济阳拗陷特殊生物降解油的初步研究

济阳拗陷草古100平19井奥陶系储层原油,饱和烃馏分均已损失殆尽,仅残余藿烷系列化合物;同时,芳烃馏分化合物也已损失殆尽,仅残余三芳甾烷系列化合物。上述芳烃化合物俱已损失殆尽的蚀变特征,在相关文献中的报道较为少见。原油中不受水洗作用影响的正构烷烃和不受生物降解作用影响的有机硫化合物(苯并噻吩和二苯并噻吩)均已损失殆尽,显然暗示了原油蚀变是遭受水洗作用和生物降解作用共同作用的结果。原油芳烃馏分的“UCM”鼓包幅度明显大于饱和烃馏分的“UCM”鼓包,暗示了芳烃化合物的降解速率平行甚至超过饱和烃的降解速率。原油中低分子量芳烃化合物的快速降解,暗示了油藏可能是在氧化条件下而非在还原条件下发生蚀变的。     

Molecular compositions of weathered petroleum and comparison with its possible source

Two surface outcrop samples and three drill core samples of oil-impregnated sandstone from the P.R. Spring Seep, Uinta Basin, Utah were analyzed. These oils exhibit in common the entire homologous series of tricyclic diterpane hydrocarbons, which have been previously described only in extracts from the Mahogany Ledge Member of the Green River Formation. Hopane and a series of degraded hopanes are also present in the oil samples, while steranes are conspicuously absent. Aliphatic alkanes are present only in the deepest core sample.The cycloalkanes are apparently not readily utilized by the petroleum oxidizing microbes, and therefore survive the weathering process. Tricyclic and tetracyclic alkylated diterpanes are unchanged, whereas the series from norhopane through tetrakisnorhopane may be interpreted as progressive bacterial degradation of the hopane molecule.The occurrence and distribution of tricyclic diterpanes, of tetracyclic diterpanes and pentacyclic triterpanes is similar to the stratigraphically nearby Mahogany Ledge Member, suggesting that the oil shales were the source rocks for the oil now exposed as the P.R. Spring Seep. The absence of steranes, which are abundant in the oil shales, is puzzling.     

Organic geochemistry and petrography of Tertiary coals and carbonaceous shales from Argentina

A series of eight Tertiary coal and carbonaceous shale samples with vitrinite reflectance values between 0.50 and 0.58% were extracted, fractionated and the saturated and aromatic hydrocarbons analysed for characteristic components by GC and GC-MS. Additionally, a microscopical study was undertaken in order to obtain a more precise picture of the samples under investigation.The saturated hydrocarbon fractions displayed the typical n-alkane distribution for coals of this rank, with CPI values between 2.0 and 3.1. Among the branched/cyclic compounds, pristane and α, β-homohopane were recognised as relevant components pointing to an oxic depositional environment. Detection of benzohopanes (C₃₂–C₃₅) in the aromatic hydrocarbon fractions suggests that bacteriohopanetetrol was a significant constituent of the coal biomass. Taking into consideration the Pr/Ph ratios, ash contents and microscopical characteristics of the samples, aspects of the possible degradation of hopanetetrol to homohopane are discussed. Resin-derived diterpenoids with the phyllocladane and kaurane skeleton were tentatively identified and, although minor compounds, they are interpreted to be a sign of the contribution of Podocarpaceae and Araucareaceae to the coal swamp.Aromatic compounds were dominated by alkylnaphthalene derivatives, presumably formed by C-ring cleavage and aromatisation of higher plant-derived pentacyclic triterpenois, which were main components in the high-boiling range of the fractions investigated. Angiosperms (especially Fagaceae) are postulated as source for these polycyclic compounds and, hence, for some of the polyalkylated aromatic bicyclics detected.     

