华北地区下古生界海相烃源岩芳烃生物标志物地球化学特征——兼论饱 …

本文详细总结了华北地区下古生界海相烃源岩中芳烃生物标志的特征,主要包括菲系列联苯系列、苯并芴系列、三芴系列、荧蒽系列、芘系列、苯并荧蒽和苯并芘系列、屈系列和三芳甾烷系列,而萘系列含量较低。我们发现三苯甾烷Ｃ２８（２０Ｓ）／Ｃ２８（２０Ｒ）比值似乎显示了较了的热演化特征。     

盐城凹陷凝析油地球化学特征

运用碳同位素、气相色谱、色谱—质谱、流体包裹体技术，研究了盐城凹陷凝析油地球化学特征，并与永安凹陷永7井凝析油、下扬子海相原油进行了对比。该凝析油碳同位素为-28．8‰—30．5‰，全油色谱中含有一定的长使正构烷烃，Pr/Ph为1．56，三环菇烷含量高，伽玛蜡烷含量低，重排甾烷含量高，C29甾烷＞＞C27甾烷＞C28甾烷。石蜡指数、庚烷值表明原油为高成熟凝析油，甲基菲指数MPI表明原油为未熟—低藏原油，C29甾烷20S／(20S 20R)值表明原油为成熟原油。这种成熟度的差异可能与不同成熟度原油的混合作用有关。油气主要充注时间为6—15Ma。凝析油的主体可能源于泰州组烃源岩，凝析油的形成与蒸发分信作用密不可分。     

西藏措勤盆地下白垩统海相灰岩的芳烃地球化学特征

详细总结了西藏措勒盆地下白垩统海相灰岩的芳烃地球化学特征，包括萘、菲、芴、四环、五环及三芳甾烃系列化合物。总体组成以菲系列化合物占优势，四环和五环芳烃含量较高，其它芳烃含量较少为特征。样品中惹烯含量高，硫芴／氧芴值较高，且检出了一定含量的北、反映出该区海相灰岩的有机母源的多样性和具有利于有机质保存的还原沉积环境。应用萘、菲、芴、多环芳烃和三芳甾烃的各项成熟度参数分析了有机质的热演化特征，表明西藏措勤盆地下白垩统处于成熟阶段。     

海拉尔盆地贝尔凹陷原油芳烃化合物组成和分布特征

通过色谱-质谱分析,对海拉尔盆地贝尔凹陷35个原油样品进行聚类分析,将之分成4类.Ⅰ类原油是贝尔凹陷原油主体,占分析样品的77%,特点足菲系列含量高,平均值为64.7%,三芳甾类化合物和三芴类化合物含量次之,分别为11.42%和11.81%.Ⅱ类原油为高三芳甾类原油,三芳甾类化合物占芳烃化合物的53.9%,是该类原油的主要成份,非系列化合物含量较低,为32.5%,萘系列含量和三芴化合物含量最低,分别为0.6%和3.54%.Ⅲ类原油为高菲系列和高萤蒽含量原油,菲系列为64%,萤蒽含量高达11%,是其它原油的16倍以上.Ⅳ类原油具有高萘、高三芴化合物和低菲系列化合物的特点,分别占原油芳烃馏分的30%、32%和26%,三芳甾类化合物含量低,占3.6%.这充分说明海拉尔箍地烃源岩沉积期间有不同的沉积环境,原油有不同的牛烃母质.Ⅱ类原油以藻类为主要生烃母质,Ⅲ类原油以高等植物为主,Ⅰ类原油介于Ⅱ类和Ⅲ类原油之间,为混合型生烃母质.Ⅳ原油沉积环境和前三类原油明显不同,为咸水强还原湖相沉积环境.     

