Kinetic Model of Gaseous Alkanes Formed from Coal in a Confined System and Its Application to Gas Filling History in Kuqa Depression, Tarim Basin, Northwest China

Based on the pyrolysis products for the Jurassic low-mature coal under programmed temperature,and chemical and carbon isotopic compositions of natural gas from the Kuqa Depression, the genetic origin of natural gas was determined,and then a gas filling model was established,in combination with the geological background of the Kuqa Depression.The active energy of CH_4,C_2H_6 and C_3H_8 was gotten after the data of pyrolysis gas products under different heating rates(2℃/h and 20℃/h)were fitted by the Gas O...     

Enrichment of nitrogen and 13C of methane in natural gases from the Khuff Formation,Saudi Arabia,caused by thermochemical sulfate reduction

Permian Khuff reservoirs along the east coast of Saudi Arabia and in the Arabian Gulf produce dry sour gas with highly variable nitrogen concentrations. Rough correlations between N₂/CH₄, CO₂/CH₄ and H₂S/CH₄ suggest that non-hydrocarbon gas abundances are controlled by thermochemical sulfate reduction (TSR). In Khuff gases judged to be unaltered by TSR, methane δ¹³C generally falls between −40‰ and −35‰ VPDB and carbon dioxide δ¹³C between −3‰ and 0‰ VPDB. As H₂S/CH₄ increases, methane δ¹³C increases to as much as −3‰ and carbon dioxide δ¹³C decreases to as little as −28‰. These changes are interpreted to reflect the oxidation of methane to carbon dioxide.Khuff reservoir temperatures, which locally exceed 150 °C, appear high enough to drive the reduction of sulfate by methane. Anhydrite is abundant in the Khuff and fine grained nodules are commonly rimmed with secondary calcite cement. Some cores contain abundant pyrite, sphalerite and galena. Assuming that nitrogen is inert, loss of methane by TSR should increase N₂/CH₄ of the residual gas and leave δ¹⁵N unaltered. δ¹⁵N of Paleozoic gases in Saudi Arabia varies from −7‰ to 1‰ vs. air and supports the TSR hypothesis. N₂/CH₄ in gases from stacked Khuff reservoirs varies by a factor of 19 yet the variation in δ¹⁵N (0.3–0.5‰) is trivial.Because the relative abundance of hydrogen sulfide is not a fully reliable extent of reaction parameter, we have attempted to assess the extent of TSR using plots of methane δ¹³C versus log(N₂/CH₄). Observed variations in these parameters can be fitted using simple Rayleigh models with kinetic carbon isotope fractionation factors between 0.98 and 0.99. We calculate that TSR may have destroyed more than 90% of the original methane charge in the most extreme instance. The possibility that methane may be completely destroyed by TSR has important implications for deep gas exploration and the origin of gases rich in nitrogen as well as hydrogen sulfide.     

松辽盆地庆深气田异常氢同位素组成成因研究

对松辽盆地徐家围子断陷庆深气田天然气组分、碳氢同位素和稀有气体同位素的分析表明,天然气以烷烃气为主,烷烃气碳同位素组成随着碳数增加呈变轻趋势,且δ13C1＆gt;-30‰, R/Ra一般大于1.0,δ13CCO2值介于-16.5‰~-5.1‰之间;氢同位素组成δD1=-205‰~-197‰,平均值为-203‰,δD2=-247‰~-160‰,平均值为-195‰,δD3=-237‰~-126‰,平均值为-163‰,且存在氢同位素组成倒转现象,即δD1＆gt;δD2＆lt;δD3。根据对庆深气田天然气不同地球化学特征分析,认为该气田烷烃气中重烃主要为有机成因,而 CH4有相当无机成因混入。庆深气田烷烃气氢同位素组成具有 CH4变化小,而重烃（δD2,δD3）变化大的特点。根据与朝阳沟地区天然气烷烃气氢同位素组成对比分析,认为 CH4主要表现为无机成因,而重烃气（δD2,δD3）主要为有机成因,且无机成因CH4氢同位素组成重于有机成因CH4。     

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.     

Geochemical characteristics of methane from sediments of the underwater high Posolskaya Bank (Lake Baikal)

The component and carbon isotope compositions were studied in the hydrocabon gases from sediments of the underwater high Posolskaya Bank (Lake Baikal). It was established that sediments of this Baikal area contain methane of microbial (C₁/C₂ >16000; δ¹³C 70 ± 3‰) and thermocatalytic (C₁/C₂ <100; δ¹³C–46 ± 3‰) origin. Some samples represent a gas mixture of thermocatalytic and microbial origin. This gas is characterized by δ¹³C of methane varying from–60 to–70‰ and contains a significant amount of ethane. The main homolog of methane in the thermocatalytic and mixed gas is ethane. Owing to biodegradation, propane and butanes are present in trace amounts.     

