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1.
The northeastern area of Sichuan Basin, southwestern China, is the area with the maximal reserve of natural gas containing higher hydrogen sulphide (H2S) that has been found among the petroliferous basins of China, with the proven and controlled gas reserve of more than 200 billion cubic meters. These gas pools, with higher H2S contents averaging 9%, some 17%, are mainly distributed on structural belts of Dukouhe, Tieshanpo, Luojiazhai, Puguang, etc., while the oolitic-shoal dolomite of the Triassic Feixianguan Fm. (T1f) is the reservoir. Although many scholars regard the plentiful accumulation of H2S within the deep carbonate reservoir as the result of Thermochemical Sulfate Reduction (TSR), however, the process of TSR as well as its residual geological and geochemical evidence is still not quite clear. Based on the carbon isotopic analysis of carbonate strata and secondary calcite, etc., together with the analysis of sulfur isotopes within H2S, sulphur, gypsum, iron pyrites, etc., as well as other aspects including the natural gas composition, carbon isotopes of hydrocarbons reservoir petrology, etc., it has been proved that the above natural gas is a product of TSR. The H2S, sulphur and calcite result from the participation of TSR reactions by hydrocarbon gas. During the process for hydrocarbons being consumed due to TSR, the carbons within the hydrocarbon gas participate in the reactions and finally are transferred into the secondary calcite, and become the carbon source of secondary calcite, consequently causing the carbon isotopes of the secondary calcite to be lower (−18.2‰). As for both the intermediate product of TSR, i.e. sulfur, and its final products, i.e. H2S and iron pyrites, their sulfur elements are all sourced from the sulfate within the Feixianguan Fm. During the fractional processes of sulfur isotopes, the bond energy leads to the 32S being released firstly, and the earlier it is released, the lower δ 34S values for the generated sulphide (H2S) or sulfur will be. However, for the anhydrite that participates in reactions, the higher the reaction degree, the more 32S is released, while the less 32S remains and the more δ 34S is increased. The testing results have proved the process of the dynamic fractionation of sulfur isotopes.  相似文献   

2.
Isotopic evidence of TSR origin for natural gas bearing high H2S contents 1961 As the hazardous component of natural gas, the ex-istence of H2S, due to its extremely strong toxicity and corrosivity, not only decreases the percentage of hy-drocarbon gas within natural gas and reduces its in-dustrial value, it also threatens each aspect of drilling and exploitation. It frequently causes serious safety accidents[1] and leads to the E&P cost and risk of natural gas with higher H2S contents be…  相似文献   

3.

Well Yingnan 2, an important exploratory well in the east of Tarim Basin, yields high commercial oil and gas flow in Jurassic. Natural gas components and carbon isotopic composition indicate that it belongs to sapropel type gas. Because this region presents many suits of hydrocarbon source rocks, there are some controversies that natural gases were generated from kerogen gas or crude oil cracking gas at present. By using the kinetics of hydrocarbon generation and carbon isotope, natural gas of Well Yingnan 2 is composed mainly of crude oil cracking gas, about 72%, it is generated from secondary kerogen gas of Cambrian-Lower Ordovician source rock and crude oil cracking gas of Mid-Upper Ordovician oil reservoir. The main oil and gas filling time is 65 Ma later in the Jurassic gas reservoir of Well Yingnan 2, so the gas reservoir belongs to late accumulation and continuous filling type.

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4.

Hetianhe gasfield in Bachu region of the Tarim Basin is mainly composed of three reservoir-caprock assembly, namely regional caprock of upper mudstone, middle mudstone and lower mudstone of the Carboniferous and reservoir of Bachu bioclastic limestone, glutenite and the Ordovician carbonate buried hill. Natural gas in Hetianhe gasfield sourced from the Cambrian source rock. It is thought that gases in Ma4 well block in the east of Hetianhe gasfield are mainly crude-oil cracked gases, while those in Ma3 and Ma8 well blocks in the west are the mixture gases of kerogen cracked gases and crude-oil cracked gases. Natural gas is rich in H2S and accumulated in multiply stages as the result of TSR. The accumulation history is divided into three stages, namely accumulation and breakage in the late Caledonian-early Hercynian, migration and dissipation in the late Hercynian and accumulation in Himalayan. The main accumulation of reformed gas reservoir is in Himalayan.

