藏北羌塘盆地晚侏罗世海相油页岩生物标志物特征、沉积环境分析及意义

胜利河油页岩位于青藏高原腹地的羌塘盆地,具单层厚度薄、区域延伸长的特点,为羌塘盆地新发现的又一处海相油页岩.采用GC-MS(IRMS)分析方法对该油页岩进行了研究,结果表明,胜利河油页岩(11层以及13层)含有丰富的正烷烃、类异戊二烯烃、萜类化合物和甾类化合物.正构烷烃呈前高后低的单峰型分布,nC15、nC16为主峰碳,轻烃组分占有绝对优势,OEP值0.96～0.97,接近平衡值1.00,Pr/Ph为0.57～0.75,显示弱的植烷优势;萜烷丰度顺序为五环三萜烷》三环萜烷》四环萜烷;规则甾烷呈不对称的"V"字型分布,表现为C27》C29》C28的分布特征.这些特征与剖面中其他岩性的生物标志物特征存在一定的差异,9层泥晶灰岩C21-/C21 值为0.86,轻烃优势并不明显;14层泥灰岩C21-/C21 值为0.41,具有明显的重碳优势;9层泥晶灰岩以及12层泥灰岩规则甾烷呈C29》C27》C28的特征也与油页岩层存在显著的差异.这些差异不仅反映了油页岩层与其他岩性间生物母源输入的差异,也反映了他们之间沉积环境的不同.胜利河地区油页岩的形成是综合因素控制的结果,古地理变化、海平面升降、生物群差异以及气候的变化均对该区油页岩的形成有一定的影响.     

辽河盆地煤系地层中特高含量的二萜类及其地质意义

从辽河盆地东部凹陷下第三系沙三段煤系烃源岩中检出了特高含量的海松烷,脱氢松香烷等三环二萜烷和扁枝烷等四环二萜烷类化合物,此外还检测到了奥利烯、乌散烯等罕见的三萜类。上述三类化合物尽管出现在同一套地层中,但它们的主要来源并不完全相同,其中三环二萜和四环二萜类分别以裸子植物和蕨类植物为主要来源,而五环三萜类则主要来源于被子植物。说明辽河盆地下第三系沙三段煤系地层中母质输入的多样性和复杂性。     

鄂尔多斯盆地西南部长8段砂岩沥青地球化学特征及其来源分析

系统采集了鄂尔多斯盆地西南部地区延长组8段沥青砂岩,对砂岩沥青的地球化学特征进行了研究,探讨了沥青的母质特征、形成环境和成熟度。研究结果表明:(1)长8段砂岩沥青中高碳数的正构烷烃优势明显,规则甾烷中C_(29)含量相对较高,萜烷系列中四环萜烷含量较高,C_(24)四环萜烷/(C_(24)四环萜烷+C_(26)三环萜烷)的值为0.26~0.52,C_(23)三环萜烷/(C_(23)三环萜烷+C_(30)藿烷)的值分布范围为0.06~0.41,这些都指示研究区长8段砂岩沥青母质来源为混合型,并且陆源有机质贡献较大;(2)砂岩沥青中Pr/Ph为0.67~1.07,同时,沥青中检测出低丰度的β胡萝卜烷,说明沥青形成环境为弱氧化—弱还原环境,较低丰度的伽马蜡烷与C_(30)+藿烷指示沥青的母质形成于淡水或微咸水湖泊环境;(3)长8段砂岩沥青的C31藿烷22S/(22S+22R)、C_(29)甾烷20S/(20S+20R)、C_(29)甾烷ββ/(αα+ββ)和C_(29)重排甾烷20S/(20S+20R)均接近或已经达到平衡值,反映沥青为成熟沥青。将研究结果与已报道潜在烃源岩的生物标志化合物特征进行对比,显示出研究区长8段砂岩沥青主要来源于延长组7段烃源岩,表明长7段烃源岩是研究区最主要的烃源岩之一。     

Depositional Environment of Es_4~u and Es_3~l Shales Based on Biomarkers from the Boxing Sag of Dongying Depression,East China

