Natural gas geochemistry of low evolutionary stage of medium- and small-sized basins in Yunnan Province, southwestern China

The biogenic gas and premature-low mature associated gases in some medium and small-sized basins of Yannan Province, such as Luliang, Yanglin, Baoshan and Jinggu basins, have beed researched. The results show that the biogenic-gas consists mainly of methane which is more than 99% in gasous hydrocarbons and of lighter carbon isotopic composition with δ13C1 values from -60.0‰ to - 75.4‰. The methane carbon isotopic compositions in the Baoshan Basin is relatively heavy (δ13C1 - 60‰- - 65‰), but those in Luliang and Yanglin basins are lighter (δ13C1, less than -70‰), which implies that the gas field of the Baoshan Basin formed earlier than the others. In the Jinggu Basin, where crude oil is premature-lower mature, the natural gas of associated oil relatively wet and the relative content of methane about 58%-95% in gasous hydrocarbons. Constituently the gas composition is much similar to associated one, but the methane carbon isotopic compositions from - 53.8‰ to - 57.8‰ are obviously richer in 12C than those of general oil fields and similarly characterize the biothermo-catalytic transitional zone gas. Their ethane carbon isotopic compositions from - 34.6‰ to -29.0‰ show that they may be derived from type Ⅰ or Ⅱ source rock. But for the associated gas from lower evolutionary stage, the heavier ethane carbon isotopic composition as well as the reversed order among the carbon isotopic composition of ethane, propylane and butane also implies that some gases from the type Ⅲ organic matter are mixed. The δ13CCo2 of the samples essentially less than - 10‰ may be generated from organic matter.     

Variations in carbon isotopic composition in the subcontinental lithospheric mantle beneath the Yangtze and North China Cratons: Evidence from in-situ analysis of diamonds using SIMS

The components and evolution of subcontinental lithospheric mantle beneath the North China Craton and the Yangtze Craton is a current topic in the geological study of China and the carbon isotopic composition of diamond is one of the most direct probes into cratonic lithospheric mantle processes.In this paper,in-situ SIMS(Secondary Ion Mass Spectrometry) techniques were used to analyze the carbon isotope compositions at different internal growth zones of diamonds from Shandong and Liaoning in the North China Craton and Hunan in the Yangtze Craton.It was found that the carbon isotopic range of diamonds from the North China Craton are rather distinct from those of the Yangtze Craton;the former has a range of 6.0‰ to 2.0‰(relative to VPDB) with an average value of 3.0‰ in their core areas,which is consistent with global peridotitic diamonds;the diamonds from the Yangtze Craton,however,have a carbon isotopic range from 8.6‰ to 3.0‰ with an average value of 7.4‰ in their core areas,being more consistent with global eclogitic diamonds.The variations of carbon isotope ratios between different internal growth zones in individual diamonds were different in the three diamond localities studied.There was a clear correlation between changes in carbon isotopic composition and phases of diamond dissolution and new growth,while no correlation was observed between δ13C and internal inclusions.The variations suggest that the carbon isotopic compositions of mantle fluids were changing during the process of diamond crystallization,and that the heterogeneity of the carbon isotopic composition in mantle carbon reservoirs was a more important factor than carbon isotope fractionation in controlling the carbon isotopic compositions and their variation in diamonds.In addition,the preliminary results of in-situ nitrogen analyses demonstrated that the variation of carbon isotopic compositions between the core and outer growth zones does not correlate with nitrogen abundances,implying either that diamonds crystallized in an open environment or that the carbon isotopic composition and nitrogen contents in mantle fluids were controlled by other,not yet understood factors.The experimental results provide hints that the isotopic composition of carbon and its original sources were different in metasomatic fluids controlling diamond formation in the mantle beneath the North China Craton and the Yangtze Craton.     

