硫化氢气藏普遍经历过较大的埋深过程(储层经历过较高温度),储层上下或储层中间均发育有膏质岩类,且气源充足,具备硫酸盐热化学还原反应(Thermochemical Sulfate Reduction,TSR)发生的物质基础和热动力条件.从气藏地质特征以及天然气组成和碳、硫同位素等方面的证据表明,四川盆地中、下三叠统和震旦系气藏的硫化氢属于TSR成因.而且TSR对烃类的大量选择性消耗一方面导致天然气干燥系数增大,另一方面导致气藏充满度降低,气藏压力系数变小.     

TSR成因H2S的硫同位素分馏特征与机制

热化学硫酸盐还原反应(TSR)是深层碳酸盐岩油气藏中硫化氢的主要成因机制,目前已在全球发现了50多个TSR成因的大中型含硫化氢天然气田。通过对中国四川盆地含硫化氢气田硫化物的采集与同位素分析,结合全球含硫化氢天然气田硫同位素分析数据,研究了TSR过程中硫同位素的地球化学行为和分馏特征。研究发现,TSR成因的高含硫化氢天然气中,硫化氢与硫酸盐的硫同位素分馏值小于15‰,主要分布范围为2.5‰~13.82‰,平均在10‰。四川盆地海相层系膏岩的硫同位素值分布较宽,并呈现阶梯状变化,而硫化氢的硫同位素则呈现出相似的分布规律,表明各主要含硫化氢气田硫化氢中的硫来自于本层系的硫酸盐,TSR主要发生在各自的储集层中。四川盆地各气田TSR发生的温度条件相似,硫同位素分馏比较接近。TSR过程中硫同位素的分馏过程与硫酸盐本身硫同位素值的高低无关,而与TSR反应程度有关。TSR反应程度越高,硫化氢的硫同位素值与地层硫酸盐的硫同位素越相近。通过系统分析整理全球含硫化氢气田的硫化物硫同位素数据,并结合四川盆地地质条件和油气演化过程,揭示了TSR过程中硫同位素的分馏特征,并绘制出四川盆地和全球各时代硫化氢和石膏的硫同位素分布曲线图,为研究含油气盆地蒸发岩沉积演化和硫化氢成因提供了参考。     

中国高含硫化氢天然气成因初探

高含硫化氢天然气主要分布在四川盆地川东北地区三叠系飞仙关组渡口河、罗家寨、普光、铁山坡等飞仙关组气藏（T1f）和渤海湾盆地冀中坳陷晋县凹陷东北部孔店组孔一段-沙河街组沙四段（Ek^1-Es^4）气藏中。硫化氢含量分布在40％～92％，属世界上硫化氢含量最高气藏之一。笔者通过对这两个地区70余口取心井的5000m岩心观察和取样测试分析，特别是对石膏、硫磺、黄铁矿和天然气的硫同位素分析，以及油、气地球化学的综合研究，认为这两个地区高含硫化氢天然气均属硫酸盐热化学还原反应（TSR）成因，     

TSR对深部碳酸盐岩储层的溶蚀改造——四川盆地深部碳酸盐岩优质储层形成的重要方式

四川盆地海相层系发现的大气藏部含或高舍硫化氢,都发育一定厚度的优质储层,而且优质储层与硫化氢分布具有密切的关系,即气藏硫化氢含量越高,储层性质越好,气藏产能也越大。研究发现,在 TSR(硫酸盐热化学还原反应)过程中,随着膏质岩类的溶解(为 TSR 反应提供 SO_4~(2-)),使储集孔隙初步得到改善;而 TSR 产生的硫化氢溶于水形成的氢硫酸,具有强烈腐蚀性,加速了储层中白云岩的溶蚀,形成孔隙极其发育的海绵状孔洞体系,并呈层状分布。电镜下可以清晰看到白云石晶面的溶蚀坑及溶孔中 TSR 产生的硫磺晶体。溶孔中自生碳酸盐的碳同位素在-10.3‰～18.2‰,而地层碳酸盐的碳同位素在 3.7‰～ 0.9‰,证实了 TSR 过程中有机-无机的相互作用,即有机成因烃类中的碳转移到次生碳酸盐岩中。包裹体分析表明,次生方解石中的包体富含硫化氢,且均一温度多数在160℃以上,具备 TSR 发生的温度条件;硫化氢和硫磺的硫同位素比地层硫酸盐的硫同位素偏轻8‰左右,是 TSR 作用的证据。因此高含硫化氢气藏的优质储层是在早期埋藏溶蚀作用的基础上,后期发生 TSR 及其形成的酸性流体对深埋碳酸盐岩储层再次进行深刻改造和强烈溶蚀作用的结果;同时可以运用硫化氢来预测碳酸盐岩优质储层的分布。     

