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.

Carbon and hydrogen isotopic composition and generation pathway of biogenic gas in 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‰<δDCH4<-200‰ and δDCH4<-250‰. The forerunners believed that the main generation pathway of biogenic 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‰<δDCH4<-200‰, the δDCH4 values may be related to the salinity of the water medium in ancient lakes. From the relevant data of the Qaidam Basin, it can be seen that the hydrogen isotopic composition of biogenic methane has the same variation trend with increasing salinity of water medium. There are biogenic 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 strong negative correlation between the carbon isotopic composition and the hydrogen isotopic composition. The generation mechanism and pathway of carbon, and the hydrogen isotopic composition of biogenic gas may be used to ascertain whether biogenic gas samples from the natural world are of industrial utilization value. In general, the biogenic gas formed by way of acetic fermentation is not propitious to the formation of gas reservoirs.

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}C-1} ranging from -50‰ to -60‰, {δ{}+{13}C-2}>-35‰, Δ values ({δ{}+{13}C-3}-{δ{}+{13}C-2})< 5‰ and C-1/∑C++-2 ratios < 40. Immature to low|mature gases display the characteristics of {δ{}+{13}C-1} ranging from -50‰ to -60‰, {δ{}+{13}C-2} < -40‰, Δ values ({δ{}+{13}C-3}-{δ{}+{13}C-2}) >7‰, and C-1/∑C++-2 ratios >60.

Noble Gas Isotopic Compositions of Cobalt-rich Ferromanganese Crusts from the Western Pacific Ocean and Their Geological Implications

Noble gas isotopic compositions of various layers in three-layered （outer, porous and compact layers） cobalt-rich ferromanganese crusts and their basaltic and phosphorite substrates from the western Pacific Ocean were analyzed by using a high vacuum gas mass spectrum. The analytical results show that the noble gases in the Co-rich crusts have derived mainly from the ambient seawater, extraterrestrial grains such as interplanetary dust particles （IDPs） and wind-borne continental dust grains, and locally formation water in the submarine sediments, but different noble gases have different sources. He in the crusts derives predominantly from the extraterrestrial grains, with a negligible amount of radiogenic He from the eolian dust grains. Ar is sourced mainly from the dissolved air in the seawater and insignificantly from radiogenic Ar in the eolian continental dust grains or the formation water. Xe and Ne derive mainly from the seawater, with minor amounts of extraterrestrial Xe and Ne in the IDPs. Compared with the porous and outer layers, the compact layer has a relatively high 4He content and lower 3He/4He ratios, suggesting that marine phosphatization might have greatly modified the noble gas isotopic compositions of the crusts. Besides, the 3He/4He values of the basaltic substrates of the cobalt-rich crusts are very low and their R/R. ratios are mostly 〈0.1 R., which are similar to that of phosphorite substrates （0.087 R.）, but much lower than that of fresh submarine MORB （8.75±14 Ra） or seamount basalts （3-43 Ra）, implying that the basaltic substrates have suffered strong water/rock interaction and reacted with radiogenic ^4He and P-rich upwelling marine currents during phosphatization. The trace elements released in the basalt/seawater interaction might favor the growth of cobalt-rich crusts. The relatively low ^3He/^4He values in the seamount basalts may be used as an important exploration criterion for the cobalt-rich ferromanganese crusts.

Carbon and oxygen isotopic composition of carbonate cements of different phases in terrigenous siliciclastic reservoirs and significance for their origin:A case study from sandstones of the Triassic Yanchang Formation,southwestern Ordos Basin,China

Early carbonate cements in the Yanchang Formation sandstones are composed mainly of calcite with relatively heavier carbon isotope(their δ18O values range from-0.3‰--0.1‰) and lighter oxygen isotope(their δ18O values range from-22.1‰--19.5‰).Generally,they are closely related to the direct precipitation of oversaturated calcium carbonate from alkaline lake water.This kind of cementation plays an important role in enhancing the anti-compaction ability of sandstones,preserving intragranular volume and providing the mass basis for later disso-lution caused by acidic fluid flow to produce secondary porosity.Ferriferous calcites are characterized by relatively light carbon isotope with δ13C values ranging from-8.02‰ to-3.23‰,and lighter oxygen isotope with δ18O values ranging from-22.9‰ to-19.7‰,which is obviously related to the decarboxylation of organic matter during the late period of early diagenesis to the early period of late diagenesis.As the mid-late diagenetic products,ferriferous calcites in the study area are considered as the characteristic authigenic minerals for indicating large-scaled hydrocarbon influx and migration within the clastic reservoir.The late ankerite is relatively heavy in carbon isotope with δ13C values ranging from-1.92‰ to-0.84‰,and shows a wide range of variations in oxygen isotopic composition,with δ18O values ranging from-20.5‰ to-12.6‰.They are believed to have nothing to do with decarboxylation,but the previously formed marine carbonate rock fragments may serve as the chief carbon source for their precipitation,and the alkaline diagenetic environment at the mid-late stage would promote this process.