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5.
Well Yingnan 2, an important exploratory well in the east of Tarim Basin, yields high commercial oil and gas flow in Jurassic. Natural gas components and carbon isotopic composition indicate that it belongs to sapropel type gas. Because this region presents many suits of hydrocarbon source rocks, there are some controversies that natural gases were generated from kerogen gas or crude oil cracking gas at present. By using the kinetics of hydrocarbon generation and carbon isotope, natural gas of Well Yingnan 2 is composed mainly of crude oil cracking gas, about 72%, it is generated from secondary kerogen gas of Cambrian-Lower Ordovician source rock and crude oil cracking gas of Mid-Upper Ordovician oil reservoir. The main oil and gas filling time is 65 Ma later in the Jurassic gas reservoir of Well Yingnan 2, so the gas reservoir belongs to late accumulation and continuous filling type.  相似文献   

6.
Well Yingnan 2,an important exploratory well in the east of Tarim Basin,yields high commercial oil and gas flow in Jurassic.Natural gas components and carbon isotopic composition indicate that it belongs to sapropel type gas.Because this region presents many suits of hydrocarbon source rocks,there are some controversies that natural gases were generated from kerogen gas or crude oil cracking gas at present.By using the kinetics of hydrocarbon generation and carbon isotope,natural gas of Well Yingnan 2 is composed mainly of crude oil cracking gas,about 72%,it is generated from secondary kerogen gas of Cambrian-Lower Ordovician source rock and crude oil cracking gas of Mid-Upper Ordovician oil reservoir.The main oil and gas filling time is 65 Ma later in the Jurassic gas reservoir of Well Yingnan 2,so the gas reservoir belongs to late accumulation and continuous filling type.  相似文献   

7.
Hetianhe gasfield in Bachu region of the Tarim Basin is mainly composed of three reservoir-caprock assembly, namely regional caprock of upper mudstone, middle mudstone and lower mudstone of the Carboniferous and reservoir of Bachu bioclastic limestone, glutenite and the Ordovician carbonate buried hill. Natural gas in Hetianhe gasfield sourced from the Cambrian source rock. It is thought that gases in Ma4 well block in the east of Hetianhe gasfield are mainly crude-oil cracked gases, while those in Ma3 and Ma8 well blocks in the west are the mixture gases of kerogen cracked gases and crude-oil cracked gases. Natural gas is rich in H2S and accumulated in multiply stages as the result of TSR. The accumulation history is divided into three stages, namely accumulation and breakage in the late Caledonian-early Hercynian, migration and dissipation in the late Hercynian and accumulation in Himalayan. The main accumulation of reformed gas reservoir is in Himalayan.  相似文献   

8.

Natural gases discovered up to now in Lishui Sag, the East China Sea Basin, differ greatly in gaseous compositions, of which hydrocarbon gases amount to 2%–94% while non-hydrocarbon gases are dominated by CO2. Their hydrocarbon gases, without exception, contain less than 90% of methane and over 10% of C2 + heavier hydrocarbons, indicating a wet gas. Carbon isotopic analyses on these hydrocarbon gases showed that δ 13C1, δ 13C2 and δ 13C3 are basically lighter than −44‰, −29‰ and −26‰, respectively. The difference in carbon isotopic values between methane and ethane is great, suggesting a biogenic oil-type gas produced by the mixed organic matter at peak generation. δ 13 \( C_{CO_2 } \) values of nonhydrocarbon gases are all heavier than −10‰, indicating a typical abiogenic gas. The simulation experiment on hydrocarbon generation of organic matter in a closed gold-tube system showed that the proportion of methane in natural gases produced by terrigenous organic matter in the Lingfeng Formation marine deposit is obviously higher than that in natural gases derived from the aquatic and terrigenous mixed organic matter in the Yueguifeng Formation lacustrine deposit, consequently the proportion of heavier hydrocarbons of the former is remarkably lower than that of the latter. Moreover, δ 13C1 values of natural gases produced by terrigenous organic matter in the Lingfeng Formation marine deposit are about 5‰ heavier than those of natural gases derived from the aquatic and terrigenous mixed organic matter in the Yueguifeng Formation lacustrine deposit while δ 13C2 and δ 13C3 values of the former are over 9‰ heavier than those of the latter. Currently the LS36-1 oil-gas pool is the only commercial oil-gas reservoir in Lishui Sag, where carbon isotopic compositions of various hydrocarbon components differ greatly from those of natural gases produced by the Lingfeng Formation organic matter but are very similar to those of natural gases derived from the Yueguifeng Formation organic matter, therefore, natural gases in the LS36-1 oil-gas pool are mainly derived from the Yueguifeng Formation lacustrine source rock rather than the Lingfeng Formation marine or Mingyuefeng Formation coal-measures source rocks.

