Isotopic compositional Characteristics of Terrigenous Natural Gases in China

The C and H isotopic compositions of the methane in more than 160 gas samples from 10 basins in China are presented in this paper.The natural gases are classified as four types: biogenic gas ,bio-thermocatalytic transitional gas, gas associated with condensate oil ,and coal-type gas. The isotopic compositions of these gases closely related to the depositional basins, the types of organic matter,the stages of thermal evolution and the genetic characteristics of different gas reservoirs.Studies of the C and H isotopic compositions of terrigenous natural gases will provide valua-ble information on the prospecting and development of natural gases of different genetic types.     

Helium and Argon Isotopic Composition of Cenozoic Alkali Basalts and Mantle-Derived Xenoliths from Kuandian, Liaoning Province, China

The noble gas isotopic composition and content data of 2 alkali basalts, 3 Iherzolite xenoliths and one clinopyroxene megacryst from the Kuandian region have confirmed the occurrence of a fractionation of noble gases during magmatism. Light noble gases such as He and Ne are high in mobility and appear to be incompatible as compared with heavy ones ( such as Kr and Xe). Therefore, light noble gases are abundant in volcanics, especially in the volcanics with bubbles; lherzolite xenoliths have relatively high heavy noble gases. The clinopyroxene megacryst has the lowest abundance of noble gases, probably due to its high P-T origin. Noble gas isotopic composition of the clinopyroxene megacryst reveals that the mantle source beneath the Kuandian area has an MORB-like reservoir with^3 He/^4He ratio of—10 Ra(Ra: atmospheric^3 He/^4He ratio) and^40 Ar/^36 Ar ratio of 345.6. The Iherzolite xenoliths possess moderate^3 He/^4He ratios of 2.59 -4.53 Ra, reflecting the loss of primary helium during rock deformation or metasomatism caused by enriched mantle fluids during the up-lifting. The alkali volcanics have very low^3 He/^4 He ratios(0.47—0.61 Ra),indicating a contribution of radiogenic^4 He, probably having resulted from crust contamination. Most of the samples have excess^21 Ne and^22 Ne as compared with atmospheric neon, but Kr and Xe isotopic compositions are indistinguishable from atmospheric values within uncertainties with only individual samples having excess^129Xe,^134Xeand^136 Xe.     

Composition and Origin of Shallow Biogenetic Gases in the Baise Basin, South China

Based on the analytical data of over 30 gas samples, combined with geochemical and geological backgrounds, the composition and distribution characteristics of shallow biogenetic gases in the Baise Basin, a Tertiary residual basin in southern China, were extensively investigated, and the origin and formation mechanism tentatively approached. The shallow gases are primarily composed of gaseous hydrocarbons, generally accounting for over 90%. The abundances of methane and C2＋ homologues show a relatively wide range of variation, mainly 50%-100% and 0%-50%, respectively, depending on the mixing proportions between biogenetic and thermogenic gases. A highly negative carbon isotope is the significant signature for the shallow gases with δ^13C1 values of -55‰ to -75‰. According to molecular and isotopic compositions and light hydrocarbon parameters, the shallow gases in the basin can be classified into three types of origins： biogenetic gas, biogenetic/thermogenic mixed gas, and oii-biodegraded gas. They exhibit regular distribution both spatially and temporally, and are believed to be associated with the maturity of adjoining gas source rocks and biodegraded oil accumulation. The Baigang and Nadu source rocks can be considered to have experienced early and late gas generation during early burial and after basin uplift respectively. A late accumulation mechanism of multiple gas sources is put forward for the formation of the shallow gas reservoirs, which is responsible for the variations in chemical and isotopic composition of the gases in depth profile.     

