塔里木盆地深层烃源岩可溶有机组分的碳同位素组成特征

塔里木盆地深层烃源岩主要是指埋深大于4000 m的寒武—奥陶系海相碳酸盐岩和三叠—侏罗系陆相泥岩、碳质泥岩和煤。研究表明,塔里木盆地深层烃源岩可溶有机组分的碳同位素组成具有母质继承效应,寒武—奥陶系海相腐泥型烃源岩可溶有机组分的碳同位素组成一般小于-28‰,而三叠—侏罗系陆相腐殖型烃源岩可溶有机组分的碳同位素组成一般大于-28‰。对于高演化的寒武—奥陶系海相深层烃源岩而言,在热力作用下,其可溶有机组分的碳同位素组成普遍发生强烈逆转,并出现饱和烃>芳烃>非烃>沥青质的完全反序分布现象,显示出深层环境下高演化烃源岩可溶有机组分的碳同位素组成特征。      

沉积有机质中稳定碳同位素逆转现象初探

本文研究了沉积有机质的可溶部分（抽提物）和不溶部分（干酪根）及抽提物的族组分（饱和烃、芳烃、非烃、沥青质）的碳同位素组成特征。通过其δ13C的分布为:干酪根>抽提物;沥青质 >非烃 >芳烃 >饱和烃。研究表明由于生源物质的不同,沉积环境的差异可构沉积有机质碳同位素组成异常。如非烃 >沥青质 >芳烃 >非烃、本文称为沉积有机质碳同位素局部逆转。当沉积有机质可溶部分>干酪根时,称之为总体逆转。湖沼相或河间湖相高等植物来源常为正常组或型;经细菌强烈改造生源以高等植物为主有低等生物为类脂组分加入常形成局部逆转的碳同位素组成。总体逆转则常现于有机质演化程度很高的海相沉积岩中。     

南羌塘侏罗系烃源岩氯仿沥青“A”组分碳同位素特征

对南羌塘侏罗系布曲组和夏里组烃源岩氯仿沥青"A"组分碳同位素分析表明,碳同位素主要受有机母质及沉积环境影响,夏里组烃源岩氯仿沥青"A"组分的碳同位素较重,而布曲组烃源岩氯仿沥青"A"中族组分的碳同位素组成相对较轻。并且它们普遍存在碳同位素逆转现象,夏里组烃源岩氯仿沥青"A"组分的碳同位素逆转表现为:δ13C饱和烃δ13C非烃δ13C芳烃δ13C沥青质,主要受有机质母源控制;布曲组烃源岩氯仿沥青"A"组分的碳同位素逆转表现为:δ13C非烃δ13C沥青质δ13C饱和烃δ13C芳烃,主要与生物降解作用有关。     

塔里木盆地塔北、塔中地区寒武-奥陶系碳酸盐岩中可溶有机组分的碳同位素逆转现象

沉积有机质可溶有机组分的碳同位素组成具有母质继承效应,同时受热力和生物降解作用等因素的影响。利用M AT 252同位素质谱仪分析了塔里木盆地塔北、塔中地区寒武系—奥陶系碳酸盐岩中可溶有机组分的碳同位素组成,发现它们的1δ3C值普遍发生了逆转。饱和烃组分明显富集13C,其1δ3C值的分布区间为-29.7‰~-26.2‰,平均值为-28.5‰,而沥青质组分明显富集12C,其1δ3C值的分布区间为-37.8‰~-27.1‰,平均值为-31.9‰,并且大部分样品的可溶有机组分的1δ3C值出现饱和烃>芳烃>非烃>沥青质的完全反序分布特征。综合分析认为该区寒武系—奥陶系碳酸盐岩中可溶有机组分碳同位素的逆转分布特征主要与热力作用及漫长的热演化史有关,而这种可溶有机组分碳同位素组成完全反序分布模式可以作为沉积有机质在高演化阶段的一个重要的地球化学标志。     