Effects of Deep Fluids on Hydrocarbon Generation and Accumulation in Chinese Petroliferous Basins

Deep fluids in a petroliferous basin generally come from the deep crust or mantle beneath the basin basement, and they transport deep substances(gases and aqueous solutions) as well as heat to sedimentary strata through deep faults. These deep fluids not only lead to large-scale accumulations of CO_2, CH_4, H_2, He and other gases, but also significantly impact hydrocarbon generation and accumulation through organic-inorganic interactions. With the development of deep faults and magmatic-volcanic activities in different periods, most Chinese petroliferous basins have experienced strong impacts associated with deep fluid activity. In the Songliao, Bohai Bay, Northern Jiangsu, Sanshui, Yinggehai and Pearl Mouth Basins in China, a series of CO_2 reservoirs have been discovered. The CO_2 content is up to 99%, with δ~(13)C_(CO2) values ranging from-4.1‰ to-0.37‰ and ~3He/~4He ratios of up to 5.5 Ra. The abiogenic hydrocarbon gas reservoirs with commercial reserves, such as the Changde, Wanjinta, Zhaozhou, and Chaoyanggou reservoirs, are mainly distributed in the Xujiaweizi faulted depression of the Songliao Basin. The δ~(13)CCH4 values of the abiogenic alkane gases are generally -30‰ and exhibit an inverse carbon isotope sequence of δ~(13)C_(CH4)δ~(13)C_(C2H6)δ~(13)C_(C3H8)δ~(13)C_(C4H10). According to laboratory experiments, introducing external H_2 can improve the rate of hydrocarbon generation by up to 147% through the kerogen hydrogenation process. During the migration from deep to shallow depth, CO_2 can significantly alter reservoir rocks. In clastic reservoirs, feldspar is easily altered by CO_2-rich fluids, leading to the formation of dawsonite, a typical mineral in high CO_2 partial pressure environments, as well as the creation of secondary porosity. In carbonate reservoirs, CO_2-rich fluids predominately cause dissolution or precipitation of carbonate minerals. The minerals, e.g., calcite and dolomite, show some typical features, such as higher homogenization temperatures than the burial temperature, relatively high concentrations of Fe and Mn, positive Eu anomalies, depletion of 18 O and enrichment of radiogenic ~(87)Sr. Due to CO_2-rich fluids, the development of high-quality carbonate reservoirs is extended to deep strata. For example, the Well TS1 in the northern Tarim Basin revealed a high-quality Cambrian dolomite reservoir with a porosity of 9.1% at 8408 m, and the Well ZS1 C in the central Tarim Basin revealed a large petroleum reserve in a Cambrian dolomite reservoir at ~6900 m. During the upward migration from deep to shallow basin strata, large volumes of supercritical CO_2 may extract petroleum components from hydrocarbon source rocks or deep reservoirs and facilitate their migration to shallow reservoirs, where the petroleum accumulates with the CO_2. Many reservoirs containing both supercritical CO_2 and petroleum have been discovered in the Songliao, Bohaiwan, Northern Jiangsu, Pearl River Mouth and Yinggehai Basins. The components of the petroleum trapped with CO_2 are dominated by low molecular weight saturated hydrocarbons.     

Geochemical characterization of secondary microbial gas occurrence in the Songliao Basin, NE China

A suite of natural gases from the northern Songliao Basin in NE China were characterized for their molecular and carbon isotopic composition. Gases from shallow reservoirs display clear geochemical evidence of alteration by biodegradation, with very high dryness (C₁/C₂₊ > 100), high C₂/C₃ and i-C₄/n-C₄ ratios, high nitrogen content and variable carbon dioxide content. Isotopic values show wide range variations (δ¹³C_CH4 from −79.5‰ to −45.0‰, δ¹³C_C2H6 from −53.7‰ to −32.2‰, δ¹³C_C3H8 from −36.5‰ to −20.1‰, δ¹³C_nC4H10 from −32.7‰ to −24.5‰, and δ¹³C_CO2 from −21.6‰ to +10.5‰). A variety of genetic types can be recognized on the basis of chemical and isotopic composition together with their geological occurrence. Secondary microbial gas generation was masked by primary microbial gas and the mixing of newly generated methane with thermogenic methane already in place in the reservoir can cause very complicated isotopic signatures. System openness also was considered for shallow biodegraded gas accumulations. Gases from the Daqing Anticline are relatively wet with ¹³C enriched methane and ¹³C depleted CO₂, representing typically thermogenic origin. Gases within the Longhupao-Da’an Terrace have variable dryness, ¹³C enriched methane and variable δ¹³C of CO₂, suggesting dominant thermogenic origin and minor secondary microbial methane augment. The Puqian-Ao’nan Uplift contains relatively dry gas with ¹³C depleted methane and ¹³C enriched CO₂, typical for secondary microbial gas with a minor part of thermogenic methane. Gas accumulations in the Western Slope are very dry with low carbon dioxide concentrations. Some gases contain ¹³C depleted methane, ethane and propane, indicating low maturity/primary microbial origin. Recognition of varying genetic gas types in the Songliao Basin helps explain the observed dominance of gas in the shallow reservoir and could serve as an analogue for other similar shallow gas systems.     

