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Characteristics of carbon and hydrogen isotopic compositions of light hydrocarbons

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Science China Chemistry 1995年第2期38卷 211-220页

作者：沈平 State key laboratory of gas-geochemistry Lanzhou 730000 China

Light hydrocarbons named in the present paper refer to the natural gas-associated light oil and condensate 46 light oil and condensate samples from 11 oil-bearing basins of China were collected and their carbon and hydrogen isotopic compositions were analysed in terms of their total hydrocarbons, saturated hydrocarbons and a part of aromatic fractions, and gas-source materials and their sedimentary environments were discussed based on the above-mentioned data and the geological background of each area. From the view of carbon and hydrogen isotopic composition of total hydrocarbons and saturated hydrocarbons, it is revealed that the condensate related to coal-bearing strata is enriched in 13C and D while that related to the source material of type I-II is enriched in 12C. In general, the isotopic composition of carbon is mainly attributed to the inheriting effect of their source materials, whereas that of hydrogen principally reflects the correlationship between hydrogen isotopes and the sedimentary environment as well as the salinity of water medium. The author proposed, based on the data available, that the light hydrocarbons with δD value of less than -150%o might be considered as generated from the fresh to brackish water environment and those with δD value of higher than - 150‰ from the brackish to marine environment. It can be concluded that the features of organic materials are controlled by sedimentary facies and the different types of organic materials characterized by different compositions of stable isotopes. Additionally, the data of Jurassic condensate of Australia are listed, and its hydrocarbon-generating environment is deduced as fresh-water swamp based on the rich H and 13C

关键词： light hydrocarbon stable isotope sedimentary environment salinity of water medium.

Comprehensive geochemical identification of highly evolved marine carbonate rocks as hydrocarbon-source rocks as exemplified by the Ordos Basin

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Science China Earth Sciences 2006年第4期49卷 384-396页

作者： Tenger key laboratory of gas geochemistry Lanzhou Institute of Geology Chinese Academy of Sciences

This study reversed the developing environments of hydrocarbon-source rocksin the Ordos Basin and evaluated carbonate rocks as hydrocarbon-source rocks and their distributionson account of the fact that China''s marine carbonate rocks as hydrocarbon-source rocks arecharacterized by intensive thermal evolution and relatively low abundance of organic matter, bytaking the Lower Paleozoic of the Ordos Basin for example and in light of the calculated enrichmentcoefficients of trace elements, the REE distribution patterns, the mathematical statistics analysisof elements and carbon isotopes and their three-dimensional diagrammatization in combination withthe necessary organic parameters. As for the Ordos Basin, TOC=0.2% is an important boundary *** have shown that in the strata where TOC is greater than 0.2%, Ba is highly enriched withpositive δ^(13)C_(carb) shifts and δ^(13)C_(org) less than -28per thousand, reflecting a thighpaleo-productivity, high burial amounts of organic matter, relatively good hydrocarbon-generatingpotentiality and intensive REE fractionation. All these indicated that the settlement rates are lowand the geological conditions are good for the preservation of organic matter, hence favoring thedevelopment of hydrocarbon-source rocks. The Klimory and Wulalik formations show certainregularities in those aspects and, therefore, they can be regarded as the potential effectivehydrocarbon-source rocks. In the strata where total TOC is less than 0.2%, the contents of Ba arelow, δ^(13)C_(carb) values are mostly negative, and δ^(13)C_(org) values range from -24perthousand—-28per thousand, demonstrating low burial amounts of organic matter, poor potentialitiesof hydrocarbon generation, weak REE fractionation and rapid settlement rates. These facts showedthat most of the hydrocarbon-source rocks were formed in shallow-water, high-energy oxidizingenvironments, thus un-favoring the development of hydrocarbon-source rocks. It is feasible to makeuse of the

关键词： effective hydrocarbon-source rock, sedimentary environment, trace element, stable isotope, identification index.

Significance of the Isotopic Composition of He and Ar in Natural gases

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Chinese Science Bulletin 1993年第20期38卷 1726-1730页

作者：刘文汇徐永昌 State key laboratory of gas-geochemistry Lanzhou 730000 PRC

To identify the oil-gas source rocks is very important for the prospection of oil and gas, and it is a key method to detect the isotopic composition of He and Ar in natural gases for retracing source rocks. The detection of Ar isotopic composition was started in 1973 by Gavrigov et al., then the time-accumulating effect of radiogenic Ar was recognized by Chinese researchers after the discovery of the fact that the content of radiogenic Ar (i. e. 40Ar) increases with the increase of the age of source rocks, and the formula to estimate the age of source rocks was established with the consideration of the K

关键词： time-accumulating effect oil-gas correlation age-calculating formula of source rocks.