Kinetic study of hydrocarbon generation of oil asphaltene from Lunnan area, Tabei uplift

The molecular compositions and molecular carbon isotopic compositions of gas hydrocarbons produced in the hydrocarbon generation of oil asphaltene from Lunnnan area were investigated by pyrolysis of asphaltene sealed in gold tube in a limited system. The experimental results indicated that oil asphaltene from Lunnan area had relatively high generation potential of methane. However, the molecular compositions and molecular carbon isotopic compositions of gas hydrocarbons in the hydrocarbon generation of oil asphaltene exhibited different characteristics from that of gas hydrocarbons by primary cracking of kerogen and secondary cracking of oil. Based on kinetic simulation with paleo-geothermal data of oil reservoir, the methane produced by cracking of oil asphatene was characterized by relatively light carbon isotopic compositions. This result could not explain relatively heavy carbon isotopic compositions of natural gas from Lunnan area. Pyrolysis of kerogen from source rocks under very high temperature probably made remarkable contributions to natural gas from Lunnan area.     

The carbon isotope study of biomarkers in the Maoming and the Jianghan tertiary oil shale

In terms of the individual carbon isotope data of biomarkers present in the typical freshwater lake sediment (Maoming oil shale) and saline lake sediment lake (Jianghan oil shale) of China, this paper discusses their precursors and depositional environments of biomarkers in both sediment samples. Our studies showed that phytane and pristane of the Maoming oil shale were derived from the phytol side chain of chlorophyll a. By comparing the isotopic composition of 4-methyl sterane with that of sterane and hopane, it is suggested that 4-methyl sterane which has a higher abundance in the Maoming oil shale come from bacteria. The isotopic composition of biomarkers from the Jianghan rock sample (saline lake sediment ) is significantly different from that of the Maoming oil shale (freshwater lake sediment). Gammacerane was derived from haloprotozoan, with δ13C being about -25.8‰, just in consistency with the value reported in previous studies. The isotopic composition of phytane and pristane in the Jianghan rock is similar to that of sterane and 4-methyl sterane derived from phytoplanktons, illustrating their commonprecursors were algae. This paper reported for the first time the carbon isotope data of porphyrin obtained by GC-IRMS techniques. The approximate δ13C of C32DPEP and C31DPEP porphyrin from the Jianghan Basin indicated that the porphyrin was derived from chlorophyll. In the Maomingoil shale C32DPEP was enriched in 13C relative to C32etio and C31DPEP, implying that C32DPEP came from chlorophyll, and C32etio and C31DPEP are of other origins.     

Carbon and oxygen isotopes analyses for the Sinian carbonates in the Helan Mountain, North China

We conducted detailed studies of the Sinian carbonates from the Helan Mountain, Ningxia by both field investigation and laboratory analyses of carbon and oxygen isotopes. The carbon isotopic compositions of the Sinian Zhengmuguan Formation shows variations with regularity in the five studied sections, the δ ¹³C values all gradually decrease from bottom to top, with a total range from ?4.51‰ to 0.11‰, and the biggest negative excursion reaches up to ?6.88‰. In addition, abundant macro-body fossils were also found from the Tuerkeng Formation in this study, similar to those found from the Dengying Formation in the South China Block. This observation firmly constrained the age for the Zhengmuguan and Tuerkeng formations to the Sinian period. Here we interpreted that the Zhengmuguan Formation formed during a glacial period when the extremely cold climate substantially decreased the amount of burial of organic matter in the ocean and thus led to the general negative δ ¹³C excursion. The increasing δ ¹³C values in the Tuerkeng Formation dolomites imply the ending of the glacial period in the Zhengmuguan epoch, biological recovery and increase of organic matter burial in the ocean occurred during this period. Comparing our obtained carbon and oxygen isotopes of the Zhengmuguan and Tuerkeng formations with those of coeval carbonate successions from other places all over the world, the Zhengmuguang-aged glacial deposits might be deposited after the Gaskiers glaciation. This study provides important information for paleo-ocean, paleogeographic and biological evolution in the North China Block during the Ediacaran period and adds new carbon and oxygen isotopes data for the global Sinian carbon-oxygen isotopes dataset.     