The Boxing Sag is located in the southwest of Dongying Depression, southern Bohai Bay Basin of East China. It is one of the main petroliferous sags in the Dongying Depression, and has two major source rocks, namely the upper 4th Member （Es4u） and lower 3rd Member （Es31） shales of Eocene Shahejie Formation, which are the new exploration targets in recent years. In this study, 16 core samples were collected from Es4u and Es31 shales in the Boxing Sag, and the saturate hydrocarbons were analyzed by gas chromatography （GC） and gas chromatography-mass spectrometry （GC-MS）, respectively. The results show that Es4u shale has obvious phytane and gammacerane predominance, higher concentration of tricyclic terpanes and regular steranes, and very low concentration of 4- methly steranes; Es31 shale has pristane predominance, lower concentration of tricyclic terpanes, gammacerane and regular steranes, and higher concentration of 4-methly steranes. The Es4u shale can be further divided into two types based on the distribution of n-alkanes in gas chromatograms： normal distribution and double peak pattern. The biomarker characteristics and sedimentary facies distribution show that Es4u shale was deposited in the saline-hypersaline semi-deep （Type A Es4u shale, sag center） to shallow （Type B Es4u shale, sag edge） lacustrine environments, Es31 shale was deposited in the freshwater-brackish semi-deep-deep lacustrine environments, and the former sedimentary facies maps of Es4u and Es31 in the Boxing Sag are further modified.     

Biomarkers in crude oil revealed by comprehensive two-dimensional gas chromatography time-of-flight mass spectrometry: Depositional paleoenvironment proxies

Crude oil samples from two basins were analyzed using comprehensive two-dimensional gas chromatography coupled to time-of-flight mass spectrometry (GC×GC–TOFMS) to better understand the compositional heterogeneity of branched-cyclic hydrocarbons. GC×GC–TOFMS and conventional GC–MS results were compared. GC×GC–TOFMS revealed a wide range of compounds, including tricyclic, tetracyclic and pentacyclic terpane series, rearranged hopanes, methyl hopanes, secohopanes, onoceranes and steranes. Assignment of methyl hopane and 8,14-secohopane series other than onocerane isomers was only possible due to the high peak capacity and sensitivity of GC×GC. The oils comprised a mixture of two end members: non-biodegraded oil with abundant tricyclic terpanes and hopanes, and severely biodegraded oil with abundant 8,14-secohopane and demethylated tricyclic terpanes. A predominance of two distinct series, 3β-methylhopane and onocerane, was detected only in the lacustrine samples (classification based on biomarker parameters). In contrast, the predominance of a 2α-methylhopane series and lack of onocerane were found only for the marine oil sample. The results suggest that the distribution of 3β- and 2α-methylhopane series and the presence or absence of onocerane isomers reflect genetic differences in the source organic matter and that these compounds are new classes of biomarkers that can used as depositional paleoenvironment proxies.     

羌塘盆地二叠系展金组烃源岩生物标记化合物特征及意义

本文对羌塘盆地二叠系展金组烃源岩的岩心样品进行了烃源岩基本特征及生物标志化合物特征研究,重点探讨了烃源岩生烃母质来源、沉积环境特征及成熟度特征。研究显示,展金组烃源岩富含正构烷烃、类异戊二烯烷烃、萜类化合物和甾类化合物。其中,正构烷烃多为前高后低的单峰型,具有低碳数优势,nC15、nC16或nC17为主峰碳;规则甾烷中C27-C28-C29呈"V"字型分布,C27占优势;萜烷具有三环萜烷>五环三萜烷>四环萜烷的相对丰度,三环萜烷/五环三萜烷值在1.1~1.96之间;生烃母质主要来源于海相低等水生生物。Pr/Ph分布范围在0.53~1.16,平均值为0.85,植烷优势较明显;五环三萜烷的Ts/(Tm+Ts)值表明烃源岩形成于还原环境。而伽马蜡烷的含量以及伽马蜡烷/αβ-C30藿烷比值,证明烃源岩沉积时水体盐度为正常盐度。甾烷的C29 ααα20S/(20S+20R)和C29 αββ/(αββ+ααα)、萜烷的C31αβ22S/(22S+22R)、Ts/(Tm+Ts)值等反映烃源岩成熟度的参数显示,烃源岩处于成熟阶段。     

Effect of water washing on hydrocarbon compositions of petroleum sandstone reservoir rocks in Tarim Basin, NW China