Experiments on the primary migration of oil from source rocks

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Chinese Journal Of geochemistry 2007年第1期26卷 66-71页

作者：马素萍雷天柱荆明夏燕青 key laboratory of gas geochemistry Institute of Geology and GeophysicsChinese Academy of Sciences

Simulation experiments on the primary migration of oil were carried out on massive samples. The results proved that oil generated from source rocks was expelled in the form of an independent oil phase. High oil-expulsion efficiency was observed. It follows that the primary migration of oil is not directly dependent on the quantity of oil generated from the source rocks. Therefore, the oil-expulsion proportion was high though some source rocks yielded only a limited amount of oil. A great deal of gas was produced at the same time of oil-generation. Thus, it can be concluded that the main expulsion energy for oil primary migration came from these gases.

关键词：源岩油气运移初次运移模拟实验

Low-mature gases and their resource potentiality

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Chinese Journal Of geochemistry 2009年第3期28卷 231-238页

作者： XU Yongchang WANG Xiaofeng SHI Baoguang the key laboratory of gas geochemistry Chinese Academy of Sciences Lanzhou 730000 China

In the 80’s of last century, based on the advances in natural gas exploration practice, the concepts of bio-thermocatalytic transitional-zone gas and early thermogenetic gas were proposed, and the lower limit Ro values for the formation and accumulation of thermogenetic natural gases of industrial importance have been extended to 0.3%–0.4%. In accordance with the two-stage model established on the basis of carbon isotope fractionation involved in the formation of coal-type natural gases, the upper limit Ro values of lowly evolved natural gases should be set at 0.8%–1.0%. This is the concept of low-mature gas which is commonly accepted at the present time. The Urengoy super-large gas field in western Siberian Basin is a typical example of low-mature gas field, where low-mature gas reserves account for 20% of the globally proven natural gas reserves, and this fully indicates the importance of this kind of resources. The proven reserves of natural gases in the Turpan-Hami Basin of China are approximate to 1000×108 m3, and the thermal evolution indices of source rocks are Ro=0.4%–0.8%. The δ13C1 values of methane are mainly within the range of -44‰– -39‰ (corresponding to Ro=0.6%–0.8%), and those of ethane are mainly within the range of -29‰– -26‰, indicating that these natural gases should be designated to the coal-type low-mature gases. The light hydrocarbon evolution indices of natural gases also provide strong evidence suggesting that they are the coal-type low-mature gases. If so, low-mature gas in the Turpan-Hami Basin has been accumulated to such an extent as to be equivalent to the total reserves of three large-sized gas fields, and their existence is of great significance in the study and exploration of China’s low-mature gases. If it is evidenced that the source rocks of low-mature gases are related mainly to coal measures, China’s abundant lowly evolved coal series resources will provide a huge resource potentiality for the generation of low-mature gases.

关键词：资源潜力低成熟气体

Carbon and hydrogen isotopic composition and generation pathway of biogenic gas in China

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Chinese Journal Of geochemistry 2009年第2期28卷 119-124页

作者： SHEN Ping WANG Xiaofeng XU Yin SHI Baoguang XUYongchang the key laboratory of gas geochemistry Chinese Academy of Sciences Lanzhou 730000 China

The carbon and hydrogen isotopic composition of biogenic gas is of great importance for the study of its generation pathway and reservoiring characteristics. In this paper, the formation pathways and reservoiring characteristics of biogenic gas reservoirs in China are described in terms of the carbon and hydrogen isotopic compositions of 31 gas samples from 10 biogenic gas reservoirs. The study shows that the hydrogen isotopic compositions of these biogenic gas reservoirs can be divided into three intervals: δDCH4>-200‰,-250‰gas under the condition of continental fresh water is acetic fermentation. Our research results showed that the generation pathway of biogenic gas under the condition of marine facies is typical CO2-reduction, the biogenic gas has heavy hydrogen isotopic composition: its δDCH4 values are higher than-200‰; that the biogenic gas under the condition of continental facies also was generated by the same way, but its hydrogen isotopic composition is lighter than that of biogenetic gas generated under typical marine facies condition: -250‰gas reservoirs formed in transitional regions under the condition of continental facies. These gas reservoirs resulted from both CO2-reduction and acetic fermentation, the formation of which may be related to the non-variant salinity of ancient water medium and the relatively high geothermal gradient, as is the case encountered in the Baoshan Basin. The biogenic gas generating in these regions has light hydrogen isotopic composition: δDCH4<-250‰, and relatively heavy carbon isotopic composition. There is a fairly stro

关键词：碳同位素组成生物气藏二氧化碳重氢中国气藏描述醋酸发酵古水介质

Novel C15 sesquiterpanes and their origin in different crude oils from the Pearl River Mouth Basin of China

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Science China Earth Sciences 2016年第8期59卷 1622-1632页

作者： BAO JianPing CHEN XiWen ZHU CuiShan key laboratory of Oil&gas Resource and Exploration Technology Geochemistry DepartmentYangtze UniversityWuhan 430100China

