Origin of the Gas Hydrate and Free Gas in the Qilian Permafrost,Northwest China:Evidence from Molecular Composition and Carbon Isotopes

The Qilian permafrost of the South Qilian Basin(SQB)has become a research focus since gas hydrates were discovered in 2009.Although many works from different perspectives have been conducted in this area,the origin of gas from gas hydrate is still controversial.Molecular composition and carbon isotope of 190 samples related to gas hydrates collected from 11 boreholes allowed exploration of genetic type,thermal maturity,biodegradation,as well as gas-source correlation of alkane gases from gas hydrates and free gases.Results indicate that alkane gases biodegraded after the formation of natural gas.According to differences in carbon isotopes of methane and their congeners(CH4,C2H6,C3H8),the thermal maturity(vitrinite reflectance,VRo)of most alkane gases ranges from 0.6%to 1.5%,indicating a mature to high mature stage.The thermal maturity VRo of a small part of alkane gas(in boreholes DK5 and DK6)is higher than 1.3%,indicating a high mature stage.Alkane gases were mainly produced by secondary cracking,consisting of crude oilcracking gases and wet gases cracking to dry gases.Genetic types of alkane gases are primarily oil-type gases generated from shales and mudstones in the upper Yaojie Formation of Jurassic,with less coal-type gases originated from the mudstones in the Triassic Galedesi Formation and the lower Yaojie Formation of Jurassic.Carbon dioxides associated with alkanes from gas hydrates and free gases indicate the thermal decomposition and biodegradation of organic matter.The origins of natural gases from gas hydrates and free gases shed light on the evaluation of petroleum resource potential,deeply buried sediments,and petroleum resource exploration in the SQB.

Fluid Inclusion and Carbon-Oxygen Isotope Studies of the Hujiayu Cu Deposit,Zhongtiao Mountains,China:Implications for Synmetamorphic Copper Remobilization

The Hujiayu Cu deposit,representative of the ＂HuBi-type＂ Cu deposits in the Zhongtiao Mountains district in the southern edge of the North China Craton,is primarily hosted in graphitebearing schists and carbonate rocks.The ore minerals comprise mainly chalcopyrite,with minor sphalerite,siegenite[（Co,Ni）_3S_4],and clausthalite[Pb（S,Se）].The gangue minerals are mainly quartz and dolomite,with minor albite.Four fluid inclusion types were recognized in the chalcopyrite-pyrite-dolomite-quartz veins,including CO_2-rich inclusions（type Ⅰ）,low-salinity,liquid-dominated,biphase aqueous inclusions（type Ⅱ）,solid-bearing aqueous inclusions（type Ⅲ）,and solid-bearing aqueous-carbonic inclusions（type Ⅳ）.Type I inclusion can be further divided into two sub-types,i.e.,monophase CO_2 inclusions（type Ⅰa） and biphase CO_2-rich inclusions（with a visible aqueous phase）,and type Ⅲ inclusion is divided into a subtype with a halite daughter mineral（type Ⅲa） and a subtype with multiple solids（type Ⅲb）.Various fluid inclusion assemblages（FIAs） were identified through petrographic observations,and were classified into four groups.The group-1 FIA,consisting of monophase CO_2 inclusions（type Ⅰa）,homogenized into the liquid phase in a large range of temperatures from-1 to 28℃,suggesting post-entrapment modification.The group-2 FIA consists of type Ⅰb,Ⅲb and Ⅳ inclusions,and is interpreted to reflect fluid immiscibility.The group-3 FIA comprises type Ⅱ and Ⅲa inclusions,and the group-4FIA consists of type Ⅱ inclusions with consistent phase ratios.The group-1 and group-2 FIAs are interpreted to be entrapped during mineralization,whereas group-3 and group-4 FIAs probably represent the post-mineralization fluids.The solid CO_2 melting temperatures range from-60.6 to56.6℃ and from-66.0 to-63.4℃ for type Ⅰa and type Ⅳ inclusions,respectively.The homogenization temperatures for type Ⅱ inclusions range from 132 to 170℃ for group-3 FIAs and115 to 219℃ for group-4 FIAs.The halite melting temperatures range from 530 to 562℃ for typeⅢ b and Ⅳ inclusions,whereas those for type Ⅲa inclusions range from 198 to 398℃.Laser Raman and SEM-EDS results show that the gas species in fluid inclusions are mainly CO_2 with minor CH_4,and the solids are dominated by calcite and halite.The calcite in the hosting marble and dolomite in the hydrothermal veins have δ^（13）C_（V-pdb） values of-0.2 to 1.2‰ and-1.2 to-6.3‰,and δ^（18）O_（v-smow） values of 14.0 to 20.8 ‰ and 13.2 to 14.3‰,respectively.The fluid inclusion and carbon-oxygen isotope data suggest that the ore-forming fluids were probably derived from metamorphic fluids,which had reacted with organic matter in sedimentary rocks or graphite and undergone phase separation at 1.4-1.8 kbar and 230-240℃,after peak metamorphism.It is proposed that the Hujiayu Cu deposit consists of two mineralization stages.The early stage mineralization,characterized by disseminated and veinlet copper sulfides,probably took place in an environment similar to sediment-hosted stratiform copper mineralization.Ore minerals formed in this precursor mineralization stage were remobilized and enriched in the late metamorphic hydrothermal stage,leading to the formation of thick quartz-dolomite-sulfides veins.