川东北飞仙关组鲕滩天然气地球化学特征与成因

四川盆地东北部下三叠统飞仙关组鲕滩气藏天然气烃类气体以甲烷为主,含量主要分布在75%～90%之间,C2 含量很少,为0%～0.15%,干燥系数为0.997 0～0.999 8,是典型的干气;非烃气体以H2S和CO2为主,含量分别为4.21%～16.24%和0.97%～10.41%.天然气δ13C1值为-29.0‰～-31.5‰,δ13C2值为-29.4‰～-32.4‰.多参数表明鲕滩气藏天然气是以腐泥型为主的高过成熟天然气.高含H2S的天然气分布区域与含石膏地层分布基本一致,这些H2S为飞仙关组气藏附近的石膏经热化学硫酸盐还原作用(TSR)而生成,CO2是其主要的副产物.在TSR过程中,C2 重烃气体比甲烷更容易与硫酸盐发生反应,也就是C2 重烃气体的消耗速率大于甲烷,从而导致发生TSR反应的天然气C2 含量低、H2S和CO2含量高.天然气δ13C1值与甲烷含量之间具有很好的负相关关系,而与天然气酸性系数[H2S/(H2S CnH2n 2)]具有正相关关系.根据同位素动力学的分馏效应,随着TSR的进行,烃类分子中的12C损耗速率大于13C,残留下来的烃类分子中则更加富集13C,也就是TSR反应使天然气碳同位素变重.     

川东宣汉地区天然气地球化学特征及成因

依据10余口探井60多个气样的化学成份和碳同位素组成数据,结合烃源岩和储层沥青分析资料,系统剖析了四川盆地东部宣汉地区普光、毛坝场等构造带天然气地球化学特征,并探讨了其成因及来源。研究结果表明:这些构造带中飞仙关组—长兴组天然气为高含硫化氢的干气,天然气化学成份表现出古油藏原油裂解气的特点。其烃类气体中以甲烷为主(高于99.5%);富含非烃气体,CO₂和H₂S平均含量分别达5.32%和11.95%。甲烷碳同位素较重(-33‰～-29‰),表征高热演化性质;乙烷δ¹³C值主要分布在-33‰至-28‰范围,属油型气。这些天然气与川东邻近气田的同层位天然气具有同源性,而与石炭系气藏天然气在化学成份、碳同位素组成上有所不同,意味着有不同的气源。硫化物硫同位素和沥青元素组成证实高含量的H₂S是气藏发生TSR作用所致。δ³⁴S值表征层状沉积成因的硬石膏是TSR作用的反应物,而脉状硬石膏则是其残余物。储层的孔隙类型可能与TSR作用强度和H₂S含量高低有联系,裂缝型气层中H₂S少,孔洞型储层中H₂S丰富。乙烷、沥青和各层系烃源岩干酪根碳同位素对比表明研究区飞仙关组—长兴组气藏天然气主要来自二叠系烃源层。     

TSR烃类化学损耗评价：Ⅱ四川盆地含硫化氢天然气藏TSR烃类损耗程度

在深层—超深层油气保存条件评价研究中,既要关注天然气的物理散失,也要关注高温高压下的烃类化学损耗。热化学硫酸盐还原(TSR)常见于含膏碳酸盐岩层系中,TSR强度越大,烃类损耗程度越大。烃类含量与干燥系数、非烃类含量与酸性气体指数和碳/硫同位素系列指标在一定程度上可以反映TSR强度,但难以满足定量评价的需要。基于四川盆地高含硫化氢或者存在强烈TSR的气藏全部为常压气藏,而邻近的硫化氢含量低且未遭受过TSR的气藏普遍为超压气藏这一基本地质事实,认为TSR烃类化学损耗在超压气藏转变为常压气藏的过程中起着关键作用。因此,利用地层条件下天然气状态参数,尝试建立了TSR烃类化学损耗定量评价方法:Zn PVT状态参数评价法。以普光、元坝、建南和威远等气田的代表性钻井为例,开展了TSR烃类损耗程度评价。结果表明:普光气田长兴组—飞仙关组气藏、元坝气田长兴组气藏、建南气田长兴组—飞仙关组气藏和威远气田灯影组气藏TSR烃类损耗分别为原始储量的18%、20%、10%和64%。该项评价结果与实际地质条件相符。     