In the saturate fractions of crude oils from the Zhu1 and Zhu2 depressions of the Pearl River Mouth Basin,two novel C_(15) sesquiterpanes have been detected except for drimanes and rearranged *** comparison with spectra and retention times in previous studies,they have been identified as 2,2,4α,7,8-pentamethyl-trans-decalin and 2,2,4α,7,8-pentamethyl-cis-decalin,respectively,which are related to the D/Eringsof18α(H)-and18β(H)-***15sesquiterpanesarerelativelyabundantincondensateoilsthathavehighPr/PhratiosandarerichinterrigenoustriterpanessuchasoleananeandbicadinanesfromtheZhu2depression,butevidentlylowinlacustrineoilsthathavelowPr/***15sesquiterpanescouldberelatedtoterrigenousorganicmatterinorigina***,thereexistcompletelydifferentcorrelationsbetweentherelativeabundancesofdifferentC15sesquiterpanesthathavedifferentsourcesandthePr/Phratio,***,thenovelC15sesquiterpanesandcadinanethatindicateterrigenousinputarepositivelycorrelatedwiththePr/Phratio,butdrimanesandrearrangeddrimaneshavingmicrobialoriginarenegativelycorrelatedwiththePr/******15sesquiterpanesaremuchmoreabundantincarbonaceousmudstone(Pr/Ph=7.39)thanindarkmudstone(Pr/Ph=2.19)fromtheEnpingformation,***,theyarenotcommoninsapropeliclacustrinesourcerocks(Pr/Ph=2.29)***ition,butanoxicenvironmentduringdepositionanddiagenesismaybeaprerequisitefortheformationofnovelC15sesquiterpanes.

关键词： Sesquiterpanes Drimanes Cadinane Oleanane Bicadinanes Crude oils Pearl River Mouth Basin

The Influence of CO on the Carbon Isotopic Composition of CH_4 in Closed Pyrolysis Experiment With Coal

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Chinese Journal Of geochemistry 2004年第4期23卷 359-365页

作者：刘全有刘文汇 State key laboratory of gas geochemistry Lanzhou Institute of Geology Chinese Academy of Sciences

A low-mature coal (R o=0.4%, from the Manjia’er depression, Tarim Basin, China) was subjected to closed system pyrolysis, in sealed gold tubes, under isothermal temperature conditions. The carbon isotopic compositions of the pyrolyst fractions (hydrocarbon, CO 2, CO, etc.) at two temperature points (350°C and 550°C) were measured. The results showed that δ 13C CH 4 value is generally heavier at 350°C than that at 550°C, because the high abundance of CO generated at low temperature would greatly influence δ 13C CH 4 value, and the retention time of CO in gas chromatograph is close to that of CH 4. But CO is formed through chemical reaction of the oxygen-containing functional group -C=O, e.g. lactones, ketones, ether, etc. at low temperature, while CO 2 comes mainly from decarboxylization. The carbon isotopic composition of coal gas from Lanzhou Coal gas Works was definitely different from that of thermally pyrolysed products from coal. The δ 13C CH 4 value of coal gas was abnormally heavier than δ 13C CO. At the same time, the reversed sequence ( δ 13C 1> δ 13C 2) of δ 13C 1 and δ 13C 2 happened. The bond energy of free ions generally decides the sequence of generation of hydrocarbon fractions according to the chemical structure, whereas the stability of pyrolysate fractions and their carbon isotope fractionation are affected by the C-C bond energy.

关键词：低级无烟煤铅热仿真试验煤气碳同位素地球化学

Characteristics and quantitative of negative ion in salt aqueous solution by Raman spectroscopy at 170℃

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Science China Earth Sciences 2006年第2期49卷 124-132页

作者： ZHANG Nai ZHANG Dajiang ZHANG Shuichang ZHANG Dijia Research Institute of Petroleum Exploration and Department Key Laboratory of Petroleum Geochemistry and Key Laboratory for Oil and Gas Reservoirs CNPC Beijing 100083 China

The results from Raman spectroscopy analysis of salt aqueous solutions at?170℃demonstrate that for those clearly sharp iron peaks whose Raman wavenumber is close to each other such as NO_(3)and CO^(2)_(3),their original shape could be restorable by the stripping technique,and that ice’s sharp characteristic peak(3090―3109 cm^(-1))is steady,while the spectrum band of the complex compound(nCl―[H^(+)―OH]_(n))chlorine ion combined chemically with water molecule is 3401―3413 cm^(-1).On the other hand,the research shows that the higher the negative iron concen-tration,the stronger its Raman characteristic peak intensity and the smaller the ice’*** on the number of data and theoretical work,the strong correlation of the molar concentration of negative ion with the S_(i)/S_(H_(2)O)band area ratio is built ***,the developed Raman method is successfully used in the component analysis of the field fluid inclusions from Silurian sandstone in Tarim basin.

关键词： Raman negative ion complex compound nCl--[H^(+)-OH-]_(n) concentration Tarim basin.