Characteristics of carbon isotopic composition of alkane gas in large gas fields in China

Exploration and development of large gas fields is an important way for a country to rapidly develop its natural gas industry.From 1991 to 2020,China discovered 68 new large gas fields,boosting its annual gas output to 1925×108m3in 2020,making it the fourth largest gas-producing country in the world.Based on 1696 molecular components and carbon isotopic composition data of alkane gas in 70 large gas fields in China,the characteristics of carbon isotopic composition of alkane gas in large gas fields in China were obtained.The lightest and average values ofδ^(13)C_(1),δ13C2,δ13C3andδ13C4become heavier with increasing carbon number,while the heaviest values ofδ^(13)C_(1),δ13C2,δ13C3andδ13C4become lighter with increasing carbon number.Theδ^(13)C_(1)values of large gas fields in China range from-71.2‰to-11.4‰(specifically,from-71.2‰to-56.4‰for bacterial gas,from-54.4‰to-21.6‰for oil-related gas,from-49.3‰to-18.9‰for coal-derived gas,and from-35.6‰to-11.4‰for abiogenic gas).Based on these data,theδ^(13)C_(1)chart of large gas fields in China was plotted.Moreover,theδ^(13)C_(1)values of natural gas in China range from-107.1‰to-8.9‰,specifically,from-1071%o to-55.1‰for bacterial gas,from-54.4‰to-21.6‰for oil-related gas,from-49.3‰to-13.3‰for coal-derived gas,and from-36.2‰to-8.9‰for abiogenic gas.Based on these data,theδ^(13)C_(1)chart of natural gas in China was plotted.

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 Tengchong magmatic component. Compared with MORB, this relative low 3He/4He ratio could be fully attributed to either deep crustal contamination, or radioactive aging, or past contamination of the local mantle by U- and Th-rich subducted crustal material. However, a combination of low 3He/4He, high radiogenic 4He/40Ar ratio and identical CO2/3He and δ13Cco2 relative to MORB may suggest addition of prior subductedd crsustal material (ca 1 %-2%) to the MORB reservoir around 1.3 Ga ago, which is essentially compatible with the LIL-elements, and Sr-Nd-Pb isotopes of volcanic rocks.

A Study of the Migration and Accumulation Efficiency and the Genesis of Hydrocarbon Natural Gas in the Xujiaweizi Fault Depression

In order to investigate the migration and accumulation efficiency of hydrocarbon natural gas in the Xujiaweizi fault depression, and to provide new evidence for the classification of its genesis, a source rock pyrolysis experiment in a closed system was designed and carried out. Based on this, kinetic models for describing gas generation from organic matter and carbon isotope fractionation during this process were established, calibrated and then extrapolated to geologic conditions by combining the thermal history data of the Xushen-1 Well. The results indicate that the coal measures in the Xujiaweizi fault depression are typical ＂high-efficiency gas sources＂, the natural gas generated from them has a high migration and accumulation efficiency, and consequently a large-scale natural gas accumulation occurred in the area. The highly/over matured coal measures in the Xujiaweizi fault depression generate coaliferous gas with a high δ^13C1 value （〉 -20‰） at the late stage, making the carbon isotope composition of organic alkane gases abnormally heavy. In addition, the mixing and dissipation through the caprock of natural gas can result in the negative carbon isotope sequence （δ^13C1 〉δ^13C2 〉δ^13C3 〉δ^13C4） of organic alkane gases, and the dissipation can also lead to the abnormally heavy carbon isotope composition of organic alkane gases. As for the discovery of inorganic nonhydrocarbon gas reservoirs, it can only serve as an accessorial evidence rather than a direct evidence that the hydrocarbon gas is inorganic. As a result, it needs stronger evidence to classify the hydrocarbon natural gas in the Xujiaweizi fault depression as inorganic gas.