In situ stable isotopic constraints on dolomitizing fluids for the hydrothermally-originated saddle dolomites at Keping, Tarim Basin

Detailed characterization of diagenetic fluid behaviour and evolution is commonly hindered by shortage of appropriate and economic methods to carry out in situ analysis in the tiny diagenetic mineral crystals. Using micromill sampling method, this study presents in situ stable isotopic data for the growth zones of saddle dolomite crystals in the hydrothermally-altered dolostones of Upper Cambrian (Furongian) at Keping, Tarim Basin, NW China. These data show minor and large variations in δ13C ( 0.7‰ to 1.5‰ VPDB) and δ18O ( 8.3‰ to 13.8‰ VPDB), respectively, from the cores to outer rims of the dolomite crystals and suggest that saddle dolomites precipitated from dolomitizing fluids with similar carbon sources but oscillatory temperatures during different formation stages. This scenario is confirmed by microthermometry of fluid inclusions within the growth zones of dolomite crystals. This study indicates that in situ isotope analysis could provide more detailed information related to the source and pathway of dolomitizing fluids, facilitating better characterization of dolomitizing fluids and processes.     

Carbon isotopic compositions of individual terpenoids in heavy oils from Karamay oilfield

The carbon isotopic compositions of individual terpenoids in the heavy oils from the Karamay oilfield were determined by using the method of enrichment of terpanes with molecular sieve 13X and GC-IRMS technique. The terpanes, selectively enriched from the biodegraded oils with molecular sieve 13X, can meet the demand of GC-IRMS analysis. The carbon isotopic compositions of the hopanoids (δ13C -31.7‰--37.8‰ ) infer that their main source is probably non-methanotrophic bacteria, and that the depositional environment of source rocks is a strongly reductive, rapidly depositional, and closed-semi-closed saline lagoon.     

兰州沙尘总悬浮微粒中有机污染物的变化及来源

比较了2006年春季沙尘天气和非沙尘天气吸附到TSP样品巾增塑剂、正构烷烃、多环芳烃(PAHs)、甾烷和藿烷类等有机污染组分特征.显示兰州TSP中增塑剂等的工业污染相当严重,煤和生物质燃烧排放以及交通排放较高.非沙尘天气时,污染物主体主要来源于交通排放藿烷和化石燃料燃烧产物释放(煤和牛物质燃烧排放为主)的PAHs;而沙尘天气时,虽然兰州地区气体颗粒物急剧增多,但由于有机污染物被沙尘暴带到东部地区,这些有机物质量分数郜明显降低.在非沙尘天气,可能是由于沙尘暴源区和沿途土壤高等植物蜡质的风成输入,生物来源的正构烷烃贡献相对增加,其中5个oxy-PAHs和邻苯二甲酸二异壬酯在大气环境研究中很少报道.     

Thermal cracking of n-octodecane and its geochemical significance

The mechanism of carbon isotopic fractionation for gaseous hydrocarbons is revealed by investigating the residual liquid hydrocarbons in laboratory pyrolysates of n-octodecane. The results indicate that cracking and polymerization in the relatively low temperatures and dispropor-tionation reactions leading to light hydrocarbons and pol-yaromatic hydrocarbons at high temperatures are probably causes for the carbon isotope reversal of gaseous hydrocarbons that is commonly observed in pyrolysis experiments. This study provides significant insight for quantitative modeling of natural gas δ13C values and aid in the identification and assessment of natural gases derived from oil cracking.     

