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.

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

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.

The evolution characteristics and fractionation mechanism of carbon isotopes in the process of “multi-stage hydrocarbon generation”

The Jiyang Sag and the Liaohe Basin are the two important areas where immature oil resources are distributed in China. From these two areas immature-low mature to mature oil samples were collected for carbon isotopic analysis. The extracts of source rocks are dominant in the Jiyang Sag while crude oils are dominant in the Liaohe Basin. The maturity index, R-o, for source rocks varies from {0.25%} (immature) to {0.65%} (mature). Studies have shown that within this range of R-o values the extracts of source rocks and crude oils, as well as their fraction components, have experienced observable carbon isotope fractionation. The carbon isotopic values tend to increase with burial depth, the oils become from immature-low mature to mature, and the rules of evolution of oils show a three-stage evolution pattern, i.e., light→heavy→light→heavy oils. Such variation trend seems to be related to the occurrence of two hydrocarbon-generating processes and the main hydrocarbon-forming materials being correspondingly non-hydrocarbons and possessing MAB characteristics, lower thermodynamic effects and other factors. In the process towards the mature stage, with increasing thermodynamic effects, the thermal degradation of kerogens into oil has become the leading factor, and correspondingly the bond-breaking ratio of {}+{12}C-{}+{13}C also increases, making the relatively {}+{12}C-rich materials at the low mature stage evolve again towards {}+{13}C enrichment.

Unusual N-Alkane Distributions in Extracts from Marine Carbonate Rocks at High Levels of Maturity and Overmaturity

N\|alkanes in extracts from possible carbonate source rocks of the Lower Ordovician Majiagou Formation in the central gas field of the Shanganning Basin and the Upper Sinian Dengying Formation in the Weiyuan gas field of the Sichuan Basin, are characterized by bimodal distributions with the dominant carbon numbers in the range C\- 17 \|C\- 21 and C\- 25 \|C\- 29 . In most samples, the lower carbon number components are present in greater abundance than the higher carbon number ones. Most samples contain significant concentrations of waxy hydrocarbons(C\- 22+ ) with C\- 21- /C\- 22+ ratios between 0.50 to 3.16, and an average value of 1.34. The n\|alkanes in extracts of outcrops and shallow core samples of Upper Proterozoic and Lower Palaeozoic carbonate rocks in the western and southern parts of the North China Basin are of unimodal distributions dominated by n\|alkanes maximizing in the C\- 25 \|C\- 29 range. These extracts have very high concentrations of waxy hydrocarbons with C\- 21- /C\- 22+ ratios all <1.0, ranging from 0 14 to 0 90 and averaging 0.36. All of the extracts have a marked odd/even predominance in the high molecular weight n\|alkane range regardless of whether they are from shallow or deep cores or outcrop samples. Simulation experiments were performed using typical sapropelic\|type kerogens from the immature Sinian Lower Xiamalin Formation carbonate\|rich shales collected at Jixian, Hebei Province, North China Basin, and the contemporary microplanktonic blue\|green algae Spirulina subsala. Results indicate that the unusual distribution of n\|alkanes in the extracts of Upper Proterozoic and Lower Palaeozoic carbonate rocks possibly originated from algae in the source rocks at high levels of maturity and overmaturity.

Geochemistry on mantle-derived volatiles in natural gases from eastern China oil/gas provinces (I)——A novel helium resource——commercial accumulation of mantle-derived helium in the sedimentary crust

Commercial accumulation of mantle-derived helium in the sedimentary shell is discussed. Generally speaking, a commercial helium pool is formed by accumulated 4He that comes from uranium and thorium via a-decay; therefore, it has a very low He/4He value in the magnitude of 10 . The helium concentration in some gas wells of eastern China oil/gas provinces is about or over 0.05%-0.1%, consequently forming commercial helium wells (pools), such as the Wangjinta Gas Pool in Songliao Basin, Huangqiao Gas Pool in North Jiangsu Basin and some gas wells in Sanshui Basin. Studies have proved that when the 3He/4He value of a helium gas pool is about 3.7×10 -6 -7.2× 10-6, namely mantle-derived helium in its total helium concentration accounts for 33. 5%-65.4%, it is a crust-mantle dual-source or dominantly mantle-derived helium gas pool, which is a novel helium resource and its formation is mainly related to the distribution of megafractures.