Carbon and oxygen isotope characteristics of foraminiferan from northern South China Sea sediments and their significance to late Quaternary hydrate decomposition

Carbon and oxygen isotope and dating analyses of foraminiferan in sediment cores collected from three different areas of the northern slope of the South China Sea were conducted, in order to examine the records of the gas hydrate decomposition events since the late Quaternary under the conditions of methane seepage. The results show that： 1） the δ13C values of the benthic foraminiferan Uvigerina spp. （size range of 0.25-0.35 ram） are from -0.212% to -0.021% and the δ180 values of the planktonic foraminiferan Globigerinoides ruber （size range of 0.25-0.35 ram） are from -0.311% to -0.060%; 2） three cores （ZD2, ZD3 and ZS5） from the bottom of a hole are aged for 11 814, 26 616 and 64 090 a corresponding to the early oxygen isotope stage （MIS） Ⅰ, Ⅲ and Ⅳ final period, respectively; 3） a negative-skewed layer of carbon isotope corresponds to that of MIS II （cold period）, whose degree of negative bias is -0.2%0; and 4） the δ13C compositions of foraminiferans are similar to those of the Blake Ridge and the Gulf of Mexico sediments of the late Quaternary. According to the analysis, the reasons for these results are that the studied area is a typical area of methane seep environment in the area during MIS II due to the global sea-level fall and sea pressure decrease. Gas hydrate is decomposed and released, and a large number of light carbon isotopes of methane are released into the ocean, dissolved to inorganic carbon （DIC） pool and recorded in the foraminiferan shells. A pyrite layer developed in the negative bias layers of the foraminiferans confirms that the δ13C of foraminiferans is more affected by methane and less by the reduction of marine productivity and early diagenesis. The use of foraminiferan δ13C could accurately determine late Quaternary hydrate release events and provide evidence for both reconstructing the geological history of methane release events and exploring natural gas hydrate.

Re-Examination of the Oil and Gas Origins in the Kekeya Gas Condensate Field,Northwest China——A Case Study of Hydrocarbon-Source Correlation Using Sophisticated Geochemical Methods

This work discussed the origins, alteration and accumulation processes of the oil and gas in the Kekeya gas condensate field based on molecular compositions, stable carbon isotopes, light hydrocarbons, diamondoid hydrocarbons and biomarker fingerprints. A comparison study is also made between the geochemical characteristics of the Kekeya hydrocarbons and typical marine and terrigenous hydrocarbons of the Tarim Basin. Natural gas from the Kekeya gas condensate field is derived from Middle–Lower Jurassic coal measures while the condensates are derived from Carboniferous–Permian marine source rocks with a higher maturity. In the study area, both natural gas and condensates have experienced severe water washing. A large amount of methane was dissolved into the water, resulting in a decrease in the dryness coefficient. Water washing also makes the carbon isotopic compositions of the natural gas more negative and partially reverse. Considering that the gas maturities are higher than once expected, gas generation intensity in the study area should be much stronger and the gas related to the Jurassic coal measures could promise a greater prospecting potential. As a result of evaporative fractionation, the Kekeya condensates are enriched in saturates and lack aromatics. Evaporative fractionation disguises the original terrigenous characteristics of the light hydrocarbons associated with the natural gas, making it appear marinesourced. Thus, alteration processes should be fully taken into consideration when gas–source correlations are carried out based on light hydrocarbons. With the condensates discovered in the study area all being ＂migration phase＂, the pre-salt Cretaceous and Jurassic reservoirs may promise great exploration potential for the ＂residual phase＂ hydrocarbons. This research not only is of significance for oil and gas exploration in the southwest Tarim Basin, but also sheds light on the oil/gas-source correlations in general.

