鄂尔多斯盆地杭锦旗地区天然气地球化学特征及气源探讨

为明确鄂尔多斯盆地杭锦旗地区不同区带天然气特征及来源上的差异,通过天然气气体组分分析和碳同位素分析等手段,对杭锦旗地区3个主要勘探区带天然气地球化学组成特征进行了详细的对比剖析,并结合各区带天然气在成藏过程中的差异,对其来源进行了分析探讨。研究区天然气烃类气体含量较高(以甲烷为主),干燥系数多低于0.95,整体呈现出湿气特征,非烃类气体主要为二氧化碳和氮气,含量较低;天然气碳同位素δ^(13)C_(1)、δ^(13)C_(2)和δ^(13)C_(3)组成表现为正碳序列分布,但不同区带天然气碳同位素组成之间存在着差异,其中什股壕区带天然气δ^(13)C_(1)值最重,而新召区带天然气δ^(13)C_(2)和δ^(13)C_(3)值要明显重于其他2个区带。成因分析结果表明,研究区3个区带天然气均为有机成因气,呈现出煤型气(腐殖型气)的特征,主体为干酪根初次裂解气,且其气源岩处于高成熟—过成熟热演化阶段。结合气源对比结果与地质背景,推测新召区带天然气主要由下伏山西组烃源岩供烃,独贵加汗和什股壕区带天然气则来源于断裂南部太原组和山西组烃源岩的共同贡献,但前者太原组烃源岩贡献比例相对更高。

鄂尔多斯盆地杭锦旗地区山西组-太原组烃源岩地球化学特征对比研究及意义

以鄂尔多斯盆地杭锦旗地区山西组太原组煤系烃源岩为研究对象,通过总有机碳测定、岩石热解分析、碳同位素测定及GC-MS分析等多种技术手段对两套烃源岩的地球化学特征进行了系统研究。结果表明,研究区山西组太原组烃源岩有机质含量均较高,有机质类型以Ⅲ型为主,生烃潜力好。其中山西组烃源岩整体生烃潜力较太原组强,而太原组烃源岩成熟度则较山西组高。通过将两套烃源岩生物标志化合物特征进行对比分析发现,山西组烃源岩具有高姥植比,高(C_(19)三环萜烷+C_(20)三环萜烷)/C_(21)三环萜烷值,高C_(24)四环萜烷、C_(29)规则甾烷、氧芴相对含量和低伽马蜡烷相对丰度的特征,反映其可能形成于氧化偏氧化的淡水环境,有机质来源以高等陆生植物为主;太原组烃源岩则具有低姥植比,低(C_(19)三环萜烷+C_(20)三环萜烷)/C_(21)三环萜烷值,低C_(24)四环萜烷、C_(29)规则甾烷相对含量,低伽马蜡烷相对丰度和高硫芴相对含量的特征,说明其形成环境可能为相对偏还原的淡水环境,有机质来源中低等水生生物的贡献较多。基于两套烃源岩生物标志化合物组成特征上的差异,选取合适的生标参数建立了相应的有机地化判识指标将两套烃源岩区分开,这对研究区后续的油源对比及油气勘探工作有着较为重要的意义。

川中隆起安岳气田古油藏成藏时间厘定

安岳气田是中国目前最大的古老和深层气田,由新元古代-早古生代地层中的古油藏经原位裂解形成。由于古油藏-裂解气藏演化程度较高、时代较老,对其成藏演化的研究,特别是古油藏成藏时间的厘定,长期以来存在较多争议,缺乏足够地球化学证据的佐证。通过最新的实测大地热流史和类似地区的烃源层生烃门限研究,利用地质类比法替代流体包裹体测温,重建关键井埋藏史-热史,厘定德阳-资阳裂陷筇竹寺组烃源层的生烃和古油藏形成和破坏的时间,分析了古油藏的演化过程。地球化学实验和相关地质分析表明,筇竹寺组烃源层生烃时间既古油藏成藏时间约为275~263 Ma,相当于早二叠世后期(孔古阶)-晚二叠世。之后的深埋使古油藏自三叠纪初期开始裂解,在中侏罗世末期-早白垩世初期古油藏被完全破坏并形成大型裂解气藏。