Kinetic Modeling the Formation of Low-mature Gases and Analysis of the Possibility to Be Accumulated

At present, shallow gases have received much attention due to low cost in exploration and production. Low-mature gases, as one significant origin to shallow gas, turns to be an important research topic. The present understanding of low-mature gases is confined within some geological cases, and few laboratory studies have been reported. Therefore, the potential and characters of low- mature gases are not clear up to now. Here, two premature samples （one coal and the other shale） were pyrolyzed in a gold confined system. The gaseous components including hydrocarbon gases and non-hydrocarbon gases were analyzed. Based on kinetic modeling, the formation of low-mature gases was modeled. The results showed that during low mature stage, about 178 mL/gTOC gas was generated from the shale and 100 mL/gTOC from the coal. Two third to three fourth of the generated gases are non-hydrocarbon gases such as H2S and CO2. The total yields of C1-5 for the two samples are almost the same, 30-40 mL/gTOC, but individual gaseous hydrocarbon is different. The shale has much lower C1 but higher C2-5, whereas the coal has higher C1 but lower C2-5. Hydrocarbon gases formed during low-mature stage are very wet. The stable carbon isotope ratios of methane range from -40‰ to -50‰ （PDB）, in good consistence with empiric criterion for low-mature gases summed up by the previous researchers. The generation characters suggest that the low-mature gases could be accumulated to form an economic gas reservoir, but most of them occur only as associated gases.     

Formation Mechanism and Controlling Factors of Natural Gas Reservoirs of the Jialingjiang Formation in the East Sichuan Basin

The Lower Triassic Jialingjiang Formation reservoirs are distributed widely in the East Sichuan Basin, which are composed mainly of fractured reservoirs. However, natural gas with high concentration of H2S, ranging from 4% to 7%, was discovered in the Wolonghe Gas pool consisting primarily of porous reservoirs, while the other over 20 fractured gas reservoirs have comparatively low, tiny and even no H2S within natural gases. Researches have proved the H2S of the above reservoirs are all from the TSR origin. Most of the Jialingjiang Formation natural gases are mainly generated from Lower Permian carbonate rocks, the Wolonghe gas pool＇s natural gases are from the Upper Permian Longtan Formation, and the natural gases of the Huangcaoxia and Fuchengzhai gas pools are all from Lower Silurian mudstone. The formation of H2S is controlled by the characteristics and temperature of reservoirs, and is not necessarily related with gas sources. The Jialingjiang Formation in East Sichuan is buried deeply and its reservoir temperature has ever attained the condition of the TSR reaction. Due to poor reservoir potential, most of the gas pools do not have enough room for hydrocarbon reaction except for the Wolonghe gas pool, and thus natural gases with high H2S concentration are difficult to be generated abundantly. The south part of East Sichuan did not generate natural gases with high H2S concentration because the reservoir was buried relatively shallow, and did not suffer high temperature. Hence, while predicting the distribution of H2S, the characteristics and temperature of reservoirs are the necessary factors to be considerd besides the existence of anhydrite.     

Origin of natural gases and their differences between the eastern and western parts of central Tarim Basin

The origin of natural gases in central Tarim Basin is very complicated and there has been no definite conclusion in this aspect. Based on the results of systematic research on their composition and carbon isotopic characteristics, natural gases in central Tarim Basin are composed mainly of hydrocarbon gas, Ordovician natural gas with the characteristics of crude oil-cracking gas, and Carboniferous natural gas not only originating from kerogen cracking, but also from oil cracking. There are significant differences in composition and carbon isotope of natural gases between the eastern and western areas. The causes for the differences in geochemical characteristics of natural gases are presented as follows: different thermal evolution degrees of organic matter. Natural gases in the western region may have generated from the Middle- Upper Ordovician source rocks, and natural gases in the eatern region may be derived from the Cambrian source rocks, which entered into high to over mature stages; the gases migrated from west to east and caused the different compositional and carbon isotopic characteristics of natural gases; difference in the strength of thermal sulfate reduction between the eastern and western parts, with the reduction in the eastern part being stronger than that in the western part.     