Characteristics of Hydrocarbon Fluid Inclusions and Their Significance for Evolution of Petroleum Systems in the Dabashan Foreland, Central China

Field investigation combined with detailed petrographic observation indicate that abundant oil,gas,and solid bitumen inclusions were entrapped in veins and cements of sedimentary rocks in the Dabashan foreland,which were used to reconstruct the oil and gas migration history in the context of tectonic evolution.Three stages of veins were recognized and related to the collision between the North China block and the Yangtze block during the Indosinian orogeny from Late Triassic to Early Jurassic(Dl),the southwest thrusting of the Qinling orogenic belt towards the Sichuan basin during the Yanshanian orogeny from Late Jurassic to Early Cretaceous(D2),and extensional tectonics during Late Cretaceous to Paleogene(D3),respectively.The occurrences of hydrocarbon inclusions in these veins and their homogenization temperatures suggest that oil was generated in the early stage of tectonic evolution,and gas was generated later,whereas solid bitumen was the result of pyrolysis of previously accumulated hydrocarbons.Three stages of hydrocarbon fluid inclusions were also identified in cements of carbonates and sandstones of gas beds in the Dabashan foreland belt and the Dabashan foreland depression(northeastern Sichuan basin),which recorded oil/gas formation,migration,accumulation and destruction of paleo-reservoirs during the D2.Isotopic analysis of hydrocarbon fluid inclusions contained in vein minerals shows that δ~(13)C_1 of gas in fluid inclusions ranges from-17.0‰ to-30.4‰(PDB) and δD from-107.7‰ to-156.7‰(SMOW),which indicates that the gas captured in the veins was migrated natural gas which may be correlated with gas from the gas-fields in northern Sichuan basin.Organic geochemical comparison between bitumen and potential source rocks indicates that the Lower Cambrian black shale and the Lower Permian black limestone were the most possible source rocks of the bitumen.Combined with tectonic evolution history of the Dabashan foreland,the results of this study suggest that oil was generated from the Paleozoic source rocks in the Dabashan area under normal burial thermal conditions before Indosinian tectonics and accumulated to form paleo-reservoirs during Indosinian collision between the North China block and the Yangtz block.The paleo-reservoirs were destroyed during the Yanshanian tectonic movement when the Dabashan foreland was formed.At the same time,oil in the paleo-reservoirs in the Dabashan foreland depression was pyrolyzed to transform to dry gas and the residues became solid bitumen.     

Geochemical comparison between gas in fluid inclusions and gas produced from the Upper Triassic Xujiahe Formation,Sichuan Basin,SW China

Natural gas in the Xujiahe Formation of the Sichuan Basin is dominated by hydrocarbon (HC) gas, with 78–79% methane and 2–19% C₂₊ HC. Its dryness coefficient (C₁/C_1–5) is mostly < 0.95. The gas in fluid inclusions, which has low contents of CH₄ and heavy hydrocarbons (C₂₊) and higher contents of non-hydrocarbons (e.g. CO₂), is a typical wet gas produced by thermal degradation of kerogen. Gas produced from the Upper Triassic Xujiahe Formation (here denoted field gas) has light carbon isotope values for methane (δ¹³C₁: −45‰ to −36‰) and heavier values for ethane (δ¹³C₂: −30‰ to −25‰). The case is similar for gas in fluid inclusions, but δ¹³C₁ = −36‰ to −45‰ and δ¹³C₂ = −24.8‰ to −28.1‰, suggesting that the gas experienced weak isotopic fractionation due to migration and water washing. The field gas has δ¹³C_CO2 values of −15.6‰ to −5.6‰, while the gas in fluid inclusions has δ¹³C_CO2 values of −16.6‰ to −9‰, indicating its organic origin. Geochemical comparison shows that CO₂ captured in fluid inclusions mainly originated from source rock organic matter, with little contribution from abiogenic CO₂. Fluid inclusions originate in a relatively closed system without fluid exchange with the outside following the gas capture process, so that there is no isotopic fractionation. They thus present the original state of gas generated from the source rocks. These research results can provide a theoretical basis for gas generation, evolution, migration and accumulation in the basin.     