川东北地区普光2井飞仙关组储层沥青地球化学特征及成因分析

根据储层中沥青的产状及类型、族组成、饱和烃色谱、生物标志化合物以及储层沥青反射率等,对普光2井飞仙关组储层固体沥青的地球化学特征及成因进行了详尽的剖析。研究结果表明,普光2井飞仙关组储层沥青为古油藏原油经裂解成气之后的残留物,属热演化的焦沥青。储层沥青的正构烷烃分布较为完整,碳数在C14~C30范围,没有受到明显的生物降解作用。Pr/Ph、Pr/nC17和Ph/nC18比值都小于1.0;OEP值1.25～1.43,CPI值0.98～1.19,无奇偶优势或偶奇优势;规则甾烷系列中C27化合物含量占优势,C27-C29规则甾烷呈不对称的“V”字型分布,甾烷异构化程度较低,明显低于异构化平衡值,认为是由于高、过成熟阶段S构型比R构型裂解速率更快的结果。飞一段、飞二段孕甾烷、升孕甾烷含量明显较飞三段高,可能是有机质生源或沉积环境性质上的不同所致。萜类化合物以五环萜烷为主,三环萜烷较为发育,其以C23三环萜烷为基峰,伽马蜡烷的含量较高。这些特征表明普光2井储层沥青主要来源于低等水生生物,有机质的热演化程度较高,主要处于高-过成熟阶段,有机母质形成于沉积水体咸度较高的海相沉积环境中。储层沥青中高含量25 降藿烷并非生物降解作用所致,而主要与源岩的热演化程度较高有关。     

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。     

鄂尔多斯盆地盐池-定边地区长7段烃源岩芳烃地球化学特征

基于鄂尔多斯盆地盐池-定边地区13口井16块长7烃源岩样品的GC-MS分析资料,研究了源岩的芳烃地球化学特征,进行了生源和沉积环境的分析,并探讨了芳烃系列成熟度评价参数在该地区的有效性。研究结果显示:研究区源岩主要以二环和三环芳烃类化合物为主,而四环和五环芳烃类化合物较低,芴含量较高,普遍含有1,2,5-TMN和1,2,5,6-TeMN且部分样品含量偏高,并检测出一定含量的惹烯、苝、和芘等陆源高等植物生物标志化合物,表明研究区源岩形成于滨浅湖弱氧化-弱还原的环境中,高等植物的输入对该地区源岩的形成占有一定贡献。芳烃中烷基萘、烷基菲和烷基二苯并噻吩等成熟度参数表明源岩样品现今正处于成熟阶段。虽然利用不同系列芳烃类化合物求取的等效镜质体反射率存在一定差异,但能定性地反映出源岩的热演化程度。     

吐哈盆地台北凹陷侏罗系煤系源岩地球化学分类及意义

烃源岩的沉积环境、母源输入与有机质性质有着密切联系,吐哈盆地台北凹陷不同层系、不同地区侏罗系煤系烃源岩由于其沉积环境、母源输入的不同,导致其地球化学指标差异;通过对源岩地球化学指标相关性分析表明,姥植比（Pr/Ph）是反映源岩沉积氧化还原环境和水体盐度的重要指标;C29ααα20R在C27～C29规则甾烷ααα20R中的相对含量也是反映沉积水体盐度的重要指标。同时发现源岩类型划分的主控指标是族组成中芳烃、沥青质组分含量及饱芳比、非沥比等四项指标,姥植比、伽马蜡烷指数为源岩类型划分的次控指标,据此将台北凹陷侏罗系煤系烃源岩划分为三类。     

利用芳烃参数研究煤系烃源岩中重排藿烷成因

研究发现鄂尔多斯盆地部分地区上古生界煤系烃源岩存在较高丰度的17α(H)-重排藿烷和早洗脱重排藿烷,在对重排藿烷分布、组成特征及生标组成特征研究的基础上,应用芳烃参数对高丰度重排藿烷的成因进行了探讨。饱和烃生物标志物组成特征显示,高重排藿烷与陆源高等植物生源关系密切,主要在弱氧化沉积环境下演化形成。具有高-异常高丰度17α(H)-重排藿烷和早洗脱重排藿烷(C₃₀*/C₃₀H>0.2、C₃₀E/C₃₀H>0.1)的烃源岩二环+三环芳烃相对含量一般大于50%,四环、五环芳烃含量相对较低,普遍低于35%,未见芳香甾萜类,研究认为其生源主要为陆生高等植物;甲基菲指数MPI₁、MPI₂和甲基菲比值F1研究结果显示,Pr/Ph>1的弱氧化环境烃源岩17α(H)-重排藿烷和早洗脱重排藿烷在进入成熟阶段后开始大量形成,并随成熟度升高而增大;Pr/Ph<1还原环境下的烃源岩重排藿烷丰度相对较低,但在进入成熟阶段后仍有随成熟度升高而增大的趋势;三芴系列化合物参数表明,沉积环境的弱氧化性质对17α(H)-重排藿烷和早洗脱重排藿烷的形成有较大的影响,沼泽相沉积环境最有利于重排藿烷的形成。     