Dibenzofuran Series in Terrestrial Source Rocks and Crude Oils and Applications to Oil-Source Rock Correlations in the Kuche Depression of Tarim Basin, NW China

Ten series of aromatic hydrocarbon compounds (biphenyl, naphthalene, phenanthrene, anthracene, retene, chrysene, benzoanthracene, dibenzofuran, fluorene, dibenzothiophene) isolated from seven Triassic and Jurassic lacustrine mudstone samples and three swamp coal samples, as well as five crude oil samples collected in the Kuche depression of the Tarim Basin, NW China, have been analysed by GC-MS techniques. It is found that the relative abundances of dibenzofuran series are higher in the three swamp coal samples than those in the lacustrine mudstone samples. Based on the similar relative abundances of dibenzofuran series, especially dibenzofuran compound, in the TICs of aromatic hydrocarbons, crude oils from wells SA3 (K), YTK5 (E, K) and QL1 (E) are thought to have been derived predominantly from the coals of the Lower Jurassic Yangxia Formation or Middle Jurassic Kezilenuer Formation, whereas those from wells YM7 (O) and YH1 (E) were derived mainly from Triassic and Jurassic lacustrine mudstones in the Kuche depression. This is the first report about how to distinguish coal-generated oils from lacustrine mudstone-generated oils in the Kuche depression in terms of the dibenzofuran series. The present paper has enlightening and directive significance for further oil-source rock correlations and oil and/or gas exploration in the Kuche depression of the Tarim Basin.

Comprehensive geochemical identification of highly evolved marine hydrocarbon source rocks: Organic matter, paleoenvironment and development of effective hydrocarbon source rocks

This study analyzed the developing environments of hydrocarbon source rocks in the Ordos Basin and evaluated carbonate rocks as hydrocarbon source rocks and their distributions on account of the fact that China’s marine carbonate rocks as hydrocarbon source rocks are characterized by the intensive thermal evolution and relatively low abundance of organic matter, by taking the Lower Paleozoic of the Ordos Basin for example and in light of the calculated enrichment coefficients of trace elements, the profile analysis of trace element contents, ratios of relevant elements, and stable isotopic compositions and their three-dimensional diagrammatization in combination with the necessary organic parameters. As for the Ordos Basin, TOC=0.2% is an important boundary value. Studies have shown that in the strata TOC>0.2%, V/(V+Ni)>0.50, Zr/Rb<2, Rb/K(×104)>30, Z>122, Th/U>0.80, Zn and Mo are enriched with a positive δ13Ccarb excursion. All these indicated a stagnant and stratified sedimentary environment that has low energy, anoxia and high salinity in bottom water. In these strata the geological conditions are good for the preservation of organic matter, hence favoring the development of hydrocarbon source rocks. These strata have δ13Corg<-28‰ (Ⅰ- Ⅱ type) and high hydrocarbon-generated potential. The Klimory and Wulalik formations show certain regularities in those aspects, therefore, they can be regarded as the potential effective hydrocarbon source rocks. In the strata TOC≤0.2%, Zr/Rb>1, V/(V+Ni)<0.50, Rb/K<30, Th/U<0.80, Cu, Zn, etc are depleted, and δ13Corg values range from -24‰ to -28‰. All these facts showed that most of the carbonate rocks or mudstones were formed in high-energy oxidizing environments, thus unfavorable to the development of hydrocarbon source rocks. It is feasible to make use of the geochemical method to comprehensively assess the highly evolved marine carbonates rocks as potential hydrocarbon source rocks and their distributions.

Low-mature gases and their resource potentiality

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.

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.

Thermogravimetry-differential thermal analysis coupled with chromatography as a thermal simulation experimental method and its application to gaseous hydrocarbons from different source rocks

In this paper a thermogravimetry-differential thermal analysis method coupled with chromatography (TG-DTA-GC) has been adopted to simulate the generation of gaseous hydrocarbons from different hydrocarbon source rocks such as coals, mudstones, and carbonate rocks with different maturities. The temperature programming for thermal simulation experiment is 20℃/min from ambient temperature to 700℃. As viewed from the quantities and composition of generated gaseous hydrocarbons at different temperatures, it is shown that low-mature coal has experienced the strongest exothermic reaction and the highest loss of weight in which the first exothermic peak is relatively low. Low-mature coal samples have stronger capability of generating gaseous hydrocarbons than high-mature samples. The amounts and composition of gaseous hydrocarbons generated are closely related not only to the abundance of organic carbon in source rocks, but also to the type of kerogen in the source rocks, and their thermal maturity. In the present highly mature and over-mature rock samples organic carbon, probably, has already been exhausted, so the production of gaseous hydrocarbons in large amounts is impossible. The contents of heavy components in gaseous hydrocarbons from the source rocks containing type-Ⅰand -Ⅱ kerogens are generally high; those of light components such as methane and ethane in gaseous hydrocarbons from the source rocks with Ⅲ-type kerogens are high as well. In the course of thermal simulation of carbonate rock samples, large amounts of gaseous hydrocarbons were produced in a high temperature range.