Origin and depositional environments of source rocks and crude oils from Niger Delta Basin: Carbon isotopic evidence

Thirty-nine crude oils and twenty-one rock samples from Niger Delta Basin, Nigeria have been characterized based on their isotope compositions by elemental analysis-isotope ratio mass spectrometry and gas chromatography-isotope ratio mass spectrometry. The bulk carbon isotopic values of the whole rock extracts, saturate and aromatic fractions range from –28.7‰ to –26.8‰, –29.2‰ to –27.2 ‰ and –28.5 ‰ to –26.7 ‰, respectively while the bulk carbon isotopic values of the whole oils, saturate and aromatic fractions range from –25.4 ‰ to –27.8 ‰, –25.9 ‰ to –28.4 ‰ and –23.5 ‰ to –26.9 ‰, respectively. The average carbon isotopic compositions of individual alkanes (nC₁₂-nC₃₃) in the rock samples range from –34.9‰ to –28.2‰ whereas the average isotopic values of individual n-alkanes in the oils range from –31.1‰ to –23.8‰. The δ¹³C isotope ratios of pristane and phytane in the rock samples range from –29.2 ‰ to –28.2 ‰ and –30.2 ‰ to –27.4 ‰ respectively while the pristane and phytane isotopic values range from –32.1‰ to –21.9‰ and –30.5‰ to –26.9‰, respectively. The isotopic values recorded for the samples indicated that the crude oils were formed from the mixed input of terrigenous and marine organic matter and deposited under oxic to sub-oxic condition in lacustrine-fluvial/deltaic environments. The stable carbon isotopic compositions were found to be effective in assessing the origin and depositional environments of crude oils in the Niger Delta Basin.     

利用包裹体中气体地球化学特征与源岩生气模拟实验探讨鄂尔多斯盆地靖边气田天然气来源

鄂尔多斯盆地上、下古生界地层包裹体气体与气藏中气体地球化学性质对比表明:上古生界气藏中气体与包裹体中气体地球化学性质相似,气藏中气体的地球化学性质能代表成藏初期气体的原始特征;而下古生界气藏中气体与包裹体中气体的地球化学性质差别很大,下古生界气藏中的气体与下古生界源岩模拟生成气体也有非常大的差别。因此,下古生界气藏中的气体不能代表来自下古生界源岩产生天然气。结合前人关于奥陶系源岩的模拟生成天然气、包裹体中气体以及靖边气田天然气的地球化学特征,提出来源于奥陶系的天然气应具有δ¹³C₁<-38‰、δ¹³C₂<-28‰的特征。下古生界地层包裹体中气体与气藏中气体地球化学性质对比表明,下古生界气田天然气乙烷碳同位素的变化范围也比甲烷碳同位素的变化范围大很多,乙烷碳同位素不适合作为判断靖边气田天然气来源的标准。在此基础上,以上古生界天然气甲烷碳同位素的平均值(-32.90‰)与下古生界δ¹³C₁<-38‰天然气甲烷碳同位素的平均值(-39.04‰)分别作为上、下古生界来源天然气甲烷碳同位素的界限值,通过简单计算认为靖边气田大约85%的天然气来源于上古生界煤系。     

Stable carbon isotope compositions and source rock geochemistry of the giant gas accumulations in the Ordos Basin, China

Ordos Basin, the second largest sedimentary basin in China, contains enormous natural gas resources. Each of the four giant gas fields discovered so far in this basin (i.e., Sulige, Yulin, Wushenqi and Jingbian) has over 100 billion cubic meters (bcm) or 3.53 trillion cubic feet (tcf) of proven gas reserves. This study examines the stable carbon isotope data of 125 gas samples collected from the four giant gas fields in the Ordos Basin. Source rocks in the Upper Paleozoic coal measures are suggested by the generally high δ¹³C values of C₁–C₄ gaseous hydrocarbons in the gases from the Sulige, Yulin and Wushenqi gas fields. While the δ¹³C_iC4 value is higher than that of the δ¹³C_nC4, the dominant ranges for the δ¹³C₁, δ¹³C₂, and δ¹³C₃ values in these Upper Paleozoic reservoired gases are −34 to −32‰, −27 to −23‰, and −25 to −24‰, respectively. The δ¹³C values of methane, benzene and toluene in gases from the Lower Paleozoic reservoirs of the Jingbian field indicate a significant contribution from humic source rocks, as they are similar to those in the Upper Paleozoic reservoirs of the Sulige, Yulin and Wushenqi gas fields. However, the wide variation and reversal in the δ¹³C₁, δ¹³C₂ and δ¹³C₃ values in the Jinbian gases cannot be explained using a single source scenario, thus the gases were likely derived dominantly from the Carboniferous-Permian coal measures with some contribution from the carbonates in the Lower Permian Taiyuan Formation. The gas isotope data and extremely low total organic carbon contents (<0.2% TOC) suggest that the Ordovician Majiagou Formation carbonates are unlikely to be a significant gas source rock, thus almost all of the economic gas accumulations in the Ordos Basin were derived from Upper Paleozoic source rocks.     