Comparative Study of Hydrogen and Carbon Isotopic Composition of Gases Generated from the Pyrolysis of a Peat under Saltwater and Freshwater Conditions

To understand the influence of the diagenetic water medium on the isotopic compositions of thermogenic coalbed gas, both hydrous and anhydrous closed-system pyrolyses were performed at temperatures of 250°C to 650°C on an herbaceous marsh peat. Compared to the results of anhydrous pyrolysis, the hydrocarbon gases generated from hydrous pyrolyses have very different hydrogen isotopic compositions. However, the carbon isotopic compositions of the hydrocarbon gases became only slightly heavier in hydrous pyrolysis, compared to that from anhydrous pyrolysis. With the progress of thermal evolution from peat to a more advanced thermal maturity of vitrinite reflectance values（Ro） of 5.5% during the pyrolysis, the difference in the average δD value increased from 52‰ to 64‰ between the hydrous pyrolysis with saltwater and anhydrous pyrolysis and increased from 18‰ to 29‰ between the hydrous pyrolysis with freshwater and anhydrous pyrolysis, respectively. The difference in the average δ^（13）C value was only 1‰–2‰ between the hydrous and anhydrous pyrolysis. The relationships between the δD values of the generated hydrocarbon gases and Ro values as well as among δD values of the hydrocarbon gas species are established. The close relationships among these parameters suggest that the water medium had a significant effect on the hydrogen isotopic composition and a minimal effect on the carbon isotopic composition of the hydrocarbon gases. The results of these pyrolyses may provide information for the understanding of the genesis of coalbed gas from herbaceous marsh material with the participation of different diagenetic water media.

Acidolysis hydrocarbon characteristics and significance of sediment samples from the ODP drilling legs of gas hydrate

To study on the significance and basis of acidolysis index to China marine gas hydrate exploring, since 2006, 111 samples derived from Leg 164 and 204 of the Ocean Drilling Program （ODP） were analyzed in the experiment center of China Petroleum Exploration Research Institute to obtain data on acidolysis hydrocarbon index and methane carbon isotopes by the gas chromatography （GC） of PE AutoSystem XL and isotope mass spectrometer （IRMS） of Finnigan MAT25 I. Through these, we study the reliability of the acidolysis method and characterize the gas hydrate potential. The results show that the acidolysis hydrocarbon index has a stable correspondence with the Gas Hydrate Stability Zone （GHSZ） in the ODE and that there are clear abnormal signs in shallow samples that might reliably reflect the existence of authigenic carbonate caused by hydrocarbon migration from bottom hydrate. We therefore propose that the ability to characterize the acidolysis hydrocarbon is crucial to submarine gas hydrate exploration in China.

Genesis of Marine Carbonate Natural Gas in the Northeastern Sichuan Basin,China

Sichuan Basin is one of the structurally stable and gas-rich basins, being regarded as one of China＇s important natural gas industry bases. Puguang and Jiannan gas fields, located in the eastern Sichuan Basin are two large fields with gas derived from Permian and Lower Triassic marine carbonate. The genesis of marine carbonate natural gas was examined using carbon isotope composition and hydrocarbon components of natural gas samples from the eastern and western Sichuan Basin, and compared with that of acidolysis gas derived from marine source rock in the eastern Sichuan Basin. It is concluded that the natural gas in the marine carbonate reservoir originated from pyrolysis of the earlier crude oil and light-oil, and then mixed with kerogen pyrolysis gas of the Permian and Lower Silurian source rock.

Mechanisms of carbon isotopic fractionation in the process of natural gas generation: Geochemical evidence from thermal simulation experiment

Low maturity coal samples were taken from the Ordos Basin to conduct gold tube thermal simulation experiment in a closed system,and the characteristics of the products were analyzed to find out the fractionation mechanism of carbon isotopes and the causes of abnormal carbon isotopic compositions of natural gas.At the heating rates of 2℃/h(slow)and 20℃/h(rapid),the low maturity coal samples of the Ordos Basin had the maximum yields of alkane gas of 302.74 mL/g and 230.16 mL/g,theδ13C1 ranges of-34.8‰to-23.6‰and-35.5‰to-24.0‰;δ13C2 ranges of-28.0‰to-9.0‰and-28.9‰to-8.3‰;andδ13C3 ranges of-25.8‰to-14.7‰and-26.4‰to-13.2‰,respectively.Alkane gas in the thermal simulation products of rapid temperature rise process showed obvious partial reversal of carbon isotope series at 550℃,and at other temperatures showed positive carbon isotope series.In the two heating processes,theδ13C1 turned lighter first and then heavier,and the non-monotonic variation of theδ13C1 values is because the early CH4 is from different parent materials resulted from heterogeneity of organic matter or the carbon isotope fractionation formed by activation energy difference of early enriched 12CH4 and late enriched 13CH4.The reversal of carbon isotope values of heavy hydrocarbon gas can occur not only in high to over mature shale gas(oil-type gas),but also in coal-derived gas.Through thermal simulation experiment of toluene,it is confirmed that the carbon isotope value of heavy hydrocarbon gas can be reversed and inversed at high to over mature stage.The isotope fractionation effect caused by demethylation and methyl linkage of aromatic hydrocarbons may be an important reason for carbon isotope inversion and reversal of alkane gas at the high to over mature stage.