中国中—新元古界地质学与油气资源勘探前景

距今1800—541Ma时期的中—新元古界是中国最古老的沉积地层。由于一直未确认可靠的早期生命和相应的生物化石,在20世纪50年代之前,国际石油地质学界普遍认为中—新元古界不会含有烃类沉积,也从未考虑将中—新元古界作为油气勘探的目的层。然而最近半个多世纪以来,古生物学家对地球元古宙早期生命演化的基础性研究取得重大进展,石油地质学家和地球化学家也发现中—新元古界古老地层中存在大量油苗、沥青和富含有机质的烃源岩,这些沉积有机质可跨越未成熟—过成熟的不同热演化阶段,部分地区至今仍处于"生油液态窗"的范畴内,以致迄今国内外发现了数十个原生油气田,探明相当规模的油气储量,并获得高产油气流,从而表明中—新元古界完全具备形成与富集规模性油气资源的条件。

冀北坳陷双洞背斜铁岭组沥青的有机地球化学特征及其地质意义

冀北坳陷双洞背斜铁岭组沥青样品是活油苗沿裂隙运移到地表后,在低温蚀变作用下形成的,未经高温蚀变,因而其有机地球化学信息丰富,能很好地反映沉积有机质原始地质信息。所分析的沥青样品中检测到了高丰度的13α(正烷基)三环萜系列、补身烷系列(包括长链的补身烷系列)、规则藿烷系列、25-降藿烷及8,14-断藿烷,未检测到甾类化合物,其中13α(正烷基)三环萜类是元古界沉积有机质中特有的一类生物标志化合物,其具体生源尚不明确。沥青样品中甾类化合物的缺失以及丰富规则藿烷类化合物的检出表明原核菌藻类生物应该是双洞背斜铁岭组沥青的主要生源;高丰度25-降藿烷和8,14-断藿烷系列的出现指示生物降解作用是导致沥青形成的重要因素之一。冀北坳陷沉积埋藏史、生烃史以及沥青样品中高丰度的13α(正烷基)三环萜类均证实,洪水庄组泥质岩应为双洞背斜铁岭组沥青的主要烃源岩。

塔里木盆地寒武系源岩地化特征及与典型海相原油对比

对27件塔里木盆地台盆区寒武系烃源岩样品进行地球化学分析及油源对比表明,寒武系烃源岩具有低姥植比、C_(21)三环萜烷/C_(23)三环萜烷比值大于1、升藿烷含量低甚至不含、伽马蜡烷含量高、C_(28)规则甾烷相对含量高、C_(27)三芳甾烷相对含量高、三芳甲藻甾烷含量高及同位素偏重等特征。寒武系烃源岩与典型寒武系、奥陶系原油油岩对比分析表明,寒武系烃源岩与T904和TD2等典型寒武系原油具有良好的亲缘性,而与台盆区大量发现的奥陶系油藏原油并无相关性,从而否定了寒武系烃源岩作为台盆区海相原油主力烃源岩的可能性。此外,塔西北地区柯坪隆起肖尔布拉克、东二沟及苏盖特布拉克等剖面烃源岩样品在生源构成上与台盆区其余寒武系烃源岩有一定差异,其母源有机质可能与奥陶系原油母源有机质具有部分相同的菌藻类构成。

中元古界沉积物中典型分子标志化合物及其地质意义——以宣隆坳陷下马岭组黑色页岩为例

分子标志化合物在前寒武纪古海洋生命演化和古环境的研究中发挥着越来越重要的作用。在华北克拉通宣隆坳陷中元古界下马岭组黑色页岩中检测到一系列典型分子标志化合物,其特征表现为明显的“UCM”鼓包,高丰度的甲基支链烷烃、C_(24)四环萜烷、C_(19)-C_(20)13β(H),14α(H)-三环萜烷、13α(正烷基)-三环萜烷系列以及四类重排藿烷化合物,甾烷系列化合物的缺失,其组成特征及其地质意义明显不同于显生宙沉积物。甾烷系列化合物缺失可能是异养微生物转化和降解的结果,不能否定真核藻类在14亿年前古海洋的局部繁盛,但生物群落仍以原核生物为主。