Geochemical Characteristics of the Upper Triassic Xujiahe Formation in Sichuan Basin, China and its Significance for Hydrocarbon Accumulation

The alternative development of coal-bearing hydrocarbon source rocks and low-porosity and low-permeability tight sandstone reservoirs of the Triassic Xujiahe Formation in the Sichuan Basin is favorable for near-source hydrocarbon accumulation. The natural gas composition of the Xujiahe Formation in the Sichuan Basin is dominated by hydrocarbon gases, of which the methane content is80.16%-98.67%. Typically, the C_2~+ content is larger than 5% in main wet gas. The dry gas is mainly distributed in the western and northern regions of the basin. The non-hydrocarbon gases mainly contain nitrogen, carbon dioxide, hydrogen, and helium, with a total content of 2%. The carbon isotope ranges of methane and its homologues in natural gas are: δ~(13)C_1 of-43.8‰ to-29.6‰, δ~(13)C_2 of-35.4‰ to-21.5‰, δ~(13)C_3 of-27.6‰ to-19.8‰,and δ~(13)C_4 of-27.7‰ to-18.8‰. δ~(13)C_3δ~(13)C_4 occurs in some natural gas with a low evolution degree; such gas is mainly coal-related gas from humic-type source rocks of the Xujiahe Formation. As for the natural gas, δ~2 H_(CH4) values ranged from-195‰ to-161‰,δ~2 H_(C2H6) values ranged from-154‰ to-120‰, and δ~2 H_(C3H8) values ranged from-151‰ to-108‰. The dry coefficient,δ~(13)C and δ~2 H_(CH4) are all positively correlated with the maturity of source rocks. The higher the maturity of source rocks is, the larger the natural gas dry coefficient is and the larger the δ~(13)C and δ~2 H_(CH_4) values are, indicative of the characteristic of near-source accumulation. The δ~2 H_(C2H6) value of natural gas is influenced by paleosalinity to a relatively large extent; the higher the paleosalinity is, the larger the δ~2 H_(C2H6) value is. The Pr/Ph value of the condensate oil ranged from 1.60 to 3.43, illustrating light oxidization-light reduction and partial-oxidization characteristics of the depositional environment of coal-bearing source rocks of the Xujiahe Formation. The natural gas light hydrocarbon(C_5-C_7) from the Xujiahe Formation presented two characteristics: the first was the relatively high aromatic hydrocarbon content(19%-32.1%), which reveals the characteristic of natural gas with humic substances of high-maturity; the second was the low content of aromatic hydrocarbon(0.4%-9.3%),reflecting water-washing during the accumulation of the natural gas. The reported research outcomes indicate a potential mechanism for natural gas accumulation in the Xujiahe Formation, which will further guide natural gas exploration in this region.     

Microbial hydrocarbon gases in the Witwatersrand Basin, South Africa: Implications for the deep biosphere

In this study, compositions and δ¹³C and δ²H isotopic values of hydrocarbon gases from 5 mines in the Witwatersrand basin, South Africa, support the widespread occurrence of microbially produced methane in millions of years-old fissure waters. The presence of microbial methane is, to a large extent, controlled by the geologic formations in which the gases are found. Samples from the Witwatersand Supergroup have the largest microbial component based on δ¹³C and δ²H signatures and CH₄/C₂+ values. Based on mixing between a microbial CH₄ component and a more ¹³C-enriched and ²H-depleted C₂+-rich end member, conservative estimates of the % contribution of microbial CH₄ to the gas samples range from >90% microbial CH₄ at Beatrix, Masimong, and Merriespruit, to between 5 and 80% microbial CH₄ at Evander, and <18% microbial CH₄ at Kloof. The Witwatersrand basin’s history of thermal alteration of organic-rich ancient sedimentary units suggests a thermogenic origin for this ¹³C-enriched end member. Alternatively, the potential for an abiogenic origin similar to hydrocarbon gases produced by water-rock interaction at other Precambrian Shield mines is discussed. Microbial methane is predominantly found in paleo-meteoric fissure waters with δ¹⁸O and δ²H values that fall on the meteoric waterline, and have temperatures between 30 to 40°C. In contrast, fissure waters with a larger component of nonmicrobial hydrocarbon gases show a trend towards more enriched δ¹⁸O and δ²H values that fall well above the meteoric waterline, and temperatures of 45 to 60°C. The enrichment in ¹⁸O and ²H in these samples, and their high salinity, are similar to the isotopic and compositional characteristics of saline groundwaters and brines produced by water-rock interaction at Precambrian Shield sites elsewhere. The reported 100 Ma ages of fissure waters from the Witwatersrand and Ventersdorp formations suggest that these microbial hydrocarbon gases are the product of in situ methanogenic communities in the deep subsurface of the Witswaterand basin. Small subunit ribosomal RNA genes were amplified using archaeal-specific primer sets from DNA extracts derived from several of these waters. Fissure waters with a high proportion of microbial methane also contained sequences resembling those of known methanogens.     