Gross compositions and distribution of saturated and aromatic hydrocarbons in Carboniferous sandstone reservoire rocks in oil and water zones for Tzhong-10 well of the Zhongyang Uplift in the Tarim Basin were studied in dteail by means of Rock-Eval Pyrolysis,thin-chromatograph-flame ionization detection(TLC-FID),gas chromatography,gas chromatography-mass spectrometry.The results suggest that the gross composition of reservoir hydrocarbons between the oil zone and the water zone show significant differences,Water wahing has a dramatic effect on saturated hydrocarbon blomarkers,especially drimane series compounds,Drimane series compounds in the water zone have been depleted completely.However,the contents of tricyclic iterpanes and pentacyclic triterpanes tend to decrease slightly,but the water-zone reservoir hydrocarbons contian a large amount of gammacerane.This suggests that gammacerane be more resistant to water washing than diterpanes and homohopanes.The contents of pregnane,homopregrane,diasteranes relastively decrease as a result of water washing.Water washing has a noticeable effect on polycyclic aromatic hydrocarbon compounds,especially aromatic sulfur compounds,and the contents of dibenzothiophene series compounds and benzonaplyiothipophene decrease significantly as a result of water washing.However,the conterts of bicyclic and tricyclic aromatic hydrocarbons decrase slightly and those of tetracyclic and pentacyclic aromatic hydrocarbons,especially benzofluoranthene and benzopyrenes,increase markedly owing to adecrease in light aromatie hydrocarbons as a result of water washing.     

Aliphatic and diterpenoid hydrocarbons and their individual carbon isotope compositions in coals from the Liaohe Basin, China

Abundant tricyclic diterpanes (i.e., pimarane, dehydroabietane and simonellite) and tetracyclic diterpanes (e.g., phyllocladane) were detected in coal samples from the third member of the Shahejie Formation, Lower-Eogene, Liaohe Basin, China. Gas chromatography–isotope ratio mass spectrometry (GC–IRMS) analyses show that the carbon isotopic composition of terrigenous tricyclic and tetracyclic diterpenoid hydrocarbons are about 4–6‰ enriched in ¹³C compared to n-alkanes in the same samples. In addition, the pimaranes and phyllocladane have comparatively narrow stable carbon isotopic compositions among the different samples, with a slightly wider range in δ¹³C compositions for the abietanes (i.e., abietane, dehydroabietane and simonellite). The n-alkanes and triterpenoids reflect the δ¹³C compositions of higher plant wax.     

四川南桐地区二叠系龙潭煤层生物标记物及其地质意义

四川南桐地区二叠系龙潭煤层具有良好的生油潜力。其生物标记物包括正构和异构烷烃,类异戊二烯烷烃,倍半萜烷,二萜烷,三环萜烷,藿烷,一种未知结构的五环三萜烷(C₃₀),甾烷,4-甲基甾烷等。煤层生物标记物特征表明在其形成过程中有藻类和细菌等微生物物质的加入。     

黔西纳雍地区下寒武统牛蹄塘组黑色岩系生物标志物的特征

以贵州纳雍地区下寒武统牛蹄塘组黑色页岩为研究对象,分析其中的生物标志化合物。结果表明：奇偶优势(OEP)均值为1.08,接近平衡值1.00,无明显奇偶优势,姥鲛烷与植烷比(Pr/Ph)均值小于1,具明显的植烷优势;萜烷丰度顺序为五环三萜烷>三环萜烷>四环萜烷,规则甾烷以C27略占优势,ΣC27/ΣC29的均值为1.41,大于1,显示有机质来源以浅海相菌藻类等低等水生生物为主;C32αβ22S/(22S+22R)平均值为0.59, Ts/(Ts+Tm)值为0.43,βα-莫烷/αβ-藿烷平均值为0.124,C29甾烷的20S/(20S+20R)平均值为0.39,C29甾烷αββ/(αββ+ααα)平均值为0.41,均表明纳雍地区黑色岩系中的有机质均接近或达到成熟阶段。根据这些特征可以推断,该区域早寒武世牛蹄塘组黑色岩系形成于浅海还原环境,有机质热演化程度较高,其母质主要来源于细菌、藻类等低等水生物。     