Helium and argon isotopic compositions of the Longquanzhan gold deposit in the Yishu fault zone and their geological implications

The Longquanzhan gold deposit hosted in granitic cataclasites with mylontization of the foot wall of the main Yishui-Tangtou fault. 3He/4He ratios in fluid inclusions range from 0. 14 to 0. 24 R/Ra,close to those of the crust-source helium. 40Ar/36Ar ratios were measured to be 289-1811, slightly higher than those of atmospheric argon. The results of analysis of helium and argon isotopes suggested that ore-forming fluids were derived chiefly from the crust. The δ18O values of fluid inclusions from vein quartz range from -1.78‰ to 4.07‰, and the δD values of the fluid inclusions vary between -74‰ and -77‰. The hydrogen and oxygen isotope data indicated that the ore-forming fluid for the Longquanzhan gold deposit had mixed with meteoric water in the process of mineralization. This is consistent with the conclusion from the helium and argon isotope data.     

安龙球粒陨石研究（Ⅰ）—K^40-Ar^40年龄和宇宙射线暴露年龄测定

The concentrations of radiogenic Ar^40 and cosmogenic Ar^32 in Anlung chondrite have been measured by the isotopic dilution technique. A ultrahigh-vacuum system have been designed for extracting and purifying the gases in the sample. These data provide a K^40-Ar^40 age of 3.28 b.y. and an exposure age of 3.0 m,y. for this chondrite.Based on these results, we have discussed the origin and the former environment of stone meteorite.     

Geochemical Characteristics and Genetic Types of Natural Gas in the Xinchang Gas Field, Sichuan Basin, SW China

The molecular compositions and stable carbon and hydrogen isotopic compositions of natural gas from the Xinchang gas field in the Sichuan Basin were investigated to determine the genetic types. The natural gas is mainly composed of methane (88.99%–98.01%), and the dryness coefficient varies between 0.908 and 0.997. The gas generally displays positive alkane carbon and hydrogen isotopic series. The geochemical characteristics and gas-source correlation indicate that the gases stored in the 5~(th) member of the Upper Triassic Xujiahe Formation are coal-type gases which are derived from source rocks in the stratum itself. The gases reservoired in the 4~(th) member of the Xujiahe Formation and Jurassic strata in the Xinchang gas field are also coal-type gases that are derived from source rocks in the 3~(rd) and 4~(th) members of the Xujiahe Formation. The gases reservoired in the 2~(nd) member of the Upper Triassic Xujiahe Formation are mainly coal-type gases with small amounts of oil-type gas that is derived from source rocks in the stratum itself. This is accompanied by a small amount of contribution brought by source rocks in the Upper Triassic Ma'antang and Xiaotangzi formations. The gases reservoired in the 4~(th) member of the Middle Triassic Leikoupo Formation are oil-type gases and are believed to be derived from the secondary cracking of oil which is most likely to be generated from the Upper Permian source rocks.     

Origin and Accumulation of Natural Gases in the Upper Paleozoic Strata of the Ordos Basin in Central China

The natural gases in the Upper Paleozoic strata of the Ordos basin are characterized by relatively heavy C isotope of gaseous alkanes with δ 13C1 and δ13C2 values ranging mainly from ?35‰ to ?30‰ and ?27‰ to ?22‰, respectively, high δ13C excursions (round 10) between ethane and methane and predominant methane in hydrocarbon gases with most C1/(C1-C5) ratios in excess of 0.95, suggesting an origin of coal-derived gas. The gases exhibit different carbon isotopic profiles for C1-C4 alkanes with those of the natural gases found in the Lower Paleozoic of this basin, and believed to be originated from Carboniferous-Permian coal measures. The occurrence of regionally pervasive gas accumulation is distinct in the gently southward-dipping Shanbei slope of the central basin. It is noted that molecular and isotopic composition changes of the gases in various gas reservoirs are associated with the thermal maturities of gas source rocks. The abundances and δ13C values of methane generally decline northwards and from the basin center to its margins, and the effects of hydrocarbon migration on compositional modification seem insignificant. However, C isotopes of autogenetic calcites in the vertical and lateral section of reservoirs show a regular variation, and are as a whole depleted upwards and towards basin margins. Combination with gas maturity gradient, the analysis could be considered to be a useful tool for gas migration.     

