Effect of maturity on carbon isotope ratios of oils and condensates

For modelling isotopic variations in oils it is convenient to differentiate the effects of oil generation ( 100–150°C) from the effects of oil to gas cracking ( 150–180°C). During generation, δ¹³C of kerogen may increase by up to 1% due to release of isotopically light oil and gas, although most kerogens show little or no chan δ¹³C of the generated oil increases by between 0 and 1% (av. 0.5%) due to mixing of isotopically heavy oil with an initial isotopically light unbound fraction, possibly of bacterial origin. The change occurs mostly over the first 20% of generation. During oil to gas cracking, kinetic isotope effects become important and the effect on δ¹³C of the remaining oil can be modelled as a Rayleigh process. δ¹³C increases by 1.5% by 50% cracking. Insufficient data are available to calibrate the effects at higher levels of cracking, and modelling these variations is hindered by a lack of understanding of the mechanism of pyrobitumen formation. However, increases greater than about 4% are unlikely to be observed. With increasing maturity, the low molecular weight fractions become isotopically heavy faster than the high molecular weight fractions. As a result, any separation of the low molecular weight fraction into a gas phase (“condensate formation”) will produce an isotopic difference between oil and condensate that depends on maturity. In the early stages of generation the condensate may be up to 1% lighter than the remaining oil. With increasing maturity, this difference at first decreases and then increases in the opposite sense. By half way through oil to gas cracking the condensate may be 1.5% heavier than the residual liquid. More subtle rearrangement reactions may result in small, but significant, changes to the shape of the isotope “type-curves” when different oil fractions are compared.     

Organic geochemistry of marine source rocks and pyrobitumen-containing reservoir rocks of the Sichuan Basin and neighbouring areas,SW China

Three bitumen fractions were obtained and systematically analysed for the terpane and sterane composition from 30 Paleozoic source rocks and 64 bitumen-containing reservoir rocks within the Upper Sinian, Lower Cambrian, Lower Silurian, Middle Carboniferous, Upper Permian and Lower Triassic strata in the Sichuan Basin and neighbouring areas, China. These bitumen fractions include extractable oils (bitumen I), oil-bearing fluid inclusions and/or closely associated components with the kerogen or pyrobitumen/mineral matrix, released during kerogen or pyrobitumen isolation and demineralization (bitumen II), and bound compounds within the kerogen or pyrobitumen released by confined pyrolysis (bitumen III). In addition, atomic H/C and O/C ratios and carbon isotopic compositions of kerogen and pyrobitumen from some of the samples were measured. Geochemical results and geological information suggest that: (1) in the Central Sichuan Basin, hydrocarbon gases in reservoirs within the fourth section of the Upper Sinian Dengying Formation were derived from both the Lower Cambrian and Upper Sinian source rocks; and (2) in the Eastern Sichuan Basin, hydrocarbon gases in Middle Carboniferous Huanglong Formation reservoirs were mainly derived from Lower Silurian source rocks, while those in Upper Permian and Lower Triassic reservoirs were mainly derived from both Upper Permian and Lower Silurian marine source rocks. For both the source and reservoir rocks, bitumen III fractions generally show relatively lower maturity near the peak oil generation stage, while the other two bitumen fractions show very high maturities based on terpane and sterane distributions. Tricyclic terpanes evolved from the distribution pattern C₂₀ < C₂₁ < C₂₃, through C₂₀ < C₂₁ > C₂₃, finally to C₂₀ > C₂₁ > C₂₃ during severe thermal stress. The concentration of C₃₀ diahopane in bitumen III (the bound components released from confined pyrolysis) is substantially lower than in the other two bitumen fractions for four terrigenous Upper Permian source rocks, demonstrating that this compound originated from free hopanoid precursors, rather than hopanoids bound to the kerogen.     

黔西南卡林型金矿床与古油藏的成因联系:有机岩相学证据

黔西南卡林型金矿床中存在两种类型的有机质,一种为具较低反射率的原地藻类体,散布于金矿石和沉积围岩中,多呈层纹状或条带状平行于层理面产出;另一种为热解沥青/焦沥青,多呈微细粒状产于蚀变及矿化岩石中,尤其是高品位矿石中,与主阶段似碧玉状石英、含砷黄铁矿、毒砂紧密共生或伴生,或呈分散的粒状被主阶段和晚阶段的石英、方解石、雄黄等热液矿物包裹。沥青以含较高的与成矿密切相关的微量元素As(4.90%～7.88%)和S(大多为7.48%～15.24%)区别于原地有机质(不含As,S含量2.72%～7.18%)。金矿石热液矿物中常见气相CH4、气液两相CH4-H2O等烃类流体包裹体。古油藏沥青多见于二叠系生物礁碳酸盐岩的溶洞、孔隙、裂缝等开放空间中,或单独产出,或与热液方解石伴生,沥青多呈镶嵌结构,显示出高热演化程度的特点。岩相学证据显示,金矿床成矿流体是一种富含金属和碳氢化合物的油水不混溶的盆地流体,金与烃类有机质一起活化、迁移,并通过不同的沉淀和捕获机制成矿、成藏。     

渝东南下志留统龙马溪组页岩有机质孔隙发育特征:基于聚焦离子束氦离子显微镜(FIB-HIM)技术

页岩中的有机质孔隙对烃类气体的赋存至关重要。为了明确渝东南下志留统龙马溪组页岩的有机质孔隙发育特征,使用聚焦离子束氦离子显微镜(FIB-HIM)技术进行观察。FIB-HIM具有极高的分辨率,分辨精度可达到亚纳米级,能够有效识别直径为0~20 nm的孔隙。结果表明:龙马溪组页岩的焦沥青内部发育大量的有机质孔隙,孔隙直径大,连通性好,大量较小直径的孔隙嵌套在直径较大的有机质孔隙中,增加了页岩有机质孔隙系统的比表面积和孔隙连通性,有利于烃类气体在页岩有机质孔隙内的赋存及有效渗流。龙马溪组页岩的固体干酪根内部有机质孔隙的发育特征与焦沥青相比存在较大差别,固体干酪根内部发育的有机质孔隙数量少,孔隙直径小,连通性差,孔隙多呈孤立状存在于固体干酪根内部。     

Geochemical features and genesis of the natural gas and bitumen in paleo-oil reservoirs of Nanpanjiang Basin, China

Bitumen from the Nanpanjiang Basin occurs mainly in the Middle Devonian and Upper Permian reef limestone paleo-oil reservoirs and reserves primarily in holes and fractures and secondarily in minor matrix pores and bio-cavities. N2 is the main component of the natural gas and is often associated with pyrobitumen in paleo-oil reservoirs. The present study shows that the bitumen in paleo-oil reservoirs was sourced from the Middle Devonian argillaceous source rock and belongs to pyrobitumen by crude oil cracking under high temperature and pressure. But the natural gas with high content of N2 is neither an oil-cracked gas nor a coal-formed gas generated from the Upper Permian Longtan Formation source rock, instead it is a kerogen-cracked gas generated at the late stage from the Middle Devonian argilla- ceous source rock. The crude oil in paleo-oil reservoirs completely cracked into pyrobitumen and methane gas by the agency of hugely thick Triassic deposits. After that, the abnormal high pressure of methane gas reservoirs was completely destroyed due to the erosion of 2000--4500-m-thick Triassic strata. But the kerogen-cracked gas with normal pressure was preserved under the relatively sealed condition and became the main body of the gas shows.