Lipids of sulfate-reducing bacteria and sulfur-oxidizing bacteria found in the Dongsheng uranium deposit

U-bearing sandstones from the Dongsheng deposit in Ordos Basin contain abundant C15-C18 fatty acids. The fatty acids may have been derived from modern and ancient organisms including organisms from the intervals of U mineralization. A certain amount of i15:0, a15:0, a17:0 fatty acids coexist with small amounts of i17:1ω7c and 10me16:0, characteristic biomarkers of Desulfovibrio and Desulfobacter sp., respectively. This indicates the existence of sulfate-reducing bacteria (SRB) in the sandstones. The presence of sulfur-oxidizing bacteria (SOB), such as Beggiatoa and Thioploca, is indicated by significant amounts of 16:1ω7c and 18:1ω7c fatty acids. The existence of the SRB in the deposit, as inferred from the fatty acids, is consistent with results from fossilized microorganisms and isotopic compositions of ore-stage pyrite. This suggests that the environment may have been favorable for the SRB to grow since ore formation (9.8-22 Ma). The bacteria may have degraded hydrocarbons directly, or indirectly utilized hydrocarbons degraded by oxic microbes in the deposits. This process may have produced 12C-rich calcite and prominent baseline humps of unresolved complex mixtures (UCM), and 25-demethylated hopanes and tricyclic terpanes. The existence of sulfur-oxidizing bacteria and sulfate-reducing bacteria in the deposit may have resulted in bacterial sulfate reduction to sulfide, re-oxidization of the sulfide to sulfate and subsequent reduction of the sulfate to sulfide. This assertion is supported by ore-stage pyrite with δ34S values as low as-39.2‰, and the lightest sulfate (about 11‰) measured during the Phanerozoic, a difference of more than 46‰.     

Geochemical identification of coal-sourced oils and interbedded shale-sourced oils as revealed by compound specific carbon isotopic analysis

To date, questions remain as to how to differentiate between coaland interbedded shale-sourced oils in coal measures. Based on the hypothesis that δ¹³C value of sedimentary organic matter is controlled by the depositional environment and productivities of biota grown in such depositional setting, this note examines compound specific carbon isotopic profiles from coal and interbedded shale extracts using the gas chromatography-isotope ratio mass spectrometry technique (GC/IRMS). The results show that compound specific carbon isotope values from coal extracts are enriched in¹³C relative to that of interbedded shale extracts, and provide useful information in characterizing coal- and interbedded shale-sourced oils in coal measures. An example for its successful application from the Turpan Basin, Northwestern China is presented.     

Stable carbon and oxygen isotopic compositions of carbonates in middle Mesoproterozoic Wumishan Formation and sea-level change

δ13C of dolostones from the Wumishan Formation (1 310-1 207 Ma) in the Ming Tombs area near Beijing ranges from - 1.5 to 1.5‰ (PDB), and generally, the δ18O ranges from - 4 to - 5‰ (PDB). The secular variation of stable carbon isotopic compositions is cyclic. δ13C displays positive shifts from a sequence boundary to 1.5 per mil (PDB), then a negative shifts to - 1.5 per mil (PDB). In some unit, where δ13C values of the rocks are negative, they have relatively high δ18O values close to -4.0‰ (PDB). These characteristics of the carbon and oxygen isotopic compositions may be associated with sea-level changes.     

Isotopic evolution of the terminal Neoproterozoic and early Cambrian carbon cycle on the northern Yangtze Platform, South China

Profound geotectonic, climatic and biological changes occur during the terminal Neoproterozoic and its transition into the early Cambrian. These are reflected in temporal variations of the chemical and isotopic composition of seawater. We are studying a sequence of sedimentary rocks at the Shatan section, northern Yangtze Platform, Sichuan Province of China. This succession comprises, in ascending stratigraphic order, predominantly calcareous sediments of the Sinian upper Dengying Formation and black shales of the lower Cambrian Guojiaba Formation (time equivalent of Niutitang Fm.). Paleoenvironmental setting represents shallow-water shelf deposits. The objective of our study is to provide temporal records for the isotopic compositions of organic and carbonate carbon throughout this time interval. Organic carbon isotope values display a range between -35.8‰ and -30.1‰ with clear stratigraphic variations. Carbonate carbon isotope data vary between -3.5‰ and +0.5‰. These secular variations are interpreted to reflect perturbations of the global carbon cycle, specifically changes in the fractional burial of organic carbon. However, local conditions have further affected the isotopic signals.     