Innovation of experimental methodology for adsorbed gases on hydrocarbon-source rocks

As compared to the device developed by our predecessors, the newly developed adsorbed gas degasification-collection device has a series of advantages such as wide sample application range, large sample inlet, high vacuum, short-time sample smashing, low crushing temperature and water-free gas collection, which ensure the geochemical characteristics of acquired adsorbed gas samples to be the same as those of the adsorbed gases on corresponding hydrocarbon-source rocks. The results showed that the acquired adsorbed gases are composed mainly of hydrocarbon gas and carbon dioxide gas, with the hydrocarbon gas accounting for more than 80%, and can be measured reliably for their δ13C1-δ13C3 data, even δ13C4-δ13C5 data. The results of carbon isotope test and analysis satisfy the needs for the geochemical study and application of adsorbed gases. The above new techniques of experimental geochemistry are helpful for establishing the new direct natural gas-source correlation method, proving that the previous usual method of indirect natural gas-source correlation is scientific and authentic, thus providing the experimental basis for the study and application of adsorbed gases on hydrocarbon-source rocks.     

Origin and Accumulation of Natural Gases in the Upper Paleozoic Strata of the Ordos Basin in Central China

The natural gases in the Upper Paleozoic strata of the Ordos basin are characterized by relatively heavy C isotope of gaseous alkanes with δ13C1 and δ13C2 values ranging mainly from-35‰ to -30‰ and-27‰ to-22‰,respectively,high δ13C excursions (round 10)between ethane and methane and predominant methane in hydrocarbon gases with most C1/(C1-C5)ratios in excess of 0.95, suggesting an origin of coal-derived gas.The gases exhibit different carbon isotopic profiles for C1.C4 alkanes with those of the natural gases found in the Lower Paleozoic of this basin.and believed to be originated from Carboniferous-Permian coal measures.The occurrence of regionally pervasive gas accumulation iS distinct in the gently southward-dipping Shanbei slope of the central basin.It is noted that molecular and isotopic composition changes of the gases in various gas reservoirs are associated With the thermal maturities of gas source rocks.The abundances and δ13C values of methane generally decline northwards and from the basin center to its margins.and the effects of hydrocarbon migration on compositional modification seem insignificant.However, C isotopes of autogenetic calcites in the vertical and lateral section of reservoirs show a regular variation,and are as a whole depleted upwards and towards basin margins.Combination with gas maturity gradient, the analysis could be considered to be a useful tool for gas migration.     

Carbon and Noble Gas Isotopes in the Tengchong Volcanic Geothermal Area, Yunnan, Southwestern China

Carbon and noble gas isotope analyses are reported for bubbling gas samples from the Tengchong volcanic geothermal area near the Indo-Eurasian suture zone. All samples contain a resolvable component of mantle-derived 3He. Occurrence of mantle-derived 3He coincides with surface volcanism. However, 3He occurs over a larger geographic areathan do surface volcanics. δ13C values for CO2 and CH4 vary from -33.4‰ to 1.6 ‰ and from -52.8‰ to -2.8‰, respectively. He and C isotope systematics indicate that CO2 and CH4 in the CO2-rich gases originated predominantly from magmatic component mixed with crustal CO2 produced from carbonate. However, breakdown of organic matter and near-surface processes accounts for the CH4 and CO2 in N2-rich gases. 3He/4He ratio distribution pattern suggests that mantle-derived He and heat sources of high-temperature system in central Tengchong originate from a hidden magma reservoir at subsurface. CO2-rich gases with the highest 3He/4He ratio (5.2 Ra) may be representative of the     