The Role of Organic Matter During Metal Enrichment in Permian Kupferschiefer of the Rudna Mine,Southwest Poland

The bulk composition of organic matter and saturated and aromatic hydrocarbons extracted from 16 samples collected from two Kuperschiefer profiles in the Rudna mine,Southwest Poland has been analyzed to study the role of organic matter during base metal enrichment in the Kupferschiefer shale.The results indicated that the extract yields and saturated hydrocarbon yields decreased with increasing base metal contents.GC and GC/MS analyses indicated that n -alkanes and alkylated aromatic compounds were depleted and may have served as hydrogen donators for thermochemical sulfate reduction.The enrichment of base metal is closely connected with the destruction of hydrocarbons.     

冀中坳陷苏桥-文安地区混源油定量识别模式研究--典型原油混合实验及混源油识别模式

通过典型原油混合实验及其产物的地球化学剖析,揭示当煤成油和下第三系原油混合时,随着下第三系原油的增加,C₁₉三环萜烷,C₂₄四环萜烷,C₃₀重排藿烷,C₂₉甾烷和重排甾烷逐渐变小;而姥鲛烷和植烷,伽马蜡烷和C27甾烷含量则逐渐增加。利用饱和烃生物标志物和芳烃化合物绝对浓度的变化规律,建立了冀中坳陷苏桥-文安地区混源油定量识别模式图版。根据混源油识别的模式,判断苏49井的混源油是由10%的下第三系原油和90%的煤成油混合而成;相反文1021井混源油则是由90%的下第三系原油和10%的煤成油混合而成。     

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.     

Saturated and aromatic diterpenoids and triterpenoids in Eocene coals and mudstones from China

Several series of saturated, diaromatic, triaromatic C-ring cleaved and triaromatic diterpenoids and triterpenoids have been detected in 4 immature coal and mudstone samples. A number of these compounds appear to represent intermediates in a series of postulated pathways for progressive aromatization of biogenic diterpenoids and triterpenoids. Diagenetic pathways for the formation of tricyclic aromatic hydrocarbons from abietane and pimarane type diterpenoid precursors and for the formation of diaromatic, triaromatic C-cleaved and triaromatic hydrocarbons from β-amyrin and other triterpenoid precursors are proposed. Saturated and aromatized abietanes, pimaranes and phyllocladanes, which are the most abundant compounds in all 4 samples, indicate a predominant higher plant input which can be related to the Coniferales group but not to individual plant families. β-Amyrin and other triterpenoid-derived triaromatic and triaromatic C-ring cleaved hydrocarbons with triterpenoid structures are thought to be characteristic for angiosperms. The relative concentrations of the triaromatic and triaromatic C-ring cleaved hydrocarbons are higher in samples 9602 (mudstone) and 9603 (coal) than samples 9601 (coal) and 9604 (mudstone) indicating samples 9602 (mudstone) and 9603 (coal) contain relatively more angiosperm derived organic matter than samples 9601 (coal) and 9604 (mudstone). The distribution patterns and the relative concentrations of saturated and aromatic diterpenoids and triterpenoids thus are valuable markers for the determination of the relative contents of biological sources of organic material in geological samples.     

东濮凹陷盐湖相烃源岩有机硫同位素分布特征及其地球化学意义

盐湖相烃源岩单体烃硫同位素分布特征和影响因素研究薄弱.采用气相色谱-电感耦合等离子体质谱,结合色谱/质谱、微量元素以及碳氧同位素技术,对东濮凹陷北部盐湖相烃源岩进行了分析.结果 表明,不同单体含硫化合物的δ34S值有较大差异,以δ34S=25.00‰为界,将烃源岩分成了两类,第一类:δ34S＞25.00‰,主要为卫城地...     