Fluid Inclusions of Calcite and Sources of Ore-forming Fluids in the Huize Zn-Pb-(Ag-Ge) District, Yunnan, China

The Huize Zn-Pb- (Ag-Ge) district is a typical representative of the well-known medium-to large-sized carbonate-hosted Zn-Pb- (Ag-Ge) deposits, occurring in the Sichuan-Yunnan-Guizhou Pb-Zn Ore-forming Zone. Generally, fluid inclusions within calcite, one of the major gangue minerals, are dominated by two kinds of small (1-10 um) inclusions including pure-liquid and liquid. The inclusions exist in concentrated groups along the crystal planes of the calcite. The ore-forming fluids containing Pb and Zn, which belong to the Na+-K+-Ca2+-Cl--F--SO42- type, are characterized by temperatures of 164-221℃, medium salinity in 5-10.8 wt% NaCl, and medium pressure at 410×105 to 661×105 Pa. The contents of Na+-K+ and C1--F-, and ratios of Na+/K+-Cl-/F- in fluid inclusions present good linearity. The ratios of Na+/K+ (4.66-6.71) and Cl-/F- (18.21-31.04) in the fluid inclusions of calcite are relatively high, while those of Na+/K+ (0.29-5.69) and Cl-/F- (5.00-26.0) in the inclusions of sphalerite and pyrite are relatively low. The ratio of Na+/K+ increases in accord with those of Cl-/F-, which indicates that ore-forming fluid of deep source participates in the mineralization. The waters of fluid inclusions have δD values from -43.5‰ to -55.4‰ of calcite. The δ18OV-SMOW values of the ore-forming fluids, calculated values, range from 17.09‰ to 18.56‰ of calcite and 17.80‰ to 23.14‰ for dolomite. δ13CV-PDB values range from -1.94‰ to -3.31‰ for calcite and -3.35‰ to 0.85‰ for the ore-bearing dolomite. These data better demonstrate that the ore-forming fluids were mainly derived from metamorphic water and magmatic hot fluid, in relation to the metamorphism of the Kunyang Group in the basement and magmatic hydrothermalism. The deposit itself might have resulted from ascending cycles of ore-forming fluid, enriched in Pb and Zn. The Huize Zn-Pb- (Ag-Ge) deposits related to carbonate-hosted Zn-Pb sulphides.

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.

Discovery and Significance of High CH_4 Primary Fluid Inclusions in Reservoir Volcanic Rocks of the Songliao Basin,NE China

Comparing compositions of the fluid inclusions in volcanic rocks to the contents and isotopes of the gases in corresponding volcanic reservoirs using microthermometry, Raman microspectroscopy and mass spectrum analysis, we found that： （1） up to 82 mole% methane exists in the primary inclusions hosted in the reservoir volcanic rocks; （2） high CH4 inclusions recognized in the volcanic rocks correspond to CH4-bcaring CO2 reservoirs that are rich in helium and with a high ^3He/^4He ratio and which show reversed order of 813C in alkane; （3） in gas reservoirs of such abiotic methane （〉80%） and a mix of CH4 and CO2, the enclosed content of CH4 in the volcanic inclusions is usually below 42 mole%, and the reversed order of δ^13C in alkane is sometimes irregular in the corresponding gas pools; （4） a glassy inclusion with a homogeneous temperature over 900℃ also contains a small portion of CH4 although predominantly CO2. This affinity between gas pool and content of inclusion in the same volcanic reservoirs demonstrates that magma-originated gases, both CH4 and CO2, have contributed significantly to the corresponding gas pools and that the assumed hydrocarbon budget of the bulk earth might be much larger than conventionally supposed.