Trace element distribution and oil yield data from the parachute creek member of the green river formation,colorado

The determination of trace element concentrations in oil shale before mining and retorting is required for proper solid-waste management planning. Using routine Fischer assay oil yield data collected during resource characterization as indicators of potential trace element concentrations could lead to a standard method of identifying strata containing high trace element levels. In order to determine a correlation between trace element concentrations and oil yield, shale samples were selected from four statigraphic zones of the Parachute Creek Member of the Green River Formation for analysis. All samples were analyzed for total elemental concentrations, mineralogy, and Fischer assay oil yield. The results of these analyses demonstrated that the Mahogany zone shales contain significantly greater trace element concentrations (antimony, arsenic, cadmium, chromium, copper, lead, lithium, mercury, molybdenum, nickel, selenium, silver, and vanadium) than the other three shale zones. These high trace element concentrations have been identified within well-defined interbedded tuff deposits in the Mahogany zone. In addition, all trace elements evaluated, except boron, show either increasing or decreasing concentrations as oil yield increases within all oil shale zones. With an increased number of analyses of existing oil shale cores, oil yield data will be correlated to specific stratigraphic units containing high trace element concentrations.     

藏北高原双湖地区中侏罗统海相油页岩生物标志化合物分布特征及其意义

重点报道了藏北双湖地区中侏罗统海相油页岩的生物标志化合物特征，首次在该层位油页岩中检出丰富的正烷烃、类异戊二烯烷烃、萜类化合物及甾类化合物。正烷烃图谱呈单峰形，nC15、nC16或nC17为主峰碳，轻烃组份占有绝对优势，OEP值0.93～1.01，无明显的奇偶碳数优势分布；Pr/Ph值为0.77～1.59，在剖面序列中呈波动分布，显示弱植烷优势或姥鲛烷优势；藿烷以C30占优势，萜烷相对丰度五环三萜烷>三环萜烷>四环萜烷；规则甾烷∑（C27+C28）>∑C29，∑C27/∑C29值为0.79～ 1.20，在剖面序列中下部C27甾烷略占优势，上部C29甾烷略占优势，重排甾烷C27/规则甾烷C27值为0.51 ～3.63，在剖面序列中具有显著的波动性，同时检出了少量孕甾烷和4-甲基甾烷。有机质母质构成中，既有丰富的藻类等低等水生生物，可能还有一定比例陆生高等植物输入混合的特点。油页岩处于成熟阶段，整个油页岩剖面序列具有一致的热演化程度。剖面中部油页岩具有极高的原始生产力，氧化-还原条件也是控制油页岩TOC和沥青“A”含量在剖面垂向变化的重要因素。     

Geochemical Characteristics of Different Kinds of Crude Oils in the Tarim Basin,Northwest China

Based on the compositions and distributions of biomarkers in thirty-five representative oil samples, oils from the Tarim Basin of northwestern China are mainly divided into two oil families. One oil family contains relatively low amounts of C₁₅-C₂₀ isoprenoid hydrocarbons and shows pristane predominance with Pr/Ph ratios ranging from 1.50 to 3.00. The GC/MS analytical data of these oils show the occurrence of abundant hopanes, and low concentrations of steranes and tricyclic terpanes with hopanes/steranes ratios from 6.25 to 12.24 and tricyclic terpanes/hopanes ratios from 0.03 to 0.24. These oils contain low drimane relative to homodrimane (C₁₅/C₁₆ < 1.0) and abundant rearranged bicyclanes in bicyclic sesquiterpanes. They are dominated by low carbon number (C₁₉-C₂₁) compounds in the tricyclic terpanes, and are rich in rearranged hopanes, C₂₉Ts and an unknown C₃₀ compound in pentacyclic triterpanes. These geochemical characteristics suggest that the oils were generated mainly from terrigenous organic matter. The other oil family shows remarkably different biomarker compositions and distributions. The oils revealed Pr/Ph ratios of about 1.0, high drimane/homodrimane ratios (>1.0), low hopanes/steranes ratios (0.65–2.50), high tricyclic terpanes/hopanes ratios (0.30–2.00) and a dominant peak at C₂₃ in tricyclic tepanes, suggesting a marine organic origin. Oil-source rock correlation indicates that these two oil families seem to have been derived from Mesozoic Jurassic-Triassic terrestrial source rocks (shales and coal seams) and Lower Paleozoic Ordovician-Cambrian marine source rocks, respectively.     

