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The mechanism of hydrogen sulfide (HS) generation plays a key role in the exploration and development of marine high-sulfur natural gas, of which the major targets are the composition and isotope characteristics of sulfur-containing compounds. Hydrocarbon source rocks, reservoir rocks, natural gases and water-soluble gases from Sichuan Basin have been analyzed with an online method for the content of HS and isotopic composition of different sulfur-containing compounds. The results of comparative analysis show that the sulfur-containing compounds in the source rocks are mainly formed by bacterial sulfate reduction (BSR), and the sulfur compounds in natural gas, water and reservoir are mainly formed by thermal sulfate reduction (TSR). Moreover, it has been shown that the isotopically reversion for methane and ethane in high sulfur content gas is caused by TSR. The sulfur isotopic composition of HS in natural gas is inherited from the gypsum or brine of the same or adjacent layer, indicating that the generation and accumulation of HS have the characteristics of either a self-generated source or a near-source. [ABSTRACT FROM AUTHOR]

A series of marginal-sea basins and fault-depression basins were formed in eastern China under the background of subduction of the West Pacific plate. Different types of helium-rich natural gas reservoirs (He>1000 ppm, 1 ppm=1 µmol mol−1) have been found in these basins: helium-rich CO2 gas reservoirs, helium-rich N2 gas reservoirs, and helium-rich hydrocarbon gas reservoirs. Based on the analysis of gas geochemical data, the source and accumulation mechanism of helium in these helium-rich natural gas reservoirs were discussed. Helium-rich natural gas has relatively high 3He/4He ratios (0.88–4.91 Ra, average 2.82 Ra). The 3He/4He ratio characteristics of mantle xenoliths and mantle-derived CO2 gas reservoirs indicate that the helium in these helium-rich natural gas reservoirs is mainly mantle-derived (>70%). The original mantle volatile is mainly CO2 with a low helium concentration (He<200 ppm), and the enrichment of mantle-derived helium in the gas reservoir is mainly related to the dissolution and mineralization of CO2. During this process, the CO2/3He ratio decreases from 2×109 to approximately 2×106. As CO2 dissolves and mineralizes, the concentration of conservative gases (He and N2) increases in the remaining CO2 gas proportionally to the loss of CO2. Large amounts of carbonate minerals, such as dawsonite, which are relatively enriched in 13C, are found in CO2 reservoirs in eastern China. The relative enrichment of 12C in residual CO2 gas is important evidence of the dissolution and mineralization of CO2. The relative abundance of mantle-derived helium and N2 gas increases thousands of times during the dissolution and mineralization of CO2, which is the main accumulation mechanism of mantle-derived helium-rich CO2 gas reservoirs and helium-rich N2 gas reservoirs. Helium-rich gas from the mantle is mixed with alkane gas generated by organic matter in the sedimentary basin to form helium-rich hydrocarbon gas reservoirs. [ABSTRACT FROM AUTHOR]

Using high pressure and geological condition simulation vessels, we conducted hydrous pyrolysis experiments of kerogen, solid bitumen and liquid hydrocarbons in southern China in order to study the processes of gas generation and derive geochemical indicators of gas genesis under approximate pressure and temperature. The results indicate that gas generation productivity of different marine material decreased in the order of crude oil (light oil and condensate), dispersed soluble organic matter (solid bitumen and heavy oil), and kerogen. Under identical temperature-pressure regimes, pyrolysates derived from kerogen and dispersed soluble organic matter display drastically different geochemical characteristics. For example, the $\delta ^{13} C_{CO_2 } - \delta ^{13} C_1 $ values of gaseous products from dispersed soluble organic matter are greater than 20‰, whereas those from kerogen are less than 20‰. The δC values of pyrolysates from different marine hydrocarbon sources generally increase with pyrolysis temperature, but are always lower than those of the source precursors. The δC values of ethane and propane in the pyrolysates also increase with increasing pyrolysis temperature, eventually approaching that of their sources, at peak hydrocarbon generation. At high-over mature stages, the δC values of ethane and propane are often greater than those of their sources but close to those of coal gases, and thus become ineffective as gas genetic indicators. Ln(C/C) can clearly distinguish kerogen degradation gas from oil cracking gas and Ln(C/C)-( δC− δC) can be an effective indicator for distinguishing oil cracking gas from dispersed soluble organic matter cracking gas. [ABSTRACT FROM AUTHOR]

The influences of water media on the hydrogen isotopic composition of organic-thermogenic natural gas were tested in three series of experiments on coal pyrolysis, with no water, deionized water