Daily Variation of Natural Emission of Methane to the Atmosphere and Source Identification in the Luntai Fault Region of the Yakela Condensed Oil/Gas Field in the Tarim Basin,Xinjiang,China

The static flux chamber method was applied to study natural emissions of methane to the atmosphere in the Luntai fault region of Yakela Condensed Oil/Gas Field in the Tarim Basin, Xinjiang Municipality, northwestern China. Using an online method, which couples together a gas chromatography/high-temperature conversion/isotope ratio mass spectrometry （GC/C/MS）, 13^C/12^C ratios of methane in flux chambers were measured and showed that methane gases are liable to migrate from deep oil/gas reservoirs to the surface through fault regions and that a part of the migrated methane, which remains unoxidized can be emitted into the atmosphere. Methane emission rates were found to be highest in the mornings, lowest in the afternoons and then increase gradually in the evenings. Methane emission rates varied dramatically in different locations in the fault region. The highest methane emission rate was 10.96 mg/m^2·d, the lowest 4.38 mg/m^2, and the average 7.55 mg/ m^2·d. The 13^C/12^C ratios of the methane in the flux chambers became heavier as the enclosed methane concentrations increased gradually, which reveals that methane released from the fault region might come from thermogenic methane of the deep condensed oil/gas reservoir.

Geological emission of methane from the Yakela condensed oil/gas field in Talimu Basin, Xinjiang, China

A static flux chamber method was applied to study natural emissions of methane into the atmosphere in the Yakela condensed oil/gas field in Talimu Basin, Xinjiang, China. Using an online method, which couples a gas chromatography/high-temperature conversion/isotope ratio mass spectrometry (GC/C/MS) together, the 13C/12C ratios of methane in the flux chambers were measured. The results demonstrated that methane gases were liable to migrate from deep oil/gas reservoir to the surface through microseepage and p...

Application of butane geochemistry of natural gas in hydrocarbon exploration

In order to distinguish the source and migration direction of natural gas by geochemical characteristics of butane,the components and carbon isotopes of natural gas from major hydrocarbonbearing basins in China were analyzed.The results showed that：（1） Oil-type gas has i-C 4 /n-C 4 0.8,δ 13 C butane -28‰,δ 13 C i-butane -27‰,δ 13 C n-butane -28.5‰,whereas coal-type gas has i-C 4 /n-C 4 0.8,δ 13 C butane -25.5‰,δ 13 C i-butane -24‰,δ 13 C n-butane -26‰.（2） When δ 13 C i-butane-δ 13 C n-butane is greater than 0,the maturity of oil-type gas is generally more than 2.4% and that of coal-type gas is greater than 1.4%,whereas when the difference is less than 0,the maturity of oil-type gas is generally less than 1.1% and that of coal-type gas is less than 0.8%.（3） When natural gas migrates through dense cap rocks,the value of i-C 4 /n-C 4 increases,whereas when it migrates laterally along a reservoir,the value of i-C 4 /n-C 4 decreases.（4） Sapropelic transition zone gas with composition and carbon isotopic signatures similar to those of oil-type gas in the low thermal evolution stage is found to have a relatively high butane content.（5） The values of i-C 4 /n-C 4 and δ 13 C n-butane δ 13 C i-butane of gas which has suffered biological degradation are significantly higher than those obtained from thermogenic and bio-thermocatalytic transition zone gas.Thus,natural gas of different genetic types can be recognized through component analysis and carbon isotopic signatures of butane,the natural gas maturity can be estimated from the difference in carbon isotopic content between isobutane and n-butane,and the migration direction of natural gas can be determined from i-C 4 /n-C 4 ratios and transport conditions,which can also be used to thermogenic and bio-thermocatalytic transition zone gas.

Origin of the hydrate bound gases in the Juhugeng Sag, Muli Basin, Tibetan Plateau