川东北飞仙关组高含H2S气藏特征与TSR对烃类的消耗作用

四川盆地川东北地区飞仙关组近年来发现了罗家寨、渡口河、铁山坡、普光等多个大、中型气田，它们均以高含硫化氢（H2S在气体组分中占10%~17%，平均为14%）为最显著特征。深入研究后发现，虽然这些大型鲕滩气藏储量规模较大，单井产量高；但是这些气藏充满度普遍偏低（在25%~91%之间），压力系数不高（大部分小于1.2）。从成藏条件来看，该区鲕粒溶蚀孔隙发育，有效储层厚度大，二叠系龙潭组、志留系龙马溪组优质烃源岩十分发育，油气源充沛，而且由断层构成的疏导体系发育，泥岩及膏质岩类组成的盖层封盖性良好，因此气藏的低充满度现象，可能是圈闭中发生过大量烃类的损耗或消耗。由于川东北飞仙关组H2S是烃类和硫酸盐在储层中发生热化学反应（TSR）形成的，气藏中硫化氢含量与压力系数、地层水矿化度、烃类含量等都存在反相关关系，因此飞仙关组高含硫化氢气藏压力系数小、充满度低，很可能是烃类被TSR大量消耗和储集空间增容所致。     

四川盆地东北部三叠系飞仙关组高含硫气藏H2S成因研究

四川盆地东北部宣汉－开县地区的下三叠统飞仙关组气藏埋深3000－4500m,地温在100℃左右,天然气中H2S含量为12％－17％。这些H2S为飞仙关组气藏附近的硬石膏经硫酸盐热化学还原作用（TSR）而成。与TSR有关的硬石膏,H2S,S^0和FeS2的δ^24S分别为＋30.4‰, 12.9‰, 19.1‰和＋19.4‰,交代硬石膏的方解石的δ^13C为－7.26‰,δ^18O为－6.41‰,其内所含两相流体包裹体的均一温度为109－151℃。这些高含硫气藏的天然气和储层沥青的热演化程度比其他地区飞仙关组气藏的更高。该区飞仙关组最大埋藏温度超过180℃,但由于后期构造抬升,大于104℃地温的埋藏时间小于20Ma,故气藏H2S含量低于20％。     

四川盆地飞仙关组气藏硫化氢成因及其依据

四川盆地东北部下三叠统飞仙关组鲕滩气藏天然气烃类气体以甲烷为主,含量主要分布在75%～90%之间,C2＋含量为0～0.15%;非烃气体以H2S和CO2为主,含量分别为5%～20%和1%～10%。已有观点认为H2S为飞仙关组气藏附近的石膏经硫酸盐热化学还原作用（TSR）而成。随着川东北气区大中型高含硫化氢气田的发现,硫化氢成因机理的研究备受关注。应用金管、高压釜和石英管等实验方法模拟了硫化氢气体的生成,同时检测了模拟生成的硫化氢和石膏、硫磺等硫化物的硫同位素。实验结果表明:硫磺与正己烷在较低温度即可生成大量的硫化氢气体,而正己烷与硫酸钙的反应总体上比较困难,且生成的H2S量较少;富含黄铁矿的低成熟泥灰岩模拟生烃过程中可以生成与甲烷相当,甚至超过甲烷含量的硫化氢气体;含硫化合物与烃类反应生成的硫化氢的硫同位素值比原始物质的硫同位素值重。地层中的SO2－4是海相地层中H2S气体形成的最初来源。含硫烃源岩直接生成高硫化氢天然气和储层中单质硫与烃类的反应是川东北飞仙关组天然气中硫化氢形成的主要原因。     

The terrestrial fauna of the Late Triassic Pant-y-ffynnon Quarry fissures,South Wales,UK and a new species of Clevosaurus (Lepidosauria: Rhynchocephalia)

Pant-y-ffynnon Quarry in South Wales yielded a rich cache of fossils in the early 1950s, including articulated specimens of new species (the small sauropodomorph dinosaur Pantydraco caducus and the crocodylomorph Terrestrisuchus gracilis), but no substantial study of the wider fauna of the Pant-y-ffynnon fissure systems has been published. Here, our overview of existing specimens, a few described but mostly undescribed, as well as freshly processed material, provides a comprehensive picture of the Pant-y-ffynnon palaeo-island of the Late Triassic. This was an island with a relatively impoverished fauna dominated by small clevosaurs (rhynchocephalians), including a new species, Clevosaurus cambrica, described here from a partially articulated specimen and isolated bones. The new species has a dental morphology that is intermediate between the Late Triassic Clevosaurus hudsoni, from Cromhall Quarry to the east, and the younger C. convallis from Pant Quarry to the west, suggesting adaptive radiation of clevosaurs in the palaeo-archipelago. The larger reptiles on the palaeo-island do not exceed 1.5?m in length, including a small carnivorous crocodylomorph, Terrestrisuchus, and a possible example of insular dwarfism in the basal dinosaur Pantydraco.     