Oil filling history of the Bashituo Oilfield in the Markit Slope,SW Tarim Basin,China

The Markit Slope is an important area for the petroleum exploration in the Tarim Basin. Elucidation of the oil filling history of discovered oilfields has great significance for recognizing the accumulation processes of the whole region. Using molecular geochemistry, fluid inclusion techniques and basin modeling, we studied the oil filling process of the Bashituo Oilfield that is located in the west of the Markit Slope. The molecular migration indexes, such as the methyldibenzothiophene ratio （4-/1-MDBT）, trimethylnaphthalene ratio （TMNr） and pyrrolic nitrogen compounds content, decrease from west to east, indicating that the charging direction and migration pathways are from west to east. Lithological analysis and homogenization temperatures of saline fluid inclusions accompanied with oil fluid inclusions suggest that two charging periods occurred in the Devonian oil reservoir. Combining the burial history and heating history of well BT4, Basinmod 1D software modeling shows the two oil filling periods are from 290 Ma to 285 Ma and from l0 Ma to 4 Ma, respectively, and later oil filling dominates. This study may be helpful to understand the accumulation process and provide useful references for oil and gas exploration in the Markit Slope.

The Occurrence of Oleananes in the Beibuwan Basin and Its Application to the Study of Maturity and Oil-Source Rock Correlation

The oleanane parameter, i.e., OP （oleananes/（oleananes＋C30hopanes）） in the two sedimentary columns of the Beibuwan Basin, South China Sea, can be used to delimit the top of oil generation window, with Ro （/%） of 0.53 in Well M1 and 0.55 in Wells H1/Hd1/Hd2, respectively. Comparing with vitrinite reflectance （Ro/%）, the OP features a dynamic range and can indicate the oil generation window more precisely. By using OP and other geochemical indices, the oil-source correlation is also conducted. It suggests that the oils in wells M1 and M2 are derived from the source rocks in situ. The mudstone in Huachang uplift is not the main source rocks for oils in this area, The OP is also a useful oil-source correlation parameter in some Tertiary lacustrine basins.

Quantitative assessment and significance of gas washing of oil in Block 9 of the Tahe Oilfield,Tarim Basin,NW China

Some Ordovician and Triassic oils in Block 9 are characterized by light oils,which have distinctly differentiated from heavy oils in other blocks in the Tahe Oilfield,Tarim Basin.Based on the whole oil gas chroma- tograms,this paper estimates the effect of oil migration and fractionation and the amount of depletion(Q)in terms of the n-alkanes depletion model.The results showed that the amount of depletion in the Ordovician reservoir is highest in the east of this block,e.g.the depletion is 97% in Well T904.The amount of Q gets lower to the west,e.g.the depletion is 53.4%in Well T115 and there is no sign of depletion in Well S69.It is suggested that the direction of gas washing is from the east to the west.The compositions and isotopic characteristics of associated gas in Ordovician oils indicated that the gas might be derived from Cambrian source rocks of the Caohu Depression which lies to the east of Block 9.In contrast,no obvious depletion of n-alkanes in Triassic oils was found,suggesting that the migration pathway of natural gas has been limited to the Ordovician karst fracture system formed in the Early Hercynian Orogeny.Different depletions of the Ordovician and Triassic oils can reveal fault activities in this region.

Applications of molecular fossils in lacustrine stratigraphy

Biomarkers,or the so-called molecular fossils,are used tentatively in the Eogene lacustrine stratigraphy study in the Jiyang Sub-basin.Notwithstanding the fact that unidentified microfossils or amorphism and acritarchae are widely distributed in lacustrine source rocks,molecular fossils are useful to identify the sources.It is helpful to reconstruct the palaeo-enviroment,palaeo-ecosystem and compartmentalize the stratigraphic sequence by using molecular fossils with which the existence and types of microbes including bacteria,archaea and certain algae can be identified.