Carbon isotopes of Middle–Lower Jurassic coal-derived alkane gases from the major basins of northwestern China

Coal-derived hydrocarbons from Middle–Lower Jurassic coal-bearing strata in northwestern China are distributed in the Tarim, Junggar, Qaidam, and Turpan-Harmi basins. The former three basins are dominated by coal-derived gas fields, distributed in Cretaceous and Tertiary strata. Turpan-Harmi basin is characterized by coal-derived oil fields which occur in the coal measures. Based on analysis of gas components and carbon isotopic compositions from these basins, three conclusions are drawn in this contribution: 1) Alkane gases with reservoirs of coal measures have no carbon isotopic reversal, whereas alkane gases with reservoirs not of coal measures the extent of carbon isotopic reversal increases with increasing maturity; 2) Coal-derived alkane gases with high δ¹³C values are found in the Tarim and Qaidam basins (δ¹³C₁: − 19.0 to − 29.9‰; δ¹³C₂: − 18.8 to − 27.1‰), and those with lowest δ¹³C values occur in the Turpan-Harmi and Junggar basins (δ¹³C₁: − 40.1 to − 44.0‰; δ¹³C₂: − 24.7 to − 27.9‰); and 3) Individual specific carbon isotopic compositions of light hydrocarbons (C_5–8) in the coal-derived gases are lower than those in the oil-associated gases. The discovered carbon isotopic reversal of coal-derived gases is caused by isotopic fractionation during migration and secondary alteration. The high and low carbon isotopic values of coal-derived gases in China may have some significance on global natural gas research, especially the low carbon isotope value of methane may provide some information for early thermogenic gases. Coal-derived methane typically has much heavier δ¹³C than that of oil-associated methane, and this can be used for gas–source rock correlation. The heavy carbon isotope of coal-derived ethane is a common phenomenon in China and it shed lights on the discrimination of gas origin. Since most giant gas fields are of coal-derived origin, comparative studies on coal-derived and oil-associated gases have great significance on future natural gas exploration in the world.     

The carbon isotopic composition of catalytic gas: a comparative analysis with natural gas

The idea that natural gas is the thermal product of organic decomposition has persisted for over half a century. Crude oil is thought to be an important source of gas, cracking to wet gas above 150°C, and dry gas above 200°C. But there is little evidence to support this view. For example, crude oil is proving to be more stable than previously thought and projected to remain intact over geologic time at typical reservoir temperatures. Moreover, when oil does crack, the products do not resemble natural gas. Oil to gas could be catalytic, however, promoted by the transition metals in carbonaceous sediments. This would explain the low temperatures at which natural gas forms, and the high amounts of methane. This idea gained support recently when the natural progression of oil to dry gas was duplicated in the laboratory catalytically. We report here the isotopic composition of catalytic gas generated from crude oil and pure hydrocarbons between 150 and 200°C. δ¹³C for C₁ through C₅ was linear with 1/n (n = carbon number) in accordance with theory and typically seen in natural gases. Over extended reaction, isobutane and isopentane remained lighter than their respective normal isomers and the isotopic differentials were constant as all isomers became heavier over time. Catalytic methane, initially −51.87‰ (oil = −22.5‰), progressed to a final composition of −26.94‰, similar to the maturity trend seen in natural gases: −50‰ to −20‰. Catalytic gas is thus identical to natural gas in molecular and isotopic composition adding further support to the view that catalysis by transition metals may be a significant source of natural gas.     