柯坪隆起阿克苏油苗的地球化学特征及其成因研究

柯坪隆起区是塔里木盆地海相烃源岩露头发育较好的地区之一,但相关的油气研究报道不多。本文详细研究了塔里木盆地柯坪隆起区油苗的有机地球化学特征并进行了相关的成因分析。阿克苏油苗经历了严重的生物降解作用,饱和烃生物标志物所能提供的成因信息十分有限。原油沥青质组分及储层吸附/包裹烃受后生作用影响较小,综合分析油苗沥青质热解产物与吸附/包裹烃的生物标志物及其碳同位素组成可以获得更多有效的成因信息。研究结果表明,阿克苏油苗与其储层吸附/包裹烃具有不同来源。油苗、沥青质以及沥青质热解产物的碳同位素特征与已经报道的多数海相原油及其沥青质较为接近,与典型的寒武系烃源来源的原油差异显著。而储层吸附/包裹烃与已报道的典型寒武系烃源岩来源油的生物标志物及碳同位素特征比较类似,可能形成于较高的热演化阶段。     

北黄海盆地LV井侏罗系油砂抽提物地球化学特征

对北黄海盆地侏罗系两块含油砂岩的抽提物进行了常规的有机地球化学分析和碳同位素测试,结果表明它们具有不同的地球化学特征:埋藏较深的油砂抽提物属正常原油,饱和烃以正构烷烃为主,色谱图显示单峰型正态分布;而埋藏较浅的油砂抽提物,在饱和烃色谱图中有明显的UCM鼓包,同时含有完整的低碳数的正构烷烃、姥鲛烷和植烷,全油及族组成碳同位素分布范围广,为-24.7‰~-32.3‰,其中,全油及沥青质碳同位素偏重,饱和烃和芳烃碳同位素轻,反映出遭受了强烈的生物降解作用。与成熟度相关的生物标志物参数显示,原油已进入成熟—高成熟阶段。生物标志物和碳同位素组成表明,母质是在水体较浅的湖相环境下沉积的,受陆源高等植物和低等水生藻类的双源控制。综合判断,研究区存在两期油气充注。     

凯里-麻江地区油苗与固体沥青的油源分析

对黔南坳陷典型古油藏、残余油气藏的精细解剖对南方海相碳酸盐岩层系油气勘探研究具有重要意义。本文运用碳同位素、饱和烃色谱、饱和烃色质及芳烃色质等技术,对黔东南地区二叠系—寒武系油苗与固体沥青进行了地球化学特征研究和油源分析。研究表明,凯里地区虎庄47井原油、洛棉志留系砂岩油苗和麻江地区奥陶系红花园组固体沥青三者同源,主要来自下寒武统牛蹄塘组的优质烃源岩。而麻江地区早二叠世茅口组油苗与虎庄47井原油明显不同,主要源于下二叠统栖霞组的优质烃源岩。     

松辽盆地北部深层凝析油及油型气的成因研究

松辽盆地北部深层发现的凝析油及油型气扩大了油田的勘探潜力.应用单体烃碳同位素、生物标志化合物等分析技术,结合地质背景对凝析油、天然气和固体沥青进行的地球化学研究表明:深层凝析油包括煤成凝析油和泥质烃源岩形成的凝析油,前者芳烃含量高、单体烃碳同位素重,后者饱和烃含量高、单体烃碳同位素轻,生物标志化合物对比,二者均来自于沙河子组烃源岩;油型气甲烷碳同位素轻,一般小于-45‰,且甲烷与乙烷之间碳同位素分馏明显,属原油裂解成气特征,油型气与煤型气混合可能是深层天然气碳同位素系列倒转的重要原因之一;火山岩储层中的固体沥青有机地球化学分析,有机碳含量0.08%～0.16%,氢指数49～297 mg/g,Ro大约为1.87%,表征固体沥青现今的成烃潜力较小,原油向天然气转化主要发生在高成熟阶段的晚期,对应的地质年代大约是嫩江组-明水组沉积末(80～65 Ma).原油向天然气转化的事实启示,深层天然气勘探要兼顾古油藏的研究.     

松辽盆地北部深层凝析油及油型气的成因研究

松辽盆地北部深层发现的凝析油及油型气扩大了油田的勘探潜力。应用单体烃碳同位素、生物标志化合物等分析技术，结合地质背景对凝析油、天然气和固体沥青进行的地球化学研究表明：深层凝析油包括煤成凝析油和泥质烃源岩形成的凝析油，前芳烃含量高、单体烃碳同位素重，后饱和烃含量高、单体烃碳同位素轻，生物标志化合物对比，二均来自于沙河子组烃源岩；油型气甲烷碳同位素轻，一般小于-45‰，且甲烷与乙烷之间碳同位素分馏明显，属原油裂解成气特征，油型气与煤型气混合可能是深层天然气碳同位素系列倒转的重要原因之一；火山岩储层中的固体沥青有机地球化学分析，有机碳含量0．08％～0．16％，氢指数49～297mg／g，R0大约为1．87％，表征固体沥青现今的成烃潜力较小，原油向天然气转化主要发生在高成熟阶段的晚期，对应的地质年代大约是嫩江组一明水组沉积末(80～65Ma)。原油向天然气转化的事实启示，深层天然气勘探要兼顾古油藏的研究。     