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9.
Kusakabe  M.  Mizutani  Y.  Kometani  M. 《Bulletin of Volcanology》1982,45(3):203-209

Sulphur isotopic compositions of pyrite, anhydrite and native sulphur in volcanic ashes discharged by the 1979 eruption of Ontake volcano, Nagano, Japan were determined. The isotopic data indicate that sulphate in anhydrite and a part of native sulphur were produced by the disproportionation reaction of sulphite formed by dissolution of SO2 in volcanic gases into water which filled a mud reservoir probably located just below the crater zone. Some part of H2S in volcanic gases was fixed as pyrite and some was oxidised to form native sulphur. Hydrothermal alteration of country rocks to form pyrite, anhydrite and clay minerals had proceeded in the mud reservoir before eruption at temperatures ranging from 110° to 185°C which were estimated by oxygen isotopic fractionation between anhydrite and water.

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10.
Natural gases discovered up to now in Lishui Sag, the East China Sea Basin, differ greatly in gaseous compositions, of which hydrocarbon gases amount to 2%–94% while non-hydrocarbon gases are dominated by CO2. Their hydrocarbon gases, without exception, contain less than 90% of methane and over 10% of C2 + heavier hydrocarbons, indicating a wet gas. Carbon isotopic analyses on these hydrocarbon gases showed that δ 13C1, δ 13C2 and δ 13C3 are basically lighter than ?44‰, ?29‰ and ?26‰, respectively. The difference in carbon isotopic values between methane and ethane is great, suggesting a biogenic oil-type gas produced by the mixed organic matter at peak generation. δ 13 \(C_{CO_2 } \) values of nonhydrocarbon gases are all heavier than ?10‰, indicating a typical abiogenic gas. The simulation experiment on hydrocarbon generation of organic matter in a closed gold-tube system showed that the proportion of methane in natural gases produced by terrigenous organic matter in the Lingfeng Formation marine deposit is obviously higher than that in natural gases derived from the aquatic and terrigenous mixed organic matter in the Yueguifeng Formation lacustrine deposit, consequently the proportion of heavier hydrocarbons of the former is remarkably lower than that of the latter. Moreover, δ 13C1 values of natural gases produced by terrigenous organic matter in the Lingfeng Formation marine deposit are about 5‰ heavier than those of natural gases derived from the aquatic and terrigenous mixed organic matter in the Yueguifeng Formation lacustrine deposit while δ 13C2 and δ 13C3 values of the former are over 9‰ heavier than those of the latter. Currently the LS36-1 oil-gas pool is the only commercial oil-gas reservoir in Lishui Sag, where carbon isotopic compositions of various hydrocarbon components differ greatly from those of natural gases produced by the Lingfeng Formation organic matter but are very similar to those of natural gases derived from the Yueguifeng Formation organic matter, therefore, natural gases in the LS36-1 oil-gas pool are mainly derived from the Yueguifeng Formation lacustrine source rock rather than the Lingfeng Formation marine or Mingyuefeng Formation coal-measures source rocks.  相似文献   

11.
The chemical composition and D/H, and ratios have been determined for the acid hot waters and volcanic gases discharging from Zaō volcano in Japan. The thermal springs in Zaō volcano issue acid sulfate-chloride type waters (Zaō) and acid sulfate type waters (Kamoshika). Gases emitted at Kamoshika fumaroles are rich in CO2, SO2 and N2, exclusive of H2O. Chloride concentrations and oxygen isotope data indicate that the Zaō thermal waters issue a fluid mixture from an acid thermal reservoir and meteoric waters from shallow aquifers. The waters in the Zaō volcanic system have slight isotopic shifts from the respective local meteoric values. The isotopic evidence indicates that most of the water in the system is meteoric in origin. Sulfates in Zaō acid sulfate-chloride waters with δ34S values of around +15‰, are enriched in 34S compared to Zaō H2S, while the acid sulfate waters at Kamoshika contain supergene light sulfate (δ34S = + 4‰) derived from volcanic sulfur dioxide from the volcanic exhalations. The sulfur species in Zaō acid waters are lighter in δ34S than those of other volcanic areas, reflecting the difference in total pressure.  相似文献   

12.
The chemical and isotopic compositions of volcanic gases at a borehole and a natural fumarole in the Owakudani geothermal area, Hakone volcano, Japan, have been repeatedly measured since 2001, when a seismic swarm occurred in the area. The CO2/H2O and CO2/H2S ratios were high in 2001. It increased in 2006 and again in 2008 when seismic swarms occurred beneath the geothermal area. The observed increases suggest the injection of CO2- and SO2-rich magmatic gas into the underlying hydrothermal reservoir, implying that the magmatic gas was episodically supplied to the hydrothermal system in 2006 and 2008. The earthquake swarms probably resulted from the injection of gas through the shallow crust accompanying the break of the sealing zone.  相似文献   