内蒙古扎鲁特盆地陶海营子剖面林西组烃源岩 生物标志化合物特征及意义

采用气相色谱、气相色谱-质谱技术,研究了扎鲁特盆地陶海营子剖面林西组烃源岩的生物标志化合物特征,剖析其蕴含的有机质生源、沉积环境、有机质热演化程度等方面的信息及地质地球化学意义.林西组烃源岩饱和烃气色谱以“前峰型”的单峰分布为主,主峰碳以C23为主,表明有机质来源以混合有机质为主;Pr/Ph值主要介于0.3～0.6之间,植烷优势较明显,指示为强还原的沉积环境.林西组烃源岩具有“长侧链的三环萜烷丰富、伽马蜡烷含量高和C27甾烷分布占优势”的分子化石组合特征,伽马蜡烷比值为0.15～0.29,平均值为0.19,说明林西组烃源岩形成于微咸水—半咸水环境;藿烷与甾烷的含量比值主要分布于0.6～1.0之间,平均值为0.84,表明细菌和藻类对有机质的贡献大致相当;C27甾烷丰度较高,C27(甾烷)/C29(甾烷)的比值为1.13,表明生烃母质生源构成是低等水生生物藻类来源的有机质特征.     

注水开发过程中原油的水洗作用初探

注水开发过程中的水洗作用是一个以往被忽略,但又十分重要的问题.通过对3口井、时间间隔为20年的6个原油样品系统的地球化学测试与对比研究,探讨了注水开发过程中水洗作用对原油的改造作用以及各种地球化学参数的变化特征和规律.结果表明,在注水开发过程中,水洗作用对芳烃的影响远大于饱和烃,主要表现在芳烃组分的含量明显降低,一些芳烃类化合物的含量和芳烃参数也发生了显著的变化.认为这些变化是注水开发过程中原油遭受水洗作用的特征性标志,并对油源对比和油气运移等研究具有参考意义.     

Prediction of source rock characteristics based on terpane biomarkers in crude oils: A multivariate statistical approach

The distributions of eight tricyclic and eight pentacyclic terpanes were determined for 216 crude oils located worldwide with subsequent simultaneous RQ-mode factor analysis and stepwise discriminate analysis for the purpose of predicting source rock features or depositional environments. Five categories of source rocks are evident: nearshore marine (i.e., paralic/deltaic); deeper-water marine; lacustrine; phosphaticrich source beds; and Ordovician age source rocks. The first two factors of the RQ-mode factor analysis describe 45 percent of the variation in the data set; the tricyclic terpanes appear to be twice as significant as pentacyclic terpanes in determining the variation among samples. Lacustrine oils are characterized by greater relative abundances of C₂₁ diterpane and gammacerane; nearshore marine sources by C₁₉ and C₂₀ diterpanes and oleanane; deeper-water marine facies by C₂₄ and C₂₅ tricyclic and C₃₁ plus C₃₂ extended hopanes; and Ordovician age oils by C₂₇ and C₂₉ pentacyclic terpanes. Although thermal maturity trends can be observed in factor space, the trends do not necessarily obscure the source rock interpretations. Also, since bacterial degradation of crude oils rarely affects tricyclic terpanes, biodegraded oils can be used in predicting source rock features. The precision to which source rock depositional environments are determined might be increased with the addition of other biomarker (e.g., steranes) and stable isotope data using multivariate statistical techniques.     

The Silurian Reservoir Bed—Differentiated Asphalts in Tarim Basin and Modeling Experiments on Their Origin

There is a type of asphalt that originated from differentiation from reservoir bed (named reservoir bed-differentiated asphalt)in the Silurian asphaltic sandstones of the Tarim Basin.These asphalts are the result of second-time charging of hydrocarbons into the Silurian reservoir,which were derived from Lower Paleozoic source rocks.Asphalt was differentiated from the reservoir bed in the hydrocarbon gathering area of secondary migration.The different-tiation is caused by changes in reservoir physical properties when pearl or chain hydrocarbons migrating through and gathering in the reservoir bed,and light components are lost and heavy ones are involved in the formation of asphalt or heavy oil.There are two kinds of occurrence of these asphalts in the Silurian system of the Tarim Basin.One is the poor heavy oil layer with lower oil saturation in trap and the other is scattered hydrocarbon distributed along the trans-port layer and unconformity surface.Reservoir bed-differentiated asphalts have two characteris-tics:total hydrocarbon content is high in extractable organic matter and the ratio of saturated to aromatic hydrocarbon is usually greater than unity.The physically modeling experiment has confirmed these characteristics and the genesis of the reservoir bed-differentiated asphalts.     