Nitrogen Contents and Isotopic Characteristics of Mesozoic and Cenozoic Granites in Northeastern China

The method of determining the nitrogen isotopic composition of granites in the northeastern part of China is described.The content and isotopic values of nitrogen released from granite samples by stepwise heating were determined as well.The results showed that the diferent areas of northeastern China hae a great difference in nitrogen content and isotopic composition.Nitrogen released from the granites is 1.64-6.23μL/g ,with the maximum at about 600℃,from rhyolite and granophyre is 108.98-755.96μL/g,with the maximum at about 900℃,It is proved that fluid is characterized by heterogeneity in the deep crust of the different areas in northeastern China.The nitrogen isotopic compositions in different ranges of temperautes are wweighted.And the nitrogen isotopic compositions in different anges of temperatures are weighted.And the nitrogen isotopic values are 9.2‰ to 17.0‰,with a variation range of 7.8‰,The nitrogen isotopic ratios may have been fractionated during degassing and the fluid released from granites is the residual component.     

Genetic identification of natural gases from shallow reservoirs in some oil- and gas-bearing basins of China

Natural gases of shallow reservoirs with the carbon isotopic compositions of methane ranging from -50‰ to -60‰ (PDB) were considered as mixed gases of biogenic and thermogenic origins previously and some of them were considered as low-mature (or low temperature thermogenic) gases lately. In this paper natural gases with the carbon isotopic compositions of methane in the above range were identified using the molecular and stable carbon isotopic compositions of methane, ethane and propane. The mixed gases of biogenic and mature thermogenic origins display the characteristics of δ 13 C1 ranging from -50‰to -60‰,δ13C2 ＞ -35‰,Δvalues (δ13C3 -δ13C2) ＜ 5‰ and C1/∑C2 ratios ＜ 40. Immature to low-mature gases display the characteristics of δ 13 C1 ranging from - 50‰ to - 60‰, δ13 C2 ＜- 40‰,Δ values (δ13C3 -δ13C2) ＞7‰, and C1/∑C 2 ratios ＞60.     

Kinetic Parameters of Methane Generated from Source Rocks in the Kuqa Depression of Tarim Basin and Their Application

In a thermal simulation experiment of gold tubes of closed-system, calculating with the KINETICS and GOR-ISOTOPE KINETICS software, kinetic parameters of gas generation and methane carbon isotopic fractionation from Triassic-Jurassic hydrocarbon source rocks in the Kuqa depression of Tarim Basin are obtained. The activation energies of methane generated from Jurassic coal, Jurassic mudstone and Triassic mudstone in the Kuqa Depression are 197-268 kJ/mol, 180-260 kJ/mol and 214-289 kJ/mol, respectively, and their frequency factors are 5.265×10^13 s^-1, 9.761×10^11 s^-1 and 2.270×10^14 s^-1. This reflects their differences of hydrocarbon generation behaviors. The kinetic parameters of methane carbon isotopic fractionation are also different in Jurassic coal, Jurassic mudstone and Triassic mudstone, whose average activation energies are 228 kJ/mol, 205 kJ/mol and 231 kJ/mol, respectively. Combined with the geological background, the origin of natural gas in the Yinan-2 gas pool is discussed, and an accumulation model of natural gas is thus established. The Yinan- 2 gas is primarily derived from Jurassic coal-bearing source rocks in the Yangxia Sag. Main gas accumulation time is 5-0 Ma and the corresponding Ro is in the range from 1.25 %-1.95 %. The loss rate of natural gas is 25 %-30 %.     