Geochemistry on mantle-derived volatiles in natural gases from eastern China oil/gas provinces (I )——Helium, argon and hydrocarbons in mantle volatiles

Researches on helium, argon, carbon dioxide and methane are very significant in studies of mantle substance characteristics and mantle evolution. A 【 -shaped pattern of the isotope composition distribution of helium and argon sourced from the mantle and the crust, abundance distribution, isotopic composition and reservoir formation of carbon dioxide, and mantle-sourced methane are discussed.

Carbon isotope characteristics,origin and distribution of the natural gases from the Tertiary salty lacustrine facies in the West Depression Region in the Qaidam Basin

The Tertiary in the West Depression Region of the Qaidam Basin has the typical inland salty lacustrine deposits in China. 34 natural gas samples were collected from 13 oil fields in the West Depression Region in the basin, the chemical compositions and carbon isotopes of methane, ethane, propane, and butane were measured. According to the carbon isotope characteristics of natural gases in combination with geochemical characteristics of the source rocks and crude oils, the natural gases can be divided into sapropelic associated gas, mixed organic matter-derived associated gas, coal-derived gas and mixed gas. The carbon isotope characteristics, origin and distribution of the natural gases are considered to be related with the types and distribution of organic inputs in lake environments with different salinities. The lake salinity can regionally forecast the distribution of the different genetic types of natural gas. Compared with the different genetic types of natural gas from other Chinese basins, the carbon isotopes of the heavy hydrocarbons of the natural gas from the Tertiary salt lacustrine facies in the Qaidam Basin are extremely heavier. Therefore, this should be considered when natural gases are genetically classified in the basin.

A New Model for the Genesis of Natural Gases--Multi-source Overlap, Multi-stage Continuity, Type Controlled by Main Source and Nomenclature by Main Stage (Ⅰ)--Multi-source Overlap and Type Controlled by Main Source

Based on the geochemical studies of natural gases in the past ten years in China, the authors have proposed a new model for their genesis--multi-source overlap, multi-stage continuity, main source-controlling type and nomenclature by the main stage.Multi-source refers to a diversity of material sources involved in the formation of natural gases, including abiogenic and biogenic material sources. In regard to biogenic sources, either oil-generating or coal-generating organic matter would produce gaseous hydrocarbon reservoirs of commercial importance. Generally, natural gases originating from these sources can overlap to form gas reservoirs. Under specific circumstances mantle-source abiogenic gases could overlap biogenic gases to form gas reservoirs. In nature, natural gases predominated by gaseous hydrocarbons may be formed from a single end-member source. However, multi-source overlap is more typical of the genesis of natural gases.

A New Model for the Genesis of Natural Gases——Multi-source Overlap, Multi-stage Continuity, TypeControlled by Main Source and Nomenclature by Main Stage (Ⅱ)——Multi-stage Continuity and Nomenclature by Main Stage

The generation of natural gases involves several stages and the various stages are of continuous transition. This is another feature of natural gas generation. The term "multi-stage" is relative mainly to oil-generating threshold value and liquid window. The evolution of organic matter is affected by different epigene agencies and natural gases differing in geochemical properties such as biogenic gas (bacterial gas), thermocatalytic gas and pyrolytic gas could be produced at different stages of the evolution of organic matter. The proposal of bio-thermocatalytic transitional-zone gas presents a pattern of mutual linking and continuous transition of natural gases originated at different stages.In the genetic classification of natural gases, the nomenclature of a certain gas is based mainly on the epigene agency which is responsible for its formation, for example, biogenic gas, pyrolytic gas. That is the "nomenclature by the main stage" described in this study. On account of the continuity of gas

Genetic Characteristics of Natural Gases——Multi-source Overlap and Multi-stage Continuity

Over a long period of time in the past, the geochemistry of natural gases was considered an attached branch of petroleum geoscience. Practice in natural gas exploration was also regarded as part of practice in petroleum exploration. As viewed from the developing history of oil/gas industry throughout the world, there has been, without any exception, a period in which integrative research is undertaken on oils and natural gases and consideration is given to both research and exploration. That is because oils and