Geochemical and isotopic approach to maturity/source/mixing estimations for natural gas and associated condensates in the Thrace Basin,NW Turkey

The Tertiary Thrace Basin located in NW Turkey comprises 9 km of clastic-sedimentary column ranging in age from Early Eocene to Recent in age. Fifteen natural gas and 10 associated condensate samples collected from the 11 different gas fields along the NW–SE extending zone of the northern portion of the basin were evaluated on the basis of their chemical and individual C isotopic compositions. For the purpose of the study, the genesis of CH₄, thermogenic C₂₊ gases, and associated condensates were evaluated separately.Methane appears to have 3 origins: Group-1 CH₄ is bacteriogenic (Calculated δ¹³C_C1–C = −61.48‰; Silivri Field) and found in Oligocene reservoirs and mixed with the thermogenic Group-2 CH₄. They probably formed in the Upper Oligocene coal and shales deposited in a marshy-swamp environment of fluvio-deltaic settings. Group-2 (δ¹³C_C1–C = −35.80‰; Hamitabat Field) and Group-3 (δ¹³C_1–C = −49.10‰; Değirmenköy Field) methanes are thermogenic and share the same origin with the Group-2 and Group-3 C₂₊ gases. The Group-2 C₂₊ gases include 63% of the gas fields. They are produced from both Eocene (overwhelmingly) and Oligocene reservoirs. These gases were almost certainly generated from isotopically heavy terrestrial kerogen (δ¹³C = −21‰) present in the Eocene deltaic Hamitabat shales. The Group-3 C₂₊ gases, produced from one field, were generated from isotopically light marine kerogen (δ¹³C = −29‰). Lower Oligoce ne Mezardere shales deposited in pro-deltaic settings are believed to be the source of these gases.The bulk and individual n-alkane isotopic relationships between the rock extracts, gases, condensates and oils from the basin differentiated two Groups of condensates, which can be genetically linked to the Group-2 and -3 thermogenic C₂₊ gases. However, it is crucial to note that condensates do not necessarily correlate to their associated gases.Maturity assessments on the Group-1 and -2 thermogenic gases based on their estimated initial kerogen isotope values (δ¹³C = −21‰; −29‰) and on the biomarkers present in the associated condensates reveal that all the hydrocarbons including gases, condensates and oils are the products of primary cracking at the early mature st age (R_eq = 0.55–0.81%). It is demonstrated that the open-system source conditions required for such an early-mature hydrocarbon expulsion exist and are supported by fault systems of the basin.     

Stable carbon isotope geochemistry of adsorbed alkane gases in near-surface soils of the Saurashtra Basin,India

The stable carbon isotopic compositions of light hydrocarbon gases adsorbed in near-surface soil and sediments from the Saurashtra basin were characterized for their origin and maturity. Saurashtra is considered geologically prospective for oil and gas reserves; however, a major part of the basin is covered by the Deccan Traps, hindering the exploration of Mesozoic hydrocarbon targets. Surface geochemical prospecting, based on micro-seepage of hydrocarbons from subsurface accumulations, could be advantageous in such areas. In light of this, 150 soil samples were collected from the northwestern part of Saurashtra, around the Jamnagar area, where a thick sedimentary sequence of about 2–3 km exists under 1–1.5 km of Deccan basalt. The concentration of acid desorbed alkane gases from soil samples was found to vary (in ppb) as: methane (C₁) = 3–518; ethane (C₂) = 0–430; propane (C₃) = 0–331; i-butane (iC₄) = 0–297; n-butane (nC₄) = 2–116; i-pentane (iC₅) = 0–31 and n-pentane (nC₅) = 0–23, respectively.Fifteen samples with high concentrations of alkane gases were measured for their δ¹³C₁; δ¹³C₂ and δ¹³C₃ compositions using gas chromatography–combustion-isotope ratio mass spectrometry (GC–C-IRMS). The values for methane varied from ? 27 to ? 45.4‰, ethane from ? 20.9 to ? 27.6‰, and propane from ? 20.4 to ? 29.1‰ versus the Vienna PeeDee Belemnite (VPDB). The carbon isotope ratio distribution pattern represents isotopic characteristics pertaining to hydrocarbon gases derived from thermogenic sources. Comparisons of carbon isotopic signatures and compositional variations with the standard carbon isotopic models suggest that hydrocarbon gases found in the shallow depths of the study area are not of bacterial origin but are formed thermally from deeply buried organic matter, likely to be mainly a terrestrial source rock with a partial contribution from a marine source. These gases may have migrated to the near-surface environment, where they represent an admixture of thermally generated hydrocarbon gases from mixed sources and maturity. The maturity scale (δ¹³C versus Log Ro %) applied to the surface sediment samples of the Jamnagar area indicated the source material to be capable of generating oil and gas. The detection of thermogenic alkane gases in near-surface sediments offers the possibility of hydrocarbons at depth in Saurashtra.     