The Juhugeng Sag,located in northwest of the Muli Basin,Tibetan Plateau,has been investigated for coal and petroleum resources during the past several decades.There have been successful recoveries of gas hydrates during recent years from the Middle Jurassic Yaojie Formation that offer insight into the origin of the hydrocarbon gases from the complex sag feature.This study examines the organic geochemical and stable carbon isotopic characteristics of shale and coal samples from the Middle Jurassic Yaojie Formation of the Juhugeng Sag,as well as compares with carbon isotopes,gas amounts and components of hydrate-bound gas.A total of 19 samples from surface mining,including 12 samples of black shale and 7 samples of coal,were analysed using a micro-photometer,a gas chromatograph,Rock–Eval and isotope methods.All the shale samples contained 100%type I kerogen,and the random vitrinite reflectance values vary from 0.65%to 1.32%and achieve thermal pyrolysis phase.Isotope values of methane(δ13C ranging from−52.6‰to−39.5‰andδD ranging from−285‰to−227‰)in the hydrate bound gases suggest that the methane originates mainly from thermogenic contributions.It is proposed that ethane from the gas hydrate is thermogenic-produced,and this conjecture is supported by the fact that most of the gas hydrate also contains more than 30%of thermogenic C2+hydrocarbons and is similar to structure II hydrate.Carbon isotope data from the gas hydrates show a positive carbon isotope series(δ13C1<δ13C2<δ13C3),with ethaneδ13C values being lighter than−28.5‰,as high consistency with source rocks from the Jurassic period indicate thermal oil-prone gas.A model of the accumulation of gas hydrate is plotted.However,the gaseous sources of gas hydrates may be a subject for more research.

Study of the gas sources of the Ordovician gas reservoir in the Central-Eastern Ordos Basin

The source of the natural gas in the Lower Paleozoic Ordovician strata in the Ordos Basin,China is a controversial issue.In the present study,the genesis and distribution characteristics of the Ordovician natural gas were qualitatively investigated based on the composition of the natural gas and the hydrocarbon isotopic composition.Then,the kinetics of the carbon isotope were analyzed to determine the proportions of the gas in the Ordovician gas reservoir contributed from the Carboniferous-Permian and Ordovician strata.The results show the following.Compared to the Upper Paleozoic natural gas,the Ordovician natural gas has a large dryness coefficient.In core areas where gypsum-salt rocks are developed,the gypsum-salt rocks completely isolate the gas sources.The weathering crust of the reservoir in the fifth member of the Majiagou Formation(Ma_(5)^(1+2))originates primarily from the Upper Paleozoic coal-measure source rocks,while the Ma_(5)^(5)and the pre-salt natural gas are mainly derived from the Ordovician source rocks.In the areas where the gypsum-salt rocks are relatively well-developed,the gypsum-salt rocks isolate the gas source to some extent,the pre-salt gas reservoir is mainly derived from the Lower Paleozoic source rocks,and this contribution gradually increases with increasing depth.In the areas where the gypsum-salt rocks are not developed,the proportion of the contribution of the Upper and Lower Paleozoic source rocks to the gas source of the Ordovician gas reservoir is mainly controlled by the volume of gas generated and the other accumulation conditions,and it does not reflect the isolation effect of the gypsum-salt rocks on the gas source.The Ordovician natural gas accumulation models in the central-eastern Ordos Basin can be divided into four types according to the differences in the gas sources.

Geochemical characteristics of Callovian-Oxfordian carbonates in Samandepe gas field,Amu Darya Basin,Turkmenistan

The Callovian-Oxfordian carbonate reservoirs are the most important hydrocarbon reservoir in the Samandepe gas field,Amu Darya basin,Turkmenistan.Based on the analysis of Fe,Mn and Sr trace elements,and carbon,oxygen and strontium isotopes,the genesis and evolutionary characteristics of the carbonate reservoirs were studied,and the conclusions were follows：1） Sustained transgressive-regressive cycles played an important role during Callovian-Oxfordian.The reservoir of reef-bank facies was well developed in the period of transgression,while the regional dense cap rocks developed in the period of regression;2） The 87 Sr/86 Sr ratio measured from rudist shells yields an age of 157.2 Ma according to the global strontium isotope curve;3） As diagenetic intensity increased,δ 13 C changed little,and δ 18 O showed strong negative deviation but was still limited to the range of Late Jurassic seawater.High Fe and Sr contents,and low Mn content,and the evolutionary trend of δ 13 C and δ 18 O all indicate that diagenesis occurred in a relatively confined environment,where the fluids were relatively reducing and contained hot brine.The stage of diagenesis reached is mesodiagenesis,which is very favorable for preservation of primary pores in carbonates;4） Strong dissolution of reef limestones,burial dolomitization and hydrothermal calcite precipitation were all the results of the interaction between the 87 Sr-rich diagenetic fluid and rocks;5） The analysis results of isotopes,fluid inclusions and vitrinite reflectance show that the diagenetic fluid was compaction-released water that originated from the deep,coal-bearing clastic strata.