黔南坳陷油苗芳烃地球化学特征及意义

为明确黔南坳陷油苗芳烃地球化学特征及意义,采用 GC-MS、GC-IRMS 等方法对其芳烃地球化学特征进行了系统分析.结果表明,油苗芳烃总体具有贫13C、低联苯、高硫芴和低氧芴特征.其芳烃δ13C 值为–31.7‰~–30.2‰,平均–31.1‰;1,2,5-三甲基萘/1,3,6-三甲基萘值为0.20~0.40,平均0.26;4-甲基二苯并噻吩/二苯并噻吩值为0.63~1.98,平均1.31;(2-甲基二苯并噻吩+3-甲基二苯并噻吩)/二苯并噻吩值为0.33~1.33,平均0.76;联苯系列占芳烃含量的0.49%~7.57%,平均1.70%;上述特征总体表明油苗为海相成因,且其成烃母质为低等生源菌藻类.油苗硫芴含量占三芴系列的57.99%~95.78%,平均87.34%,氧芴含量很低,为0.96%~5.96%,平均2.26%; Pr/Ph 与二苯并噻吩/菲相关性分析以及芳基类异戊二烯烃的检出等均表明油苗成烃母质形成于还原-强还原环境.油苗饱芳比较高,均大于1.0;油苗三甲基萘比值2(TNR2)值为0.95~2.19,平均1.29,换算成等效镜质体反射率值为0.97%~1.71%,平均1.18%;甲基菲指数1(MPI1)值为0.31~1.01,平均0.66,其等效镜质体反射率值为0.59%~1.01%,平均0.80%;由4,6-二甲基二苯并噻吩/1,4-二甲基二苯并噻吩值换算油苗的等效镜质体反射率值为0.86%~1.47%,平均1.05%; C28三芳甾烷20S/(20S+20R)为0.48~0.58,平均0.55, TA(I)/TA(I+II)值为0.15~1.55,平均0.45;均指示油苗主要为成熟-高熟原油.油苗芳烃地球化学特征总体表明油苗为源自低等菌藻类生源的海相原油,成烃母质形成于还原-强还原环境,油苗总体为成熟-高熟原油;结合油苗碳、硫同位素及饱和烃特征,综合认为油苗具有相似的来源.     

不同沉积环境湖相低熟原油的芳烃分布特征

研究表明,不同沉积环境湖相的低熟原油芳烃生物标志物分布具有较大的差异。淡水湖相低熟原油芳烃以萘和菲系列化合物为主要组份、膏岩盐湖相低熟原油芳烃以脱羟基维生素Ｅ和三芳甾烷为主要组份、盐岩湖相低熟原油芳烃则以三芳甾烷为主要组份、其它生物标志化合物组份的相对丰度均较低。本次研究的低熟原油芳烃中普遍检测出明显的苯并藿烷系列化合物、盐湖相低熟原油芳烃中还检测出藿烷酮化合物,表明该地区古环境中细菌、微生物发育     

美国南佛罗里达盆地Sunniland原油和油源岩中芳烃的地球化学

本文用GC-MS技术分析了美国南佛罗里达盆地Sunnliand原油和油源岩抽提物中的芳烃,以便探讨碳酸盐岩环境中芳烃的分布特征,并用来重建古环境.Sunnliand原油和油源岩中含较半富的萘、菲、二苯并噻吩和三芳甾烷等化合物,甲基二苯并噻吩异构体呈V型分布.芴、氧芴和硫芴三系列化合物的相对含量以及其他地球化学特征如:Pr/Ph<1、正烷烃在C₂₂-C₃₀范围内呈偶碳优势、无或很少有二环倍半萜、含丰富的含硫芳烃等,指示Sunnliand原油和油源岩形成于海相强还原高盐环境.Sunnliand原油和油源岩中检出的一些化合物如:D环芳构化8,14-断藿烷、长链烷基苯、长链烷基苯并噻吩以及很高的延伸藿烷(C₃₁-C₃₅)和C₂₄、C₂₆四环萜烷表明Sunniland有机质有细菌输入.成熟度参数指示Sunniland原油和油源岩属未成熟至低成熟.     

北部湾盆地不同凹陷原油生物标志物分布与组成特征

通过对取自北部湾盆地不同凹陷典型原油样品中各类生物标志物的分布与组成特征的系统分析，发现盆地北部的涠西南凹陷和乌石凹陷所产原油具有姥植比低和奥利烷与各类重排构型生物标志物含量低，而C26+长链三环萜烷系列和C304 甲基甾烷含量高的特点，且其三环萜烷系列呈现以C23为主峰的正态分布，指示了该类原油的烃源岩沉积时水体较深，还原性相对较强，且原始生烃母质以藻类为主；而南部福山凹陷和迈陈凹陷所产的原油则具有姥植比高和奥利烷与各类重排构型生物标志物含量高的特征，而C26+长链三环萜烷系列和C304 甲基甾烷含量低，且其三环萜烷系列呈现C19—C26阶梯状依次降低，表明这类原油的烃源岩沉积时水体较浅，还原性相对较弱，且原始生烃母质中被子植物来源的陆源有机质贡献较大。由此表明北部湾盆地南北不同凹陷第三纪的沉积特征和有机质生源构成存在显著差异。     