Application of Carbon Isotopic Composition of Natural Gases to the Gas Migration——Taking the Liaohe Basin as an Example

Primary and secondary migration generally takes place during the forming of oil-gas field. The study on carbon isotopic composition of natural gases, gas components and so on is taken as one of the effective methods used in the identification of source rocks and migratory distances of natural gases in the oil- and gas-bearing basins with the characteristics of multi-generative strata, multi-source rocks, complexed tectonics and developed fractures. The changes of gas components and their isotopic compositions are

Carbon isotope distribution in aromatic nuclei and aliphatic side chains of sedimentary organic matter

Isotope composition analysis is an important technique in researches on oil-gas-sourcecorrelation and evolution of sedimentary organic matter. Many δ13C1-Ro relationship mod-els for natural gas have been suggested, and almost all of them indicate that naturalgas derived from the type-Ⅲ kerogen is isotopically heavier than that from the type-Ⅰ

Sedimentological evidence of the piracy of fossil Zoige Lake by the Yellow River

The Yellow River, the birthplace of China’s culture, is well known over the world forits huge sediment yield and unruly temper. The origin of the river was considered bymany foreign and domestic scholars through long-term studies as: the Yellow River turnedgradually to the present features through the way that the river was eroded headwards

Discovery and its geological significance of the mantle- derived helium in the inclusions of the Ordovician oil-bearing reservoir rocks in the Huanghua depression,China

The values of the helium isotopes in the inclusions of the Ordovician reservoir rocks in the Kongxi buried hill belt in the Huanghua depression were first measured and the source of helium and its geological significance were investigated in comparison with those of the helium isotopes in the conclusions in the Ordovician rocks in the Ordos basin and the Tarim basin. The input of the mantle-derived helium into the inclusions in the carbonate reservoir rocks was found from the Konggu 3 well, the Konggu 4 well, and the Konggu 7 well in the Kongxi buried hill belt. The 3He/4He and R/Ra in the conclusions in the Ordovician oil-bearing reservoir rocks in the Konggu 7 well average 2.54×10-6(3) (sample quantity, the same below) and 1.82(3), respectively. The percent of the mantle-derived helium in the inclusions of the reservoir rocks in the Konggu 7 well reaches up to an average of 23.0%(3). The age of the contribution of the mantle-derived helium to the inclusions in the Kongxi buried hill belt is in the Late Triassic or the Early Tertiary. The finding of the mantle-derived helium shows that the interaction of the deep crust with mantle and the activity of deep faults occurred, the terrestrial heat flow value was high, and mantle-derived inorganic gas pools might be formed in the Kongxi buried hill belt. The finding of the mantle-derived helium in the inclusions of oil-bearing reservoir rocks also provides a new way for researching the activity of mantle-derived matter and its associated geological problems.

Isotopic composition charac-teristics and identification of immature and low-mature oils

Isotopic composition characteristics and the significance of immature and low-mature oils are first systematically discussed. The carbon isotopes of the whole oil can be divided into two groups, one has δ13C main peak values ranging from -30‰ to -29 and the other from -27‰ to -25‰, they are related to lacustrine and salt-lake facies or swamp facies, respectively. The carbon isotopic fractionation among different group components is relatively small, usually less than 2‰ and the biggest difference in fractionation often occurs between saturated and aromatic fractions. Their δD values vary between -180‰ and -130‰. The main peak of their δD values concentrates between -170‰ and -150‰, suggesting a domination of lacustrine facies. However, the secondary peak ranges from -160‰ to -150‰, showing a frequent salinization of paleo-water bodies. The average δ13C values of the methane vary between -50‰ and -52‰, about 10‰ lighter than those of mature oils. There is a relatively good

Helium and argon isotopes of the Tertiary basic igneous rocks from Shandong Peninsula and implications for the magma origin