Molecular geochemical characteristics of source rock in faulted lacustrine basin: A case study of the Lishu Fault Depression in southern Songliao Basin, China

Terrestrial faulted lacustrine basin is considered as a favorable place for the development of source rocks,especially the fault basins in eastern China.Based on molecular composition study of saturated and aromatic hydrocarbons in the extracts of source rocks of the Yingcheng and Shahezi formations in the Lishu Fault Depression,it is revealed that the extracts of source rocks are provided with low ratio of Pr/Ph,low content of C24 tetracyclic terpanes,high content of tricyclic terpanes and gammacerane,relatively high content of C27 steranes in the sag belt and its periphery;relatively high ratio of Pr/Ph,relatively high content of tetracyclic terpanes and gammacerane,low content of C27 steranes and obvious advantages of C29 steranes in its gentle slope belt;with high ratio of Pr/Ph,high content of C19,C20 tricyclic and C24 tetracyclic terpanes,very low content of gammacerane and C27 steranes,and high content of C29 steranes in the edge of fault depression.According to the organic matter input and sedimentary environment,three types of source rocks have been established,which,respectively,are the mode of mixing organic matter input in deep and semi-deep lake,the advantage of terrigenous input in shallow lake and terrigenous input in shore-shallow lacustrine.The first mode is supposed to generate oil and gas,while the second one tends to generate oil.The distribution characteristics of oil and gas in the Lishu Fault Depression are very likely to be controlled by hydrocarbon generating characteristic of different source rock types.     

Distribution and Significance of Methyl Steranes in Bohai Bay Basin, East China

31 samples of shales and mudstones developed in reducing hypersaline and freshwater setting and 20 oil samples of Bamianhe oilfield, Bohai Bay basin were collected for a detailed study of petroleum system. Composition and distribution, especially significance of steroids, are discussed as a part of those. Abundant steroidal biomarkers, including C27-29 regular steranes, C28-30 4-methyl steranes, dinosteranes and aromatic steranes, were detected. Results show that the composition and distribution of the steroids in samples studied are functions of thermal maturity, organic source, paleoenvironment and lithology of potential source rocks. Alga-rich Es4 shales (brackish water) developed in the south slope of depocenter (Niuzhuang sag) were found particularly rich in steroidal biomarkers including C30 4-methyl steranes and dinosteranes. Es3 mudstones (fresh water) were found devoid of dinosteranes. Distribution patterns of regular steranes are completely different from methyl steranes indicating different origins of the specific compounds of the fraction. Diagnostic distribution of steranes in rock extracts of diverse intervals makes the compounds to be essential indictors of source-rock tracing. Methyl steranes prove to be much more useful in oil-source rock correlation than regular steranes. Results also show that alga-rich Es4 shales located in the south slope are not likely the primary source rock responsible for the oils discovered based on the composition and distribution of steroids.     

Identification of some diterpenoid hydrocarbons in petroleum

19-Norisopimarane and isopimarane have been synthesized from isopimara-9(11), 15-diene-3β, 19-diol. Analysis of the alkane fractions of an Australian crude oil by GC-MS showed the presence of nine diterpenoid hydrocarbons (diterpanes), of which one was bicyclic two were tricyclic and six were tetracyclic.19-Norisopimarane and isopimarane were identified by comparison of their mass spectra and GC retention times with those of the synthetic standards. ent-Beyerane, 16a(H)-phyllocladane, 16)β(H)-phyllocladane, ent-16α(H)-kaurane and labdane were also identified by comparison with authentic reference compounds. The remaining two compounds were tentatively identified as rimuane and as a 17-nortetracyclic diterpane on the basis of mass spectral evidence. The diterpanes are probably derived from conifer resins.     