兰州市和太原市环境空气中NMHCs的碳同位素组成特征

研究了兰州市和太原市环境空气中非甲烷烃(NMHCs)的污染状况及来源。利用Tenax-TA吸附管采样,热解析-色谱-同位素质谱联用仪(TD-GC-IRMS)测定了两个城市夏季不同功能区环境空气中NMHCs的稳定碳同位素组成。得出,兰州市和太原市居民区苯的δ(13C)分别为-26.4‰和-25.0‰;正烷烃的δ(13C)分别为-33.9‰~-26.1‰,-32.8‰~-27.4‰;两市交通枢纽区环境空气中检测出的C4—C7之间的NMHCs化合物相同,δ(13C)相差不大,兰州市为-30.8‰~-25.6‰,太原市为-31.0‰~-26.4‰。结果表明,两市交通枢纽区苯主要来源于汽车尾气和油类挥发,工业区石化行业类主要排放的NMHCs污染物为苯和烷烃类化合物,电厂等大型企业主要排放异丁烯、顺-2-戊烯等。控制汽车尾气、油类挥发、工业排放是降低环境空气中NMHCs污染的关键。     

Carbon and sulfur isotopic compositions of basal Datangpo Formation, northeastern Guizhou, South China: implications for depositional environment

Isotopic compositions of Mn-carbonate and organic carbon from the same individual samples and sulfur isotopic compositions of pyrites in the basal Datangpo Formation were analyzed. Highly 34S-enriched pyrites （834Spyrite =31.7-59.4‰） were precipitated in rel- atively occlusive pore water under anoxic condition in sediments, which is consistent with the observation of large and scattered pyrite framboids. The sulfidic deep ocean was not ＂oxidized＂ in the early Datangpo interglacial interval, thus the level of seawater sulfate remained low and marine δ34Ssulphate remained high. Low δ13Ccar （average -7.4‰） and abnormal relationship between δ13Ccar and fractionation （ΔCar-ors） imply that the negative δ13CCar excursion may have resulted from oxidation of part of a large organic carbon reservoir. High Δcar-org （average 25.1‰） implicates high CO2 level in the atmosphere. Small standard deviation （1.0‰） of δ13CCar values indicates the Mn-carbonate was precipitated near the water-sediment interface under dysoxic conditions rather than in occlusive pore water in sediments.     

抚顺油页岩及其残渣的热解性能

用热重分析法研究了抚顺油页岩及其残渣的热解性质与热解动力学.结果显示,油页岩和油页岩渣的热解反应为两个过程:在常温~200℃,主要是水分的挥发,油页岩及其残渣中水的挥发量分别为2.446%和3.202%;在200~600℃,主要是固定碳的热解,失重率分别为16.048%和6.524%.采用Coats-Redfern方法得到了热解反应两个部分的动力学常数,抚顺油页岩的活化能分别为51.84和28.14 kJ/mol,频率因子分别为62.35和0.003 25 min-1;抚顺油页岩渣的活化能分别为36.62和55.05 kJ/mol,频率因子分别为0.009 76和0.341 min-1.另外油...     