塔里木盆地塔东2井稠油地球化学研究

运用棒色谱、碳同位素、色谱、色谱—质谱、色谱—质谱—质谱、流体包裹体技术研究了塔里木盆地中央隆起带东段的TD2井寒武系储层中的稠油。该稠油具有ω(Pr)／ω(Ph)高,伽马蜡烷、24—降胆甾烷、C28甾烷、甲藻甾烷、三芳甲藻甾烷、4—甲基—24—乙基胆甾烷及芳构化甾烷含量均高的特点,地质分析与油源对比结果表明原油来源于寒武系。原油中含有25—降藿烷系列,指示原油曾发生过生物降解作用,芳烃馏分中存在大量的菲、葸、苯并葸、苯并荧葸、芘等化合物及流体包裹体均一化温度均表明原油曾经历过热蚀变作用。流体包裹体均一化温度和埋藏史的分析表明TD2井的原油是在450—440Ma间形成的。     

4­‐­甲基甾烷在油源对比中的应用--以渤南洼陷北部陡坡带为例

同一洼陷不同次洼的烃源岩及生成的原油,由于古气候、古沉积环境较为相似,其常规生物标志化合物和同位素特征差别非常小,给油源分析带来困难。通过GC-MS分析提取原油和烃源岩中分子化石信息,主要依据4 甲基甾烷的相对含量和不同构型的4 甲基甾烷的分布特征来进行油源对比,为类似地区的油源分析提供了一种新思路。渤南洼陷发育Es4s和Es3x两套主力烃源岩,中部次洼、西部次洼和渤南深洼Es3x烃源岩的4 甲基甾烷/C29甾烷值分别为4.51、2.79、1.27,是由于烃源岩中沟鞭藻有机质占总有机质的比例不同所造成。不同地区原油C20、C21、C23三环萜烷和ααα20RC27、C28、C29规则甾烷等特征非常相似,成熟度相当,中、西、东三个地区原油的4 甲基甾烷/C29甾烷值分别为2.89,2.39和2.06,区别明显,各个地区4 甲基甾烷的构型也不同。对比结果表明,渤南洼陷北部陡坡带Es4s和Es3x油气均为近源成藏,主要来源于其临近次洼的Es3x烃源岩。     

Geochemical characteristics of aromatic hydrocarbons in saline lacustrine crude oils and their significance as exemplified by the south area of western Qaidam Basin

Based on quantitative GC-MS analysis of 40 crude oil samples collected from the south area of western Qaidam Basin,one of the largest saline lacustrine basins in China,the geochemical characteristics of aromatic hydrocarbons in oils were studied systematically in this paper.Among those constitutes,naphthalene(43% 59%),phenanthrene(12% 21%) and taromatic-sterane series(6% 28%) were the main ones of aromatic hydrocarbons.The ratio of aromatic hydrocarbon maturity parameter vs.saturated hydrocarbon maturity parameter C 29 20S/(20S+20R) shows that some aromatic hydrocarbon maturity parameters are not suitable for low-mature oils,including MPI,MNR,DNR,etc.Meanwhile,maturity parameters for dibenzothiophene and taromatic-sterane series are more appropriate for low maturity saline lacustrine crude oils.Based on the ratio of 4,6-DMDBT/1,4-DMDBT,the R c values are within the range of 0.59% 0.72%.However,the abundance of dibenzothiophene(DBT) is low,and the dibenzofuran(DBF) content is even lower,suggesting that the crude oils were formed in a saline lacustrine anaerobic environment.The high abundance of C 26 triaromatic steroid also indicates that the source material is brackish water-saline water with strong reducibility.     