Evolution characteristics of saturated hydrocarbons of enclosed organic matter in carbonate minerals in Tieling limestone under high temperature and high pressure

The enclosed organic matter chiefly releases lower carbon-number n-alkanes under high temperature and high pressure,while the kerogen mainly produces higher carbon-number n-alkanes.The rsidual hydrocarbons generated by both kerogen and enclosed organic matter in the Tieling limestone contain abundant tricyclic terpanes,pentacyclic triterpanes and steranes,but the contents of tetracyclic terpanes and 25-norhopane are lower.The residual enclosed orgainc matter shows the same distribution characteristics of n-alkanes,steranes and terpanes as that of the original bitumaen A,i.e.,the higher contents of triterpanes and tetracyclic terpanes,the higher ratios of 25-norhopanes over regular hopanes and markedly degraded steranes.By comparing the residual hydrocarbon.residual enclosed orgainc matter and original enclosed orgainc matter.it can be concluded that steranes and terpanes in the residual hydrocarbons are produced mainly by the kerogen and subordinately by the residual enclosed organic matter,the steranes and terpanes do not enter into the residual enclosed organic matter,and the thermal evolution of the residual enclosed organic matter maintains its unique character.Furthermore,pressure retards the pyrolysis of higher carbon-number alkanes and influences the isomerization ratios of C29-steranes,making 20S/(20S 20R) lower under the higher pressure than that under lower pressure,Higher pressure retards the thermal evolution of organic matter.     

Analysis of steranes and triterpanes in geolipid extracts by automatic classification of mass spectra

A computer method is described for the automatic classification of triterpanes and steranes into gross structural type from their mass spectral characteristics. The method has been applied to the spectra obtained by GC-MS analysis of two mixtures of standards and of hydrocarbon fractions isolated from the Green River and Messel oil shales. Almost all of the steranes and triterpanes identified previously in both shales were classified, in addition to a number of new components. The results indicate that classification of such alkanes is possible with a laboratory computer system. The method has application to diagenesis and maturation studies, and to oil/oil and oil/source rock correlations, in which rapid screening of large numbers of samples is required.     

辽西地区北票组烃源岩生物标志化合物特征的差异性

北票组是辽西地区重要的一套煤系地层,被认为是该区油气勘探的重要目的层.坤头营子剖面和卧龙剖面是该区较为有代表性的北票组地层剖面,对于研究北票组的沉积环境、有机质来源等具有重要意义.采用气相色谱-质谱（GC-MS）等技术对2个剖面的烃源岩样品进行了分析测试,结果显示两组样品表现出不同的地球化学特征.坤头营子剖面的烃源岩样品抽提物正构烷烃的质量色谱图均为单峰态,主峰碳数以C19为主,姥鲛烷/植烷比值（Pr/Ph）在3.0~4.0之间;甾烷系列中以C29甾烷为优势,C23三环萜烷含量相对较低,伽马蜡烷指数低（平均0.08）.取自卧龙剖面的样品质量色谱图大部分呈现双峰态,Pr/Ph值低;甾烷系列中C27占优势,萜烷系列中C23三环萜烷含量高,具有较高的伽马蜡烷含量（平均0.23）,且各项生标成熟度参数均已达到异构平衡化阶段.结合样品的全岩分析显微组分分析结果,认为两者主要差异可能是剖面附近的侵入岩造成,北票组烃源岩有机质具有陆源高等植物和低等水生生物双重来源,以陆源高等植物为主.     

羌塘盆地胜利河油页岩有机地球化学特征及意义

通过对藏北羌塘盆地胜利河地区2008年新发现的油页岩剖面进行系统采样和GC—MS分析,结果显示该地区油页岩具有较高C29ααα20S/ααα(20S+20R)（0.38~0.44）、C29αββ/(ααα+αββ)（0.37~0.47）和C3122S/(22S+22R)（0.52~0.59）比值,表明其有机质已进入生油阶段。分析的油页岩样品具有较高的C27甾烷含量（32.82%~43.6%）和较高4 甲基甾烷/规则甾烷（0.04~0.22）、甾/藿（0.80~1.04）比值,显示浮游植物为主的生物母源对油页岩的贡献。此外,油页岩具有较高的γ 蜡烷指数（0.34~0.50）、C35升藿烷指数（0.076~0.102）和较低的Pr/Ph比值（0.32~0.49）,表明胜利河地区油页岩沉积期水体处于相对闭塞还原和盐度较高的沉积环境。