Geochemical Characterization and Origin of High-Sulfur,Heavy Oils in Jiyang Sub-Basin,East China

High-sulfur,heavy petroleum is widely occurring in the Tertiary lacustrine Jiyang sub-basin, Bohai Bay Basin.They are differentiated into two families based on the bulk properties and biomarker compositions.Family 1 is characterized by high resins（40%-71%）and sulfur（2%-4%）,and low wax （l%-6%）,with n-alkanes removed by biodegradation,whereas family 2 is characterized by extremely abundant sulfur（3%-10%）,and high asphaltenes（7%-31%）and wax（2%-19%）,with no evidence of microbial attack.The oils of family 1 are distributed in the reservoir,lower than 1500 m throughout the sub-basin.Biomarker assemblages,such as low pristane/phytane ratios（1 Pr/Ph）and a high abundance of carotane,gammacerane,and dinosterane,suggest that they are derived from the calcareous mudstones and shales among the stratified,saline Es_4~u unit,in addition to the in situ biodegradation-concentrated sulfur content.However,the oils of family 2 are identified only in the western Zhanhua and eastern Chezhen depressions,with a depth deeper than 1700 m.Physical properties,together with biomarker ratios,including even-numbered n-alkanes,1 Pr/Ph,trace diasteranes,higher C35 homohopanes,and abundant dibenzothiophene series,with1 dibenzothiophene/phenanthrene,indicate an origin from carbonate source rocks.The X-ray diffraction analysis showed that the carbonate source rock is limited in the Es_4~u unit of the Bonan sag,which is different from most other source rocks in the same horizon.It is suggested that the high-sulfur,heavy oils are generated at the early stage of the oil window.Bacterial sulfate reduction might be responsible for the occurrence of sulfur species in the high-sulfur,heavy oils,while heavy biodegradation will enhance sulfur concentrations.

A GC×GC-ToFMS Investigation of the Unresolved Complex Mixture and Associated Biomarkers in Biodegraded Petroleum

Heavy biodegraded crude oils have larger numbers of coeluting compounds than nonbiodegraded oils, and they are typically not resolved with conventional gas chromatography（GC）. This unresolved complex mixture（UCM） has been investigated using comprehensive two-dimensional gas chromatography–time-of-flight mass spectrometry（GC×GC-To FMS） within a set of biodegraded petroleums derived from distinct sedimentary basins, including northwestern Sichuan（Neoproterozoic, marine）, Tarim（Early Paleozoic, marine）, Bohai Bay（Eocene, saline/brackish） and Pearl River Mouth（Eocene, freshwater）. In general, the hydrocarbons that constitute the UCM in petroleum saturate fractions can be classified into three catalogues based on the distributions of resolved compounds on two dimensional chromatograms. Group 1 is composed mainly of normal and branched alkanes, isoprenoid alkanes and monocyclic alkanes; Group 2 comprises primarily terpanes ranging from two to five rings, and Group 3 is dominated by monoaromatic hydrocarbons such as tetralins and monoaromatic steranes. In addition, the UCM is source dependent and varies between oil populations. i.e., the UCM of petroleum derived from Precambrian and Early Paleozoic marine, Eocene saline/brackish and freshwater source rocks is specifically rich in higher homologues of A-norsteranes, series of 1,1,3-trimethyl-2-alkylcyclohexanes（carotenoid-derived alkanes）, and tetralin and indane compounds, respectively.

Geochemical analysis of mixed oil in the Ordovician reservoir of the Halahatang Depression,Tarim Basin,China