辽河油田生物降解原油沥青质热解产物中单体化合物碳同位素组成

生物降解原同在我国分布广泛并且在重油资源中占有一定的比例。本文通过采用单体化合物碳同位素分析技术对取自辽河油田西部凹陷的重油以及它们沥青质组分的热解产物进行单体碳同位素测定,来研究原油沥青质热解产物中正构烷烃单体碳同位素的组成及其一物降解油的指示意义。研究结果表明,沥青质热解产物中正构烷烃组分的单体碳同位素组成可用于生物降解较严重的重油样品进行油／油相比,并且与原油中的正构烷烃单体碳同位素组成的对     

生排烃过程中正构烷烃单体碳同位素组成的变化特征及其研究意义

通过对生排烃模拟实验产物 (残留油和排出油 )中正构烷烃单体碳同位素组成的测定,揭示出生排烃过程中正构烷烃碳同位素组成的变化特征。研究表明,生烃初期,液态正构烷烃主要来自干酪根的初次裂解,它们的碳同位素组成不论是在排出油中还是在残留油中,随温度的变化都不明显,呈现较相似的分布特征;在生烃高峰期,早期形成的沥青质和非烃等组分的二次裂解以及高碳数正构烷烃可能存在的裂解,使得正构烷烃单体碳同位素组成明显富集13 C,尤其在高碳数部分呈现出较大的差异。另外,实验结果显示排烃作用对液态正烷烃单体碳同位素组成的影响不太显著。     

华南下寒武统Ni-Mo-Se多金属层S-Se同位素体系

为了进一步理解华南下寒武统Ni-Mo-Se多金属层的物质来源及形成环境,文中分析了遵义中南村和张家界后坪两个Ni-Mo-Se矿层及其围岩的黄铁矿硫同位素和全岩的硒同位素组成。硫同位素组成显示两个Ni-Mo-Se矿层形成时的环境存在区域性差别,中南村矿层形成于间歇开放的海洋环境,而后坪矿层形成于封闭的缺氧（静海）环境。较大的硫同位素范围暗示硫酸盐还原菌控制硫同位素的分馏,而热液流体可能提供了大量金属元素,从而导致矿层富集大量的硫化物和稀有金属。硒同位素组成指示牛蹄塘组底部热液流体的Se可能重新经历了氧化还原循环,而Se的富集过程可能受有机质和粘土矿物吸附或类质同象过程控制。因此,控制多金属富集的因素主要为富集金属的热液流体的参与和缺氧环境下的自生沉积。     

The occurrence of ultra-deep heavy oils in the Tabei Uplift of the Tarim Basin,NW China

Deeply buried heavy oils from the Tabei Uplift of the Tarim Basin have been investigated for their source origin, charge and accumulation time, biodegradation, mixing and thermal cracking using biomarkers, carbon isotopic compositions of individual alkanes, fluid inclusion homogenization temperatures and authigenic illite K–Ar radiometric ages. Oil-source correlation suggests that these oils mainly originated from Middle–Upper Ordovician source rocks. Burial history, coupled with fluid inclusion temperatures and K–Ar radiometric ages, suggests that these oils were generated and accumulated in the Late Permian. Biodegradation is the main control on the formation of these heavy oils when they were elevated to shallow depths during the late Hercynian orogeny. A pronounced unresolved complex mixture (UCM) in the gas chromatograms together with the presence of both 25-norhopanes and demethylated tricyclic terpanes in the oils are obvious evidence of biodegradation. The mixing of biodegraded oil with non-biodegraded oil components was indicated by the coexistence of n-alkanes with demethylated terpanes. Such mixing is most likely from the same phase of generation, but with accumulation at slightly different burial depths, as evidenced by overall similar oil maturities regardless of biodegradation level and/or amount of n-alkanes. Although these Ordovician carbonate reservoirs are currently buried to over 6000 m with reservoir temperatures above 160 °C, no significant secondary hydrocarbon generation from source rocks or thermal cracking of reservoired heavy oil occur in the study area. This is because the deep burial occurred only within the last 5 Ma of the Neogene, and there has not been enough heating time for additional reactions within the Middle–Upper Ordovician source rocks and reservoired heavy oils.     