泥炭的热模拟研究──过渡带气形成机理探讨

本文对现代泥炭进行了低温长时间模拟实验研究,并探讨了过渡带气的形成机理。甘南泥炭气、液态烃产率高。液态烃由热解油和残余气仿沥青“Ａ”两部分组成,热解油中以Ｃ_５─Ｃ_１４较轻馏分为主,残余氯仿沥青“Ａ”则以非烃、沥青质为主。随热演化程度增高,烃类增加,非烃和沥青质急剧减少。模拟气体组成以非烃气体（ＣＯ_２等）为主,随温度升高,气态烃产率升高,烃类气体中以甲烷为主。２００℃～４００℃温度下产生的甲烷碳同位素δ１３Ｃ为－５３.８２～－３３.６６‰。研究表明低热演化阶段伴随腐殖物质的降解和干酪根的分子重排作用能产生甲烷同位素较轻的生物－热催化过渡带气。     

内蒙古西部额济纳旗祥探8井华力西期风化壳 原油地球化学特征

根据对祥探8井华力西末期风化壳原油地球化学特征的分析,原油具有饱和烃含量高,芳烃、非烃、沥青质含量低和全油C同位素轻的特点,生物标志化合物藿烷系列具有C30藿烷含量高,伽马蜡烷含量相对较高等特点,指示生烃母质类型好,沉积环境为高含盐的还原环境,烃源岩演化程度较高。与祥探9井烃源岩生物标志化合物特征一致,指示与石炭系烃源岩具有良好的亲缘关系。     

新疆西北部和什托洛盖盆地侏罗系低熟煤系烃源岩地球化学特征及生烃条件分析

新疆西北部和什托洛盖盆地勘探程度较低,侏罗系煤系烃源岩较为发育,选取了和什托洛盖盆地和布克河凹陷与白杨河凹陷的四条侏罗系野外地质剖面,对侏罗系烃源岩进行了系统的地球化学实验室分析测试,确定了该盆地生烃潜力。研究表明,侏罗系八道湾组、三工河组以及西山窑组煤系烃源岩有机碳含量、氯仿沥青“A”、总烃以及生烃潜力值均达到中等—好的烃源岩有机质丰度标准。煤系烃源岩有机质显微组分镜质体较为富集,壳质组相对含量达到20%,为孢子体、角质体、树脂体以及木栓质体,泥岩富集部分藻类体,荧光特征较强,惰质体不发育,母质类型为Ⅱ2型,部分为Ⅲ型,煤为Ⅲ型,煤中氯仿沥青“A”与族组分同位素偏重,暗色泥岩略低,煤系烃源岩族组分非烃的同位素值均明显偏轻,芳烃同位素略重,受控于煤系烃源岩中多环芳烃较为发育,更为富集δ13C,非烃组分N、S、O化合物富集δ12C。实测Ro值较低,烃源岩成熟度偏低,但盆地模拟结果表明研究区凹陷中心区源岩已进入生烃门限。研究区低熟煤系烃源岩分子标志化合物也存在其特殊性,正构烷烃以高碳数的分布为主,煤的Pr/Ph值明显高于泥岩,无β 胡萝卜烷、孕甾烷与升孕甾烷分布、伽玛蜡烷指数低,表明侏罗系煤以湖沼相的氧化环境为主,而西山窑组泥岩主要以弱氧化环境沉积特征为主,另外萜烷系列化合物几乎无倍半萜、二环倍半萜以及三环萜烷的分布,藿烷系列存在ββ生物构型分布,为热演化程度较低的标志,分子标志化合物参数的相关性表明,弱氧化的湖沼相的沉积水体有利于此类化合物的分布,煤抽提物中规则甾烷C27、C28、C29呈反“L”型分布,主要以高等植物的陆源输入为主,而侏罗系泥岩存在“V”型分布,有低等水生藻类的贡献,与富氢组分中存在藻类体有较好的的匹配关系,具有更有利的生烃条件。