Définition d'une limite multicritère ; stratigraphie du passage Campanien–Maastrichtien du site géologique de Tercis (Landes,SW France)Definition of a multi-criteria boundary; stratigraphy of the Campanian–Maastrichtian interval of the geological site at Tercis (Landes,SW France)

Lithostratigraphy, physicochemical stratigraphy, biostratigraphy, and geochronology of the 77–70 Ma old series bracketing the Campanian–Maastrichtian boundary have been investigated by 70 experts. For the first time, direct relationships between macro- and microfossils have been established, as well as direct and indirect relationships between chemo-physical and biostratigraphical tools. A combination of criteria for selecting the boundary level, duration estimates, uncertainties on durations and on the location of biohorizons have been considered; new chronostratigraphic units are proposed. The geological site at Tercis is accepted by the Commission on Stratigraphy as the international reference for the stratigraphy of the studied interval. To cite this article: G.S. Odin, C. R. Geoscience 334 (2002) 409–414.     

The effect of water on accessory phase solubility in subaluminous and peralkaline granitic melts

The solubilities of columbite, tantalite, wolframite, rutile, zircon and hafnon were determined as a function of the water contents in peralkaline and subaluminous granite melts. All experiments were conducted at 1035 °C and 2 kbar and the water contents of the melts ranged from nominally dry to approximately 6 wt.% H₂O. Accessory phase solubilities are not affected by the water content of the peralkaline melt. By contrast, solubilities are affected by the water content of the subaluminous melt, where the solubilities of all the accessory phases examined increase with the water content of the melt, up to 2 wt.% H₂O. At higher water contents, solubilities are nearly constant. It can be concluded that water is not an important control of accessory phase solubility, although the water content will affect diffusivities of components in the melt, thus whether or not accessory phases will be present as restite material. The solubility behaviour in the subaluminous and peralkaline melts supports previous spectroscopic studies, which have observed differences in the coordination of high field strength elements in dry vs. wet subaluminous granitic glasses, but not for peralkaline granitic glasses. Lastly, the fact that wolframite solubility increases with increasing water content in the subaluminous melt suggests that tungsten dissolved as a hexavalent species.     

Quaternary stresses revealed by calcite twinning inversion: insights from observations in the Savonnières underground quarry (eastern France)

Calcite samples were extracted both from the rock matrix and the superficial coating of a karstified fault plane of an underground quarry, located in the eastern border of the Paris basin. The karstification is dated as Quaternary. Analysis of mechanical calcite twinning reveals that only the calcite matrix has also undergone a compression trending WNW that can be attributed to the Mio-Pliocene alpine collision. Both coating and matrix have undergone a strike-slip regime with σ₁ roughly trending north–south, that could correspond to the regional present-day state of stress, a strike-slip compression rather trending NNW, modified by local phenomena. To cite this article: M. Rocher et al., C. R. Geoscience 335 (2003).     

HYDROGEOLOGY

正20141756 Chen Ruige(Mathematical College,China University of Geosciences,Beijing100083,China);Zhou Xun Numerical Simulation of Groundwater Level Fluctuation in a Coastal Confined Aquifer with Sloping Initial Groundwater Level Induced by the Tide(Geological Bulletin of China,ISSN1671-2552,CN11-4648/P,32(7),2013,p.1099-1104,6 illus.,16 refs.) Key words:confined water,groundwater level     

METAMORPHIC PETROLOGY

正20141408 Cai Jia(Institute of Geology,Chinese Academy of Geological Sciences,Beijing100037,China);Liu Fulai Petrogenesis and Metamorphic P-T Conditions of Garnet-Spinel-Biotitebearing Paragneiss in Danangou Area,Daqingshan-Wulashan Metamorphic Complex Belt(Acta Petrologica Sinica,ISSN1000-0569,CN11-1922/P,29(7),     

SERIALS

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GEOPHYSICAL EXPLORATION

正20142386An Guoying(China Aero Geophysical Survey and Remote Sensing Center for Land and Resources,Beijing 100083,China)Application of Satellite Remote Sensing in Regional Hydrogeological Investigation:Taking Cenozoic Strata in Wenquan Sheet(1∶250 000)of Karakoram Range as an Example(Geosci-     

QUATERNARY GEOLOGY & GEOMORPHOLOGY

正20141016An Chengbang(Key Laboratory of Western China’s Environmental Systems,Ministry of Education,Lanzhou University,Lanzhou 730000,China);Zhao Yongtao Lake Records during the Last Glacial Maximum from Xinjiang,NW China and Their Climatic Impli-     

PETROLEUM GEOLOGY

正20141538 Cao Qing(School of Earth Sciences and Engineering,Xi’an Petroleum University,Xi’an 710065,China);Zhao Jingzhou Characteristics and Significance of Fluid Inclusions from Majiagou Formation,Yichuan Huangling Area,Ordos Basin(Advances in Earth Science,ISSN1001-8166,CN62-1091/P,28(7),2013,p.819-828,7 illus.,3 tables,43 refs.)