The characteristics and sources of natural gases from Ordovician weathered crust reservoirs in the Central Gas Field in the Ordos Basin

The Central Gas Field is a famous large-sized gas field in the Ordos Basin of China. However, identification of main gas sources of the Ordovician reservoirs in this gas field remains puzzling. On the basis of a lot of geochemical data and geological research on natural gases, the characteristics and sources of natural gases from Ordovician weathered crust reservoirs in the Central Gas Field in the Ordos Basin were studied. The results indicated that natural gases from Ordovician weathered crust reservoirs in the Central Gas Field in the Ordos Basin have similar chemical and isotopic compositions to highly mature and over-mature dry gases. Both coal-derived gases and oil-type gases coexist in the Central Gas Field in the Ordos Basin. The former was derived mainly from Carboniferous-Permian coal measures and the latter from Lower Paleozoic marine carbonates. It is suggested that coal-derived gases occur in the eastern part of the Central Gas Field while oil-type gases may be produced mainly in the northern, western and southern parts of the Central Gas Field in the Ordos Basin.     

Geochemical Characteristics and Origin of Natural Gases in the Qaidam Basin, China

Sixty-five natural gas samples were collected from 19 oil-gasfields in the Qaidam basin, China. The chemical composition and carbon isotope values of the samples were measured, and the geochemical characteristics and origin of the natural gases were studied. The gases can be divided into biogenic gases, sapropelic oil-type gases, mixed type oil-type gases, coal-type gases and mixed gas. The δ13Ci values of the biogenic gases are very small and the C2+ contents of them are very low, ranging from -68.2‰ to -61.8‰ and 0.06% to 0.20% respectively. They have heavy δD and δ13Cco2> showing a CC>2 reduction pathway. They are distributed in the East depression region and derived from the Quaternary source rocks. The sapropelic oil-type gases have small δ13C2 values and high C2+ ranging from -36.6‰ to -28.6‰ and from 33.01% to 47.15% respectively. The mixed type oil-type gases have <5I3C2 values and C2+ contents varying from -28.6‰ to -24.8‰ and from 4.81% to 26.06% respectively. Both sapropelic oil-typ     

Nitrogen in Chinese coals

Three hundred and six coal samples were taken from the main coal mines of twenty-six provinces, autonomous regions, and municipalities of China. The method of Kjeldahl-Gunning Analysis was used to measure the nitrogen contents in the samples. Nitrogen in coals is principally of organic nature. A weak positive correlation between coal rank and nitrogen content is inferred in the study. The distribution of nitrogen in each geological age, coal-cumulating area and province＇s coals was studied. The contents of nitrogen in Chinese coals show approximately a normal distribution, and 90% of the values range from 0.52% to 1.41%, the average nitrogen content in Chinese coals is designated as the arithmetic mean, 0.98%.     

Geochemical characteristics and possible origin of natural gas in the Taibei Depression,Turpan-Hami Basin,China

292 chemical composition data and 82 isotopic composition data of gas samples collected from the Taibei Depression of the Turpan-Hami Basin, West China, were used in the study of their origin. Non-hydrocarbon gas is poor in most samples whereas abundant nitrogen in some samples is positively correlated with δ13C1. Although methane is the main constituent, higher molecular gaseous hydrocarbons, from ethane to pentane, are detected in most samples, in accordance with the distribution of oil reservoirs. The stable carbon isotope ratios of methane, eth-ane and propane are defined as d13C1: -45.5‰ to -33.5‰, d13C2: -30.2‰ to -10.5‰, and d13C3: 27.6‰ to -11.2‰, respectively. According to the distribution of carbon isotope ratios, 2 families of gas can be grouped, most showing normal distribution of carbon isotopes, and others having obvious heavier carbon isotopes and being of abnormal distribution. Based on the isotopic composition, the disagreement between the relationship of Δ(d13C1-d13C2) and d13C2 and that of Δ(d13C1-d13C2) and d13C2, and the calculated Ro, there are oil-associated gas, coal-derived gas and mixture of them. Other samples with obviously heavier isotopic compositions from the Yanmuxi oilfield of the Taibei Depression have been degraded by organisms.