Geological and Geochemical Characteristics and Exploration Prospect of Coal‐Derived Tight Sandstone Gas in China: Case Study of the Ordos,Sichuan, and Tarim Basins

This work extensively investigated global tight sandstone gas, and geologically and geochemically analyzed the tight sandstone gas in China's Ordos, Sichuan, and Tarim basins. We compared typical tight sandstone gas in China with that in North America. We proposed six conditions for the formation of China's tight sandstone gas, and illustrated the geological characteristics of tight sandstone gas. In China, gas-bearing tight sandstones were mainly deposited in continental lake deltas and marine-terrigenous facies basin environments, associated with coal-measure strata, and were mostly buried deeper than 2000 m under a formation pressure of 20–30 MPa, with pressure coefficients varying from overpressure to negative pressure. In other countries, tight gas bearing sandstones were dominantly deposited in marine to marine-terrigenous facies environments, occurred in coal-measure strata, and were mostly buried shallower than 2000 m in low-pressure systems. We systematically analyzed tight sandstone gas in the Ordos, Sichuan, and Tarim basins in terms of chemical compositions, geochemical characteristics of carbon isotopes, origins, and sources. Tight sandstone gas in China usually has a hydrocarbon content of 95%, with CH4 content 90%, and a generally higher dry coefficient. In the three above-mentioned large tight sandstone gas regions, δ13 C1 and δ13 C2 mainly ranges from-42‰ to-28‰ and from-28‰ to-21‰, respectively. Type III coal-measure source rocks that closely coexist with tight reservoirs are developed extensively in these gas regions. The organic petrology of source rocks and the carbon isotope compositions of gas indicate that tight sandstone gas in China is dominantly coal-derived gas generated by coal-measure strata. Our analysis of carbon isotope series shows that local isotope reversals are mainly caused by the mixing of gases of different maturities and that were generated at different stages. With increasing maturity, the reversal tendency becomes more apparent. Moreover, natural gas with medium-low maturity(e.g., Xujiahe Formation natural gas in the Sichuan Basin) presents an apparent reversal at a low-maturity stage, a normal series at a medium-maturity stage, and a reversal tendency again at a high-maturity stage. Finally, we proposed four conditions for preferred tight sandstone gas "sweep spots," and illustrated the recoverable reserves, proven reserves, production, and exploration prospects of tight sandstone gas. The geological and geochemical characteristics, origins, sources, and exploration potential of tight sandstone gas in China from our research will be instructive for the future evaluation, prediction, and exploration of tight sandstone gas in China and abroad.     

Origin of Paleofluids in Dabashan Foreland Thrust Belt:Geochemical Evidence of 13C,18O and 87Sr/86Sr in Veins and Host Rocks

In the last ten years, with important discoveries from oil and gas exploration in the Dabashan foreland depression belt in the borderland between Shanxi and Sichuan provinces, the relationship between the formation and evolution of, and hydrocarbon accumulation in, this foreland thrust belt from the viewpoint of basin and oil and gas exploration has been studied. At the same time, there has been little research on the origin of fluids within the belt. Based on geochemical system analysis including Z values denoting salinity and research on δ13C, δ18O and 87Sr/86Sr isotopes in the host rocks and veins, the origin of paleofluids in the foreland thrust belt is considered. There are four principal kinds of paleofluid, including deep mantle-derived, sedimentary, mixed and meteoric. For the deep mantle-derived fluid, the δ13C is generally less than ?5.0‰PDB, δ18O less than -10.0‰PDB, Z value less than 110 and 87Sr/86Sr less than 0.70600; the sedimentary fluid is mainly marine carbonate-derived, with the δ13C generally more than ?2.0‰PDB, δ18O less than ?10.0‰PDB, Z value more than 120 and 87Sr/86Sr ranging from 0.70800 to 0.71000; the mixed fluid consists mainly of marine carbonate fluid (including possibly a little mantle-derived fluid or meteoric water), with the δ13C generally ranging from ?2.0‰ to ?8.0‰PDB, δ18O from ?10.0‰ to ?18.0‰ PDB, Z value from 105 to 120 and 87Sr/86Sr from 0.70800 to 0.71000; the atmospheric fluid consists mainly of meteoric water, with the δ13C generally ranging from 0.0‰ to ?10.0‰PDB, δ18O less than ?8.0‰PDB, Z value less than 110 and 87Sr/86Sr more than 0.71000. The Chengkou fault belt encompasses the most complex origins, including all four types of paleofluid; the Zhenba and Pingba fault belts and stable areas contain a simple paleofluid mainly of sedimentary type; the Jimingsi fault belt contains mainly sedimentary and mixed fluids, both consisting of sedimentary fluid and meteoric water. Jurassic rocks of the foreland depression belt contain mainly meteoric fluid.