鄂尔多斯盆地陇东地区延长组原油地球化学特征及成因类型划分

利用原油与岩样抽提物的族组成分离与定量分析、饱和烃色谱色质、芳烃色谱色质等分析测试资料,系统分析了陇东地区延长组原油的地球化学特征,并研究了原油的成因类型。研究表明,陇东地区延长组原油均为正常油,组分以饱和烃馏分为主;原油的母质来源为低等水生生物与陆源高等植物的双重贡献;形成环境为淡水微咸水的水体环境、弱氧化还原的沉积环境;原油为成熟油,属于烃源岩生烃高峰时期的产物。根据C30重排藿烷的相对含量,可将原油划分为3类,第Ⅰ类原油C30重排藿烷含量最低,第Ⅱ类原油C30重排藿烷含量中等,第Ⅲ类原油C30重排藿烷含量最高。其中第Ⅰ类原油最多,来自于长7油页岩,该类原油分布广泛,白豹、西峰、合水、华庆以及姬塬地区均以该类原油为主;第Ⅱ、Ⅲ类原油样品较少,与暗色泥岩关系密切,零星分布于镇北以北,西峰以东地区。     

Toxicity and compositional analysis of aromatic hydrocarbon fractions of two pairs of undegraded and biodegraded crude oils from the Santa Maria (California) and Vienna basins

The monoaromatic and total aromatic hydrocarbon fractions of two pairs of undegraded and moderately biodegraded crude oils from the Santa Maria basin (California) and the Vienna basin (Austria), all dominated by unresolved complex mixtures, were studied regarding their composition and toxicity towards the feeding rate of the marine mussel Mytilus edulis. Total aromatic and monoaromatic hydrocarbon fractions from sulphur-rich Monterey Formation crude oils were slightly more toxic than the fractions isolated from sulphur-lean Vienna basin oils. The ecotoxicity tests did not show any significant differences in toxicity of aromatic compounds from undegraded or in-reservoir biodegraded crude oils from the same oilfield although some differences in composition were observed. Organic sulphur compounds are suspected to cause the slightly higher toxicity of the aromatic hydrocarbon fractions from the Monterey oils.     

Dibenzofuran Series in Terrestrial Source Rocks and Crude Oils and Applications to Oil-Source Rock Correlations in the Kuche Depression of Tarim Basin, NW China

1IntroductionTheTarimBasin ,NWChina,istheonlybasininChinawherenotonlymarine ,butalsoter restrialindustrialoilandgaspoolsaredeveloped .TheterrestrialoilandgaspoolshavebeenfoundintheKuchedepressioninthenorthernpartofthebasinanditsfrontupliftarea (Fig .1) .ThesourcerocksoftheterrestrialoilandgaspoolsareTriassicandJurassiclacustrinemudstonesandswampcoals.ThebiomarkersfromthesaturatedfractionsofTriassicandJurassicterrestrialsourcerocksandFig .1 .LocationofTriassicandJurassicterrestrialsource…     

羌塘盆地隆鄂尼地区油苗芳烃分布特征及意义

芳烃作为原油和烃源岩中可溶烃的一个重要组分,能提供烃源岩沉积环境、有机质来源、热演化程度和油源对比等多方面信息,并且其比饱和烃具有更强的抗生物降解作用的能力,因此广泛用于生物降解油的相关研究。生物降解油广泛分布于中国青藏高原羌塘盆地,为了有效开展羌塘盆地油源对比研究工作,本文对隆鄂尼地区油苗开展了系统的芳烃有机地球化学特征研究,样品中检测出的15类化合物系列中菲系列含量极高,其次为三芴系列,萘系列含量较低,但同样检测出一定量的源于陆源高等植物母质的化合物,如卡达烯、惹烯和海松烯等,这表明羌塘盆地生油母质以海相低等水生生物为主,同时有一定量陆源高等植物输入。芳烃成熟度参数研究表明,甲基萘指数由于受到混源影响而不能单独用于成熟度评价,而甲基菲指数和甲基二苯并噻吩指数是羌塘盆地原油成熟度研究的有效指标,综合各类成熟度指标研究表明,羌塘盆地原油属于成熟油。     