石油碳、氢同位素组成的研究

通过对我国18个含油气区、385个石油样品进行碳、氢同位素和部分馏份碳同位素分析,将所获数据对两种不同性质的石油如正常原油和轻质（凝析）油分别研究其碳、氢同位素地球化学特征,提出轻质（凝析）油的碳同位素值（δ13C为-32.5‰～ -24.3‰）比正常原油δ13C为-34.4‰～ -24.6 ‰．6‰）相对偏高;石油馏份中芳烃碳同位素组成的变化受母质继承效应更为明显。因此,用芳烃碳同位值可以判识不同母质来源的石油。与海相有关的轻质（凝析）油的氢同位素值大于-15.0‰,而非海相轻质（凝析）油的δD值( δD为-21.0‰～-1.05‰）基本覆盖了海相轻质油的分布范围,从淡水－微咸水－半咸水和海水环境其氢同位素有明显变重趋势,表明氢同位素主要与沉积环境密切相关。     

Correlation of crude oils and oil components from reservoirs and source rocks using carbon isotopic compositions of individual n-alkanes in the Tazhong and Tabei Uplift of the Tarim Basin,China

Carbon isotopic compositions were determined by GC–IRMS for individual n-alkanes in crude oils and the free, adsorbed and inclusion oils recovered by sequential extraction from reservoir rocks in the Tazhong Uplift and Tahe oilfield in the Tabei Uplift of Tarim Basin as well as extracts of the Cambrian–Ordovician source rocks in the basin. The variations of the δ¹³C values of individual n-alkanes among the 15 oils from the Tazhong Uplift and among the 15 oils from the Triassic and Carboniferous sandstone reservoirs and the 21 oils from the Ordovician carbonate reservoirs in the Tahe oilfield demonstrate that these marine oils are derived from two end member source rocks. The major proportion of these marine oils is derived from the type A source rocks with low δ¹³C values while a minor proportion is derived from the type B source rocks with high δ¹³C values. Type A source rocks are within either the Cambrian–Lower Ordovician or the Middle–Upper Ordovician strata (not drilled so far) while type B source rocks are within the Cambrian–Lower Ordovician strata, as found in boreholes TD2 and Fang 1. In addition, the three oils from the Cretaceous sandstone reservoirs in the Tahe oilfield with exceptionally high Pr/Ph ratio and δ¹³C values of individual n-alkanes are derived, or mainly derived, from the Triassic–Jurassic terrigenous source rocks located in Quka Depression.The difference of the δ¹³C values of individual n-alkanes among the free, adsorbed and inclusion oils in the reservoir rocks and corresponding crude oils reflects source variation during the reservoir filling process. In general, the initial oil charge is derived from the type B source rocks with high δ¹³C values while the later oil charge is derived from the type A source rocks with low δ¹³C values.The δ¹³C values of individual n-alkanes do not simply correlate with the biomarker parameters for the marine oils in the Tazhong Uplift and Tahe oilfield, suggesting that molecular parameters alone are not adequate for reliable oil-source correlation for high maturity oils with complex mixing.     

Geochemistry of Palaeozoic marine petroleum from the Tarim Basin, NW China: Part 3. Thermal cracking of liquid hydrocarbons and gas washing as the major mechanisms for deep gas condensate accumulations

The Lunnan Lower Uplift in the Tarim Basin, NW China contains a composite petroleum system with mainly biodegraded heavy oil in the west, normal oil in the center and gas condensate in the east. Twenty-three gas samples and 37 oil samples taken from three major hydrocarbon bearing intervals in the Lunnan lower bulge were analyzed for their stable carbon isotopes and molecular biomarkers. On the basis of their isotopic compositions, biomarkers, especially diamondoids, and integrating the physical properties of the hydrocarbons including densities, GOR and PVT relationships, it has been concluded that the recently discovered deep (6500 m) eastern Lungu giant Ordovician gas condensate pool with an estimated reserve of 723 million bbl oil equivalent is a secondary hydrocarbon accumulation derived from the mixing of an early formed oil and a late formed gas. The extremely dry gases with a gas dryness of >0.98 were derived from thermal cracking of crude oils and charged to an existing oil reservoir causing extensive gas washing and secondary alteration. Compared with most of the hydrocarbons in the Lunnan area, the gas from the eastern Lungu gas condensate pool has a heavier carbon isotopic composition, higher dryness and a higher maturity level. The unique physical, chemical and isotopic compositions of the gas condensate are believed to be a direct result of gas flushing of an early formed eastern Lungu oil pool by a late formed dry gas from oil cracking. The eastern Lungu gas condensate pool is presently characterized by containing “dry gas, heavy oil, abundant aromatics and high wax”.     