Carbon and hydrogen isotopic compositions and their evolutions of gases generated by herbaceous swamp peat at different thermal maturity stages

Coalbed methane (CBM) accumulation models include continuous gas accumulation and staged gas accumulation.However,studied on the geochemical characteristics and indices to evaluate staged accumulation CBM are lacking.This study for the first time obtained the carbon and hydrogen isotopic compositions of methane and ethane generated at different evolution stages using thermal simulation of samples prepared by treating an herbaceous swamp peat at different temperatures.The results showed that the carbon isotopic compositions of methane and ethane were obviously affected by the thermal evolution level of the starting sample,while the hydrogen isotopic compositions were closely related to the maturity of gases.The carbon and hydrogen isotopic compositions of gases generated by coal-forming organic matter with Ro values from 1.2%,1.7%,2.4%,3.2% and 3.7% to 5.2% were determinated.The relationship between Ro values and the carbon and hydrogen isotopic compositions of gases generated by coal-forming organic matter at different evolution stages as well as the carbon or hydrogen isotopic relationships between methane and ethane were established.The results provide a scientific basis for studying the genesis of CBM generated at different maturity intervals and understanding the geochemical characteristics of staged accumulation CBM.These results were applied to a case study on CBM from the southern Qinshui basin,and it was found that the CBM accumulated after the Middle Jurassic and was characteristic of staged gas accumulation.This is consistent with the result of geological studies,and further showed that the results of thermal simulation experiments are very important for evaluating the genesis of natural CBM.     

Stable isotopic geochemistry of organic carbon and pyrite sulfur from the Early Cambrian black shales in Northwestern Hunan, China

The early Cambrian black shale sequence in Northwestern Hunan Province has been investigated for its stable isotopic geochemistry of organic carbon and pyrite sulfur. The relatively low δ 13C values of organic matter, -29.7‰～-34.2‰, are interpreted as caused by the high CO2 concentration in atmosphere/ocean and an anoxic depositional environment in early Cambrian. Variable, but significantly positive δ 34S values, 10.2‰～ 28.2‰, for sedimentary pyrite reveals bacterial sulfate reduction as the pyrite-forming process but under sulfate-limited conditions. A protected anoxic basin, which had very limited access to open ocean, and its sediments, where metabolizable organic matter was rich and bioturbation was absent, are supposed to be the sulfate-limited environments and might have existed in South China in the early Cambrian.     

Carbon isotope composition of low molecular weight hydrocarbons and monocarboxylic acids from Murchison meteorite

The origin of the organic matter in carbonaceous meteorites remains controversial despite extensive study over the past 20 yr. Motivated by the expectation that the patterns of isotopic variation with molecular structure among the organic compounds would contain important clues to their origin, we have measured the carbon isotopic compositions for individual hydrocarbons and monocarboxylic acids from Murchison meteorite, a C2 carbonaceous chondrite which fell in Australia in 1969. With few exceptions, notably benzene, the volatile products are substantially isotopically heavier than their terrestrial counterparts, signifying their extraterrestrial origin. For both classes of compounds, the ratio of 13C to 12C decreases with increasing carbon number in a roughly parallel manner, and each carboxylic acid exhibits a higher isotopic ratio than the hydrocarbon containing the same number of carbon atoms. These trends are consistent with the kinetically controlled synthesis of higher homologues from lower ones. The results suggest the possibility that the production mechanisms for hydrocarbons and carboxylic acids may be similar; they also impose constraints on the identity of the reactant species.     

塔里木盆地塔东英南2气藏气源分析

英南2凝析气藏天然气属富氮湿气,烃类气体体积分数一般为78.86%~87.67%;甲烷68.92%~76.67%,重烃气体为9.17%~14.01%,非烃气体氮气为13.89%~21.07%,甲烷和乙烷的碳同位素分别为-38.6‰~-36.2‰和-30.9‰~-34.7‰.根据天然气组分、天然气碳同位素的特征,认为英南2凝析气藏的天然气来源于高过成熟的下古生界海相寒武系—下奥陶统腐泥型干酪根形成的原油裂解气,同时应用ln(C2/C3)-ln(C1/C2)及δ13C2-δ13C3与ln(C2/C3)判识模式也印证了英南2气藏气源为原油裂解气,气藏凝析油中存在高含量的金刚烷,指示原油经历了裂解,裂解程度为80%~90%.