山东东营凹陷八面河油田稠油成因分析

东营凹陷八面河地区原油物性呈规律性的变化,偏离生油中心的构造高部位主要分布稠油,靠近生油中心的构造低部位主要分布正常油。对原油族组成与化学成分的分析表明,八面河油田稠油具有低饱芳比、饱和烃含量低、链烷烃与低分子量萘、菲等轻质馏分严重缺失等轻度-中等降解油特征,邻区草桥油田稠油含较为完整的生物降解标志物--25-降藿烷系列,系严重降解油,反映该区稠油的形成与次生变化有关。同区具有相同或相似油气成因的沙子岭原油的成熟度（C₂₉甾烷ααα20S/(S+R)值为0.24~0.25）低于八面河的（C₂₉甾烷ααα20S/(S+R)值为0.31~0.44）,为典型未熟-低熟油。沙子岭的轻度或未降解油同样表现为正常油,反映八面河地区低温成烃与稠油无必然的联系,进一步验证八面河稠油主系次生成因。处于构造高部位的油藏由于埋深浅、保存条件差,导致水洗、生物降解等次生变化相对较强,最终形成稠油。     

Dibenzofuran Series in Terrestrial Source Rocks and Crude Oils and Applications to Oil-Source Rock Correlations in the Kuche Depression of Tarim Basin, NW China

Ten series of aromatic hydrocarbon compounds (biphenyl, naphthalene, phenanthrene, anthracene, retene, chrysene, benzoanthracene, dibenzofuran, fluorene, dibenzothiophene) isolated from seven Triassic and Jurassic lacustrine mudstone samples and three swamp coal samples, as well as five crude oil samples collected in the Kuche depression of the Tarim Basin,NW China, have been analysed by GC-MS techniques. It is found that the relative abundances of dibenzofuran series are higher in the three swamp coal samples than those in the lacustrine mudstone samples. Based on the similar relative abundances of dibenzofuran series, especially dibenzofuran compound, in the TICs of aromatic hydrocarbons, crude oils from wells SA3 (K), YTK5(E,K) and QL1 (E) are thought to have been derived predominantly from the coals of the Lower Jurassic Yangxia Formation or Middle Jurassic Kezilenuer Formation, whereas those from wells YM7 (O) and YHI (E) were derived mainly from Triassic and Jurassic lacustrine mudstones in the Kuche depression. This is the first report about how to distinguish coal-generated oils from lacustrine mudstone-generated oils in the Kuche depression in terms of the dibenzofuran series.The present paper has enlightening and directive significance for further oil-source rock correlations and oil and/or gas exploration in the Kuche depression of the Tarim Basin.     

中国泥盆纪煤有机地球化学特征

中国泥盆纪煤是形成于特定地质历史条件的特种煤，因而具有独特的地球化学特征：显微组成以富含角质体为特征；可溶有机质含量高于泥岩，低于正常腐植煤；芳烃中含丰富的多环芳烃，并检测出芳香倍半萜和芳香二萜及芳香断藿烷；热模拟表明角质体在R0达到0．95％时达到生烃高峰；丰富的四环二萜化合物随成熟度增加，由环状化合物裂解为链状烷烃。     

Hydrous pyrolysis of sediments: Composition and proportions of aromatic hydrocarbons in pyrolysates

Hydrous pyrolysis (closed vessel autoclaving in the presence of excess water) of organic-rich rocks is said to generate oils which closely resemble natural crude oils in their broad characteristics and composition. However there are only a few accounts of the proportions and compositions of hydrocarbons in hydrous pyrolysates and none of these discuss the aromatic hydrocarbon composition in detail. The present paper presents some data on the latter.Hydrous pyrolysis (3 days) of a dolomitic siltstone (Permian, Marl Slate) at 280, 300,320, 340 and 360°C produced significant amounts of oils in which the aromatic hydrocarbons were one and a half to two times as abundant as the saturated hydrocarbons.The overall composition of the aromatic hydrocarbons was similar to most crude oils; the major components isolated by our methods from natural oils and from pyrolysates were C_1–4 alkylnaphthalenes. At the lowest pyrolysis temperature (280°C) the distributions of the more minor components of the pyrolysates (e.g. alkylphenanthrenes, aromatic steroids) were also generally similar to those found in natural crudes. However, a number of components (e.g. methylanthracenes, Diels' hydrocarbon) which are not usually reported in crudes, were also detected and the relative proportions of these increased at the higher temperatures. Hydrous pyrolysis (340°C) of an organic-rich oil shale (Jurassic, Kimmeridge) and an asphaltic-material containing no minerals produced pyrolysates in which many of these unusual compounds were also present. In addition the pyrolysate of the oil-shale contained higher proportions of organic sulphur compounds. It appears that the formation of the unusual compounds is not simply a function of the type of organic matter or mineralogy but rather of the high temperatures or fast heating rates employed.