In this study,12 crude oil samples were collected and analyzed from the Ordovician reservoir in the Halahatang Depression,Tarim Basin,China.Although the density of oil samples varies considerably,based on saturated hydrocarbon gas chromatographic(GC),saturated and aromatic hydrocarbon gas chromatographic-mass spectrometric(GC/MS) and stable carbon isotopic composition analyses,all the samples are interpreted to represent a single oil population with similar characteristics in a source bed or a source kitchen,organic facies and even in oil charge history.The co-existence of a full suite of n-alkanes and acyclic isoprenoids with UCM and 25-norhopanes in the crude oil samples indicates mixing of biodegraded oil with fresher non-biodegraded oil in the Ordovician reservoir.Moreover,according to the conversion diagram of double filling ratios for subsurface mixed crude oils,biodegraded/non-biodegraded oil ratios were determined as in the range from 58/42 to 4/96.Based on oil density and oil mix ratio,the oils can be divided into two groups:Group 1,with specific density>0.88(g/cm3) and oil mix ratio>1,occurring in the north of the Upper Ordovician Lianglitage and Sangtamu Formation pinchout lines,and Group 2,with specific density<0.88(g/cm3) and oil mix ratio<1,occurring in the south of the pinchout lines.Obviously,Group 2 oils with low densities and being dominated by non-biodegraded oils are better than Group 1 oils with respect to quality.It is suggested that more attention should be paid to the area in the south of the Upper Ordovician Lianglitage and Sangtamu Formation pinchout lines for further exploration.

Determination of HCH and DDT in soils following Wenchuan 5.12 Violent Earthquake in China

A large number of disinfectants and insecticides were used on a large scale after the Wenchuan 5.12 Violent Earthquake. The disinfectants and insecticides, including HCH (hexachlorocyclohexane) and DDT (dichlorodiphenyltrichoroethane) as representative OCPs, could lead to serious environmental problems. In order to disclose the residues of HCH and DDT in soils following the Wenchuan 5.12 Violent Earthquake, surface soils in Dujiangyan City and Beichuan County were sampled in 2009. The samples were analyzed by GC/MS after pre- treatment by ultrasonic solvent extraction. It has been found that the concentra-tions of γ-HCH, β-HCH and 4,4'-DDT in soils of Beichuan County were 94–102.4, 14.1–36.1 and 2.9–4.3 times high their concentrations in those of the Wolong Nature Reserve, and the concentrations in soils of Dujiangyan City were 52.4–61.6, 8.8 –45.3 and 5.4–6.2 times high their concentrations in soils of the Wolong Nature Reserve, respectively. According to the isomers of HCHs and metabolites of DDTs, it could be concluded that these areas may have additional inputs of lindane and 4,4'-DDT.

Alkyl Naphthalenes and Phenanthrenes:Molecular Markers for Tracing Filling Pathways of Light Oil and Condensate Reservoirs

Condensates and light oils are generally characterized by high maturity, low concentration of sterane and terpane biomarkers and low content of non-hydrocarbon fraction. As a result, some commonly-used sterane, terpane and carbazole migration parameters in conventional oil reservoirs may have a certain limitation in condensate and light oil reservoirs for their poor signal-noise ratios in the gas chromatography-mass spectrometry （GC-MS）. Naphthalene, phenanthrene and their methylated substituents, however, are present in significant concentrations in condensates and light oils. Taking the Fushan depression （in the Beibuwan Basin, Northern South China Sea） as an example, this paper attempts for the first time to use polycyclic aromatic hydrocarbon （PAH）-related parameters to trace migration directions and filling pathways for condensate and light oil reservoirs. The result shows that TMNr （i.e. 1, 3, 7-TMN/（1, 3, 7-TMN ＋ 1, 2, 5-TMN）, TMN： trimethylnaphthalene））, MPI-1 （i.e. 1.5×（2-MP ＋ 3-MP）/（P ＋ 1-MP ＋ 9-MP）, P： phenanthrene MP： methyiphenanthrene）, MN/DMN （∑methylnaphthalene/∑dimethylnaphthalene, %） and MN/TMN （∑nethylnaphthalene/∑trimethylna- phthalene, %） can be used to trace the filling pathways of condensate and light oil reservoirs. These parameters, together with geological consideration and other bulk oil properties （e.g. the gas to oil ratio and density）, suggest that the condensates and light oils in the Huachang oil and gas field are mainly sourced from the Bailian sag that is located to the northeast of the Huachang uplift in the Fushan depression.