13.
High abundant sulfur-containing steroids were identified and detected in saturate hydrocarbon fractions of heavy oil with a high sulfur content in the Jinxian Sag,Bohai Bay Basin,North China.These sulfur-containing steroids were structurally merged into the D-ring of steroid nucleus with thiophene ring and/or combined into the C-22 in the side-chain.Based on the previous reports of sulfur-containing steroids with methylthio-steroids and intra-molecular form,four formation mechanisms of sulfur-containing steroids and diagenetic pathway of steroids under S-rich conditions were proposed in this paper according to the double bond positions in the sterene compounds.Hydrogenation and sulfurization both occurred in the diagenetic processes of olefinic bond in the side-chain of steroids:abiogenic chemical hydrogenation of H2S and HS-leads to the formation of regular steranes;a successful sulfurization process leads to the formation of the side-chain sulfur-containing steroids whereas unsuccessful cyclization and/or sulfurization result in the generation of short-chain steranes.This kind of mechanism of hydrogenation/sulfurization of side-chain olefinic bond provides a potential genesis clue for the occurrence of high abundance of short-chain steranes(higher than the common regular steroids,phytane and n-alkanes)in S-rich heavy oils and source rocks in the Jinxian Sag,Bohai Bay Basin,North China.  相似文献   

14.
TSR is an interaction between sulfate and hydrocarbons, occurring widely in carbonate reservoirs. Because this process can produce a large amount of noxious acidic gases like H2S, it has drawn seri- ous concern recently. This paper reports an experiment that simulated an interaction between different minerals and hydrocarbon fluids under different temperature and time using a confined gold-tube system. The results showed that the main mineral that initiates TSR is MgSO4, and adding a certain amount of NaCl into the reactive system can also promote TSR and yield more H2S. The H2S produced in TSR is an important incentive for the continuous oxidative degradation of crude oils. For instance, the yield of oil-cracking gases affected by TSR was twice of that not affected by TSR while the yield of TSR-affected methane was even higher, up to three times of that unaffected by TSR. The carbon iso- topes of wet gases also became heavier. All of the above illustrated that TSR obviously motivates the oxidative degradation of crude oils, which makes the gaseous hydrocarbon generation sooner and increases the gas dryness as well. The study on this process is important for understanding the TSR mechanism and the mechanism of natural gas generation in marine strata.  相似文献   

15.
Methods used previously to remove compositional modifications from volcanic gas analyses for Mount Etna and Erta'Ale lava lake have bean employed to estimate the gas phase composition at Nyiragongo lava lake, based on samples obtained in 1959. H2O data were not reported in 11 of the 13 original analyses. The restoration methods have been used to estimate the H2O contents of the samples and to correct the analyses for atmospheric contamination, loss of sulfur and for pre- and pest-collection oxidation of H2S, S2, and H2. The estimated gas compositions are relatively CO2-rich, low in total sulfur and reduced. They contain approximately 35–50% CO2 45–55% H2O, 1–2% SO2, 1–2% H2., 2–3% CO, 1.5–2.5% H2S, 0.5% S2 and 0.1% COS over,he collection temperature range 102° to 960° C. The oxygen fugacities of the gases are consistently about half an order of magnitude below quartz-magnetite-fayalite. The low total sulfur content and resulting low atomic S/C of the Nyiragongo gases appear to be related to the relatively low fO2 of the crystallizing lava. At temperatures above 800°C and pressures of 1–1.5 k bar, the Nyiragongo gas compositions resemble those observed in primary fluid inclusions believed to have formed at similar temperatures and pressures in nephelines of intrusive alkaline rocks. Cooling to 300°C, with fO2 buffered by the rock, results in gas compositions very rich in CH4 (50–70%) and resembling secondary fluid inclusions formed at 200–500°C in alkaline rocks. Below 600°C the gases become supersaturated in carbon as graphite. These inferences are corroborated by several reports of hydrocarbons in plutonic alkaline rocks, and by the presence of CH4-rich waters in Lake Kivu — a lake on the flanks of Nyiragongo volcano.  相似文献   

16.

The composition of fluid inclusions (FI) often represents the initial geochemical characteristics of palaeo-fluid in reservoir rock. Influence on composition and carbon isotopic composition of gas during primary migration, reservoir-forming and subsequent secondary alterations are discussed through comparing fluid inclusion gas with coal-formed gas and natural gas in present gas reservoirs in the Ordos Basin. The results show that primary migration of gas has significant effect on the molecular but not on the carbon isotopic composition of methane. Migration and diffusion fractionation took place during the secondary migration of gas in Upper Paleozoic gas reservoir according to carbon isotopic composition of methane in Fls. Composition and carbon isotopic composition of natural gas were nearly unchanged after the gas reservoir forming through comparing the FI gases with the natural gas in present gas reservoir.