Oxidant-elemental sulfur as an effective promoter for transformation of organic matter to hydrocarbons at moderate-low temperatures

Elemental sulfur is widely dispersed in the hydrocarbon source rocks and its depositional environment is usually thought as a reducing environment. The presence or absence of free oxygen is a key to identify oxidizing or reducing environment. But elemental sulfur is often present as an oxidant in this environment. When elemental sulfur meets with organic matter, redox reaction will occur. In our simulation experiments at 200-400℃, the existence of elemental sulfur can sharply increase the amounts of hydrocarbons, hence leading to the production of immature or low-mature oils and natural gases. At the temperature of 300℃, the addition of elemental sulfur will further enhance the relative yields of hydrocarbons, and the final yield of total extracts and gaseous hydrocarbons of similitude kerogens by more than 463% and 2760%, respectively, while those of oil shales are increased by about 71% and 2044%, respectively. But at the temperature of 450℃, elemental sulfur plays a negative role in liquid hydrocarbon formation. The presence of elemental sulfur is probably a key factor in the gypsolyte environment leading to the formation of immature or low-mature oils, as well as the coexistence of immature or low-mature oils and natural gases.

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.

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.

Experiments on the primary migration of oil from source rocks

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.

Interaction of copper with fatty acids in Soxhlet extraction and its influence

Treatment with metallic copper for the removal of elemental sulfur from bitumen extracted from sedimentary rocks or petroleum is the most widely used method. Little attention has been paid, however, to its disadvantages. It was observed that copper can interact with some polar organic substances during conventional sulfur removal, which can strongly influence the quantitative and qualitative determination of bitumen, as has been confirmed by interaction of long-chain fatty acids with copper. The copper soap generated was analyzed by element analysis, inductively coupled plasma optical emission spectrometry (ICP-OES), thermal analysis (TG-DSC) and Fourier Transform Infrared spectroscopy (FTIR). Mechanism of the interaction was investigated and elucidated. Our experimental results would necessitate improvement of the present method for sulfur removal and/or a search for a new one.

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.

Evolution of the CBM reservoir-forming dynamic system with mixed secondary biogenic and thermogenic gases in the Huainan Coalfield,China

The secondary biogenic gas is an important original type of the coalbed methane (CBM) in China. Based on the analyses of sedimentary and burial history of the Permian coal-bearing strata, combined with thermal history and gas generation process of coals, the CBM reservoir-forming dynamic system with mixed secondary biogenic and thermogenic gases in the Huainan Coalfield is subdivided into four evolutionary stages as follows: (i) shallowly-buried peat and early biogenic gas stage; (ii) deeply buried coal seams and thermogenic gas stage; (iii) exhumation of coal-bearing strata and adsorbed gas lost stage; and (iv) re-buried coal-bearing strata and secondary biogenic gas supplement stage. The Huainan CBM reservoir-forming model has the features of the basin-centered gas accumulation. The evolution of the reservoir-forming dynamic system proves that the thermogenic gas is not the main gas source for the Huainan CBM reservoir. Only the secondary biogenic gases as an additional source replenish into the coal bed after basin-uplift, erosional unroofing and subsequent scattering of thermogenic gases. Then this kind of mixed CBM reservoirs can be formed under suitable conditions.

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.

Secondary biogenic coalbed gas in some coal fields of China

The secondary biogenic coalbed gas, a new genetic and energy source type of coalbed gas in China, has been found in Xinji, Liyazhuang and Enhong areas. The essential characteristics of this type of gas are: (i) the major component of the gas is methane, with C1/C1-5 value higher than 0.99, indicating that the gas is part of dry gas; (ii) theδ13C1 value is in the range of -61.7‰to -47.9‰, mostly lower than -55‰, which is much lower than the estimatedδ13C1 value of thermogenic methane according to the thermal evolution degree of the coal rocks (with R0 value from 0.87% to 1.43%), showing the characteristics of the secondary biogenic gas; (iii) theδ5D value of methane ranges from -244‰to -196‰; (iv)δ13C 2 value ranges from -26.7‰to -15.9‰andδ13C 3 value ranges from -10.8‰to -25.3‰, indicating that the heavier hydrocarbons have a thermogenic origin; (v) the content of CO2 is very low, andδ13CCO2 value changes greatly, reflecting a characteristic of secondary change; (vi)δ15N2 value ranges mainly from -1‰to +1‰, indicating N2 derived significantly from air. The negative linear correlation between the contents of N2 and CH4 reflects the activity of bacteria bearing surface water infiltrating into coal beds. The comprehensive tracing indices show that the coalbed gas in the studied areas is the mixed gas of primarily secondary biogenic gas and a part of remnant thermogenic gas. The uplift of coal beds and the development of faults in the studied areas create favorable conditions for the formation of the secondary biogenic gas.