Carbon isotope geochemistry of Paleozoic oils from Big Horn Basin

Twenty crude oils from Paleozoic reservoirs in the Big Horn Basin. Wyoming were fractionated into light hydrocarbons, saturates, monoaromatics. diaromatics, polyaromatics-and-polars. and asphaltenes. Amounts and isotopic composition of each fraction were found to be internally consistent with the degree of maturation of the oil. confirming the established single source origin for these oils. A variation of approximately three per mil in the carbon isotopic composition of the whole oil and individual fraction was explained as being caused by maturation. The isotope-type-curves for these oils, the variations in isotopic composition as a function of compound group-type, were not found to be as simple as commonly believed. Other alteration processes, such as migration and deasphalting, might have influenced the pattern of the isotope distributions among fractions. The conservative nature of mass balance and subsequent isotope flows among various fractions of crude oil showed that the maturation of crude oil consists of consecutive processes leading from larger and more polar components into smaller and less polar components culminating in natural gas. Calculations were made to project the amount of condensates associated with the crude oils, and the amount of natural gas which had been generated from crude oils of a given maturity.     

塔里木盆地哈拉哈塘凹陷天然气地球化学特征

哈拉哈塘凹陷位于塔里木盆地塔北隆起中部,具有良好的石油地质条件,是近期油气勘探的重点区带。天然气地球化学特征研究表明,该区天然气干燥系数较低,表现出典型湿气的特征,普遍含有微量的H2S;烷烃气δ13C1和δ13C2值分别为-50.5‰~-42.6‰和-40.2‰~-35.5‰,δD1值介于-262‰~-156‰之间,碳氢同位素系列表现出典型正序特征; C7轻烃组成具有正庚烷优势分布, C5~7轻烃组成以正构和异构烷烃为主。哈拉哈塘凹陷及周缘奥陶系天然气均为海相油型气,既有干酪根裂解气,也有原油裂解气,其中哈拉哈塘天然气中混入了相当比例的原油裂解初期形成的湿气,主要来自于南部阿满过渡带地区的中上奥陶统烃源岩,天然气中具有高δ13C值特征的CO2主要来自碳酸盐岩储层在酸性地层水作用下发生的溶蚀, H2S主要源自含硫化合物的热裂解。其中天然气发生的同位素部分倒转主要源自原油伴生气与原油裂解气的混合。     

塔里木盆地北部奥陶系油气相态及其成因分析

塔里木盆地北部地区奥陶系是最重要的勘探层系,油气资源丰富;同时油气相态复杂多样,既有凝析气藏、正常油藏,也有稠油油藏、沥青等。通过对油气藏形成演化与保存过程的系统分析,结合油气地球化学和流体包裹体等分析数据,发现油气相态的多样性与油气多期次充注与次生蚀变作用有关。提出塔北隆起的东部奥陶系存在三期油气充注过程,分别发生在加里东运动晚期-海西早期、海西运动晚期、喜马拉雅运动晚期,原油主要来源于中、上奥陶统烃源岩,天然气主要来自与寒武系烃源岩有关的液态烃的裂解;塔北隆起的中西部奥陶系的油气充注主要发生在海西运动晚期。塔北奥陶系油藏形成以后,经历了三期明显的调整改造过程:海西早期构造抬升导致志留-泥盆系遭受剥蚀,东部源自寒武系油气的古油藏遭受破坏,形成沥青;三叠系沉积前的晚海西运动,使得奥陶系生源的油藏大范围遭受降解稠化;晚喜山期,来自于满加尔坳陷的天然气自东向西充注,致使隆起东部早期形成的油藏发生强烈的气侵改造,形成次生凝析气藏。而中西部奥陶系油藏在三叠系沉积前遭受降解稠化后,一直处于沉降深埋过程,油藏得到有效保存;由于成藏时间较早,轻质组分散失较多,气油比极低,油质较稠。研究认为,油气相态的多样性主要受晚海西期构造运动的抬升造成的生物降解作用和喜马拉雅晚期构造运动造成的天然气自东向西大规模充注对油藏进行气洗改造两大过程的控制。