Characteristics of Oil and Gas Accumulation in Yong'an-Meitai Area of the Fushan Depression,Beibuwan Basin,South China Sea

The Yong＇an-Meitai area is the focus of the present exploration in the Fushan Depression, Beibuwan Basin, South China Sea. All oils from this area are geochemically characterized by higher Pr/Ph ratio, higher proportion of heavy molecular weight hydrocarbons, and higher proportion of C29 regular steranes, which indicate that the organic matter of source rocks might have been deposited in an oxidizing palaeoenvironment and be dominated by higher plant organic matter input. The oil from E3w2 （the second member of Weizhou Fro. of the Oligocene） has a much higher density, relatively higher Pr/nC17 and Ph/nC18 ratios, and a ＂UCM--unresolved complex mixture＂ on gas chromatograms, which indicate that it has been slightly biodegraded. CPI and other terpane and sterane isomer ratios suggest they are all mature oils. The timing of oil charging in E3w2 and E2I1 （the first member of the Liushagang Fro. of the Eocene） determined by the homogenization temperatures of fluid inclusions and thermal evolution history are from 9-3 Ma and 8-3 Ma, respectively. Thus, the interpretation of E3w2 as a secondary reservoir is unlikely. The timing of oil charging is later than that of hydrocarbon generating and expulsion of Liushagang Fin. source rocks and trap formation, which is favorable for oil accumulation in this area. All molecular parameters that are used for tracing oil filling direction decrease with shallower burial depth, which suggests vertical oil migration. The widely occurring faults that penetrate through the source rocks of the Liushagang Fro. may serve as a fine oil charging conduit.

Immature Oils in China and Their Genetic Mechanisms

Immature crude oils are a kind of unconventional petroleum resources. They are generated through early low-temperature biochemical/chemical reactions of some specific organic matter. Their geological reserves explored are as high as several hundred million tons in China. Based on a detailed organic geochemical study, five genetic mechanisms of immature oils have been proposed in this paper for early hydrocarbon generation from suberinite, resinite, bacteria-reworked terrestrial organic matter, biolipids and sulphur-rich macromolecules respectively.

The calculation of hydrocarbon-generating temperature——Theory and practice

How to quantitatively evaluate the maturity of crude oils is still an open question. Mango discovered a remarkable compositional invariance of four isoheptane ratios in crude oils, and proposed a steady-state catalytic model for the origin of light hydrocarbons. According to this model, 2,4/2,3 dimethylpentane ratio is a pure temperature parameter. Bement, Mango et al. established the functional equation between the two parameters-light hydrocarbon temperature and burial temperature and applied it to the calculation of hydrocarbon-generating temperature, which provided a new choice for the study of oil maturity. In this paper, the Mango's parameters for hydrocarbons from the Tazhong area were calculated, the average K1 value is 1.06, which is in good consistency with the Mango's proposal that the K1 value is relatively stable. Calculated with the functional formula of hydrocarbon-generating temperature, the hydrocarbon-generating temperatures are with the range of 120-129℃, and the converted vitrinite reflectance (Ro) varies from 0.88% to 0.90%. This is well consistent with the maturity characteristics of neohopanes. The results have verified the reliability of this method.

沉积物和原油中重排藿烷的生物来源和成因机制

重排藿烷逐渐在各类沉积物和原油中被检测,但其生物来源与形成转化机制等尚不清楚.在中元古界下马岭页岩和侏罗系湖相原油系统地鉴定了四类重排藿烷.基于各类重排藿烷相对丰度的变化关系和形成转化路径,明确了研究区各类重排藿烷的相对丰度和生成速率主要受控于生源构成或甲基重排反应过程.其中,早洗脱重排藿烷和21-甲基-28-降藿烷的形成过程比17α(H)-重排藿烷系列更为复杂,使得二者在沉积物和原油中分布相对局限.18α(H)-新藿烷不仅可源自细菌藿多醇,还可源自里白醇和里白烯,故其在地质样品中分布更为广泛.重要的是,虽然富含重排藿烷的烃源岩和原油屡见报道,但它们可能并非源自无处不在的细菌,而更可能仅存在于局限环境下的少数细菌种属.