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17.
Gas samples were collected by aircraft entering volcanic eruption clouds of three Guatemalan volcanoes. Gas chromatographic analyses show higher H2 and S gas contents in ash eruption clouds and lower H2 and S gases in vaporous gas plumes. H isotopic data demonstrate lighter isotopic distribution of water vapor in ash eruption clouds than in vaporous gas plumes. Most of the H2O in the vaporous plumes is probably meteoric. The data are the first direct gas analyses of explosive eruptive clouds, and demonstrate that, in spite of atmospheric admixture, useful compositional information on eruptive gases can be obtained using aircraft.  相似文献   

18.
Yang  Chun  Luo  Xia  Li  Jian  Li  ZhiSheng  Liu  QuanYou  Wang  YuLin 《中国科学:地球科学(英文版)》2008,51(1):140-147

The Xushen gas field, located in the north of Songliao Basin, is a potential giant gas area for China in the future. Its proved reserves have exceeded 1000×108 m3 by the end of 2005. But, the origin of natural gases from the deep strata is still in debating. Epimetamorphic rocks as a potential gas source are widely spreading in the northern basement of Songliao Basin. According to pyrolysis experiments for these rocks in the semi-confined system, gas production and geochemistry of alkane gases are discussed in this paper. The Carboniferous-Permian epimetamorphic rocks were heated from 300°C to 550°C, with temperature interval of 50°C. The gas production was quantified and measured for chemical and carbon isotopic compositions. Results show that δ 13C1 is less than −20‰, carbon isotope trend of alkane gas is δ 13C1<δ 13C2<δ 13C3 or δ 13C1<δ 13C2>δ 13C3, these features suggest that the gas would be coal-type gas at high-over maturity, not be inorganic gas with reversal trend of gaseous alkanes (δ 13C1>δ 13C2>δ 13C3). These characteristics of carbon isotopes are similar with the natural gas from the basin basement, but disagree with gas from the Xingcheng reservoir. Thus, the mixing gases from the pyrolysis gas with coal-typed gases at high-over maturity or oil-typed gases do not cause the reversal trend of carbon isotopes. The gas generation intensity for epimetamorphic rocks is 3.0×108–23.8×108 m3/km2, corresponding to R o from 2.0% to 3.5% for organic matter.

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19.
By measuring carbon and hydrogen isotope compositions for C1, C2 and C3 of 74 gas samples, natural gases from the Tarim Basin can be divided into six groups on the basis of their origins: (1) coal-type gas derived from coal measures; (2) coal-type gas generated from the T-J lacustrine mudstones; (3) oil-type gas derived from the Cambrian and low Ordovician marine source rocks; (4) oil-type gas from the source rocks deposited in the marine-transitional facies; (5) mixing gas between gas derived from the Carboniferous transitional source rocks and the Mesozoic humic gas, and (6) mixing gases of thermal genetic gas and little deep gas in the Southwest depression of the Tarim Basin. The δ D values of methane in natural gases originating from different type kerogens are affected by both palaeo-environments of the source rock formation (kerogen types) and thermal maturity, with sedimentary environment (kerogen type) as the main controlling factor. Under the similar thermal maturity, the hydrogen isotope composition of methane is more enriched in deuterium in marine environments than lacustrine one. With the increase of thermal maturity and the increase of carbon atomic numbers of gaseous alkanes, the hydrogen isotopes become enriched in deuterium. The δ D values of ethane and propane (δ D2, δ D3) are controlled mainly by thermal maturity and to a lesser degree by sedimentary environment of the source rock formation. The partial reversal of hydrogen isotopes for gaseous alkanes would be related to the microbial oxidation, mixing of sapropelic and humic gases and / or mixing of gases from similar kerogen sources with various thermal maturities. In the oil-type gas, the sulfate reduction reaction would result in the reversed order of δ D1 and δ D2 (e.g. δ D1>δ D2).  相似文献   

20.
A field gas chromatograph, built in 1978, was used in the field to directly analyse volcanic gases before water vapor condensation. Tested in Vulcano (Italy), Kilauea (Hawaii) and Merapi (Indonesia), this field measurement technique provides the actual composition of the volcanic gas mixture. The technique avoids the depletion of sulfur gases and the dissolution of the acid gases in the condensed water during the cooling. Thus the mixture of H2S and SO2 in fumarolic and high temperature gases (up to 819°C) in equilibrium at the emission temperature was examined.  相似文献   

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