Helium (He) and Argon (Ar) isotopic compositions of the Tertiary basic igneous rocks were determined by the high temperature melting extraction method. The selected samples for the studies included al-kaline basalts and diabases from the Jiyang basin,and the surrounding Shanwang and Qixia outcrops in the Shandong Peninsula,eastern China. The results show that the Paleogene basalts and diabases from the Jiyang basin yielded a wide range of P4 PHe abundance of (73.70-804.16)×10 P-8 Pcm P3 P STP·g P-1 P,with P3 PHe/ P4 PHe ratios of 0.374-2.959 Ra,which was lower than the MORB but evidently higher than the con-tinental crust value. The Neogene alkaline basalts from the Jiyang basin,Shanwang and Qixia outcrops have variable P4 PHe abundances ((42.34-286.72)×10-8 Pcm P3 P STP·g-1 P),and "continental crust-like" P3 PHe/ P4 PHe ratios (0.013-0.074 Ra). All of them contain atmospheric-like P40 PAr/ P36 PAr ratio (395.4-1312.7),reflecting the mantle sources with air components. Their low P3 PHe/ P4 PHe ratios are interpreted as the enrichment of the radiogenic P4 PHe mainly inherited from the mantle. He and Ar systematics show the mixing of MORB-type,air and a P4 PHe enriched member in the mantle source,suggesting that these igneous rocks originated from the depleted asthenospheric mantle mixed with an EMI component. Therefore,the present He and Ar isotopes do not support the viewpoints that the Cenozoic igneous rocks of Eastern North China were the products of mantle plume(s) activities.

δ^(13)C values and hydrogen index records in sediment organic matter of RH core of Zoige Basin,eastern Qing-Zang(Tibet)Plateau and their environmental significance

Total organic carbon （TOC） content correlates very well with hydrogen index （HI） in the sedi-ments of RH core in the Zoig Basin.And the δ13C values of TOC become more positive while both TOCcontent and HI decline,indicating the subaerial exposure or the lake sedimonts approaching to the water lev-el.On the basis of the above,RH core sediments are divided into 23 climatic fluctuation stages,including 12 warm-humid stages and 11 dry-cold stages,which can he compared with oceanic oxygen isotopestages,loess profile and polar ice-core records.

The relationship between carbon and oxygen isotopic composition characteristics of carbonates in loess sediments and paleoclimate

Based on the carbon and oxygen isotopic compositions of carbonates in loess sediments meas-ured by the methods of stepwise heating and phosphoric acid decomposition from five pieces of samples ofpaleosol,loess and eolian sand,respectively,the distributive characteristics in different temperature steps andthe fractionation mechanisms of carbon and oxygen isotope and their relation to the paleoclirnate are discussed.The preliminary results show that,by means of stepwise heating,different carbon and oxygen isotopiccompositions are obtained in different temperature steps and carbon and oxygen isotopic compositions ofpaleosol,loess and eolian sand are in a different distributive pattern in the range of studied temperaturesteps.The results also show that the δ13C ratios in 700-800℃ are more sensitive tracers of paleoclimatethan those measured by the method of phosphoric acid decomposition.The susceptibility to climatic changesof δ18O ratios analysed by the method of phosphoric acid decomposition is higher than those analysed by themethod of stepwise heating,but the δ18O ratios measured by these two methods do not effectively reflect cli-matic changes.

Distribution of Helium Isotopes in Western Pacific Upper Layer

3He/4He ratios in samples of sea water obtained at depths from surface to 300 m in the upper layer of the Western Pacific Ocean were measured by a mass spectrometer VG5400. The lateral and vertical distribution of He isotopes in the studied area was discussed in detail on the basis of 3He/4He ratios. Excess and depleted 3He. in relation to δ3He value of surface water in equilibrium with air has been discussed in the area, which may be mainly attributed to the incorporation of the North Pacific Intermediate Water with the Equatorial Upwelling and the exchange of water masses between the South China Sea and the Western Pacific, respectively. The present work in Western Pacific has also indicated that He isotopes may be used as a tracer for mixing processes of water masses and oceanic circulation.

Oil-gas microseapage and shallow hydrocarbon anomaly in craton basin

Although it has been accepted that oil and gas can migrate a long distance throughfaults, surface of unconformity and fractures in vertical and horizontal directions, it isuncertain whether deep oil-gas can reach the surface in stable craton basin in which faultsand fractures are poorly developed. The vertical changes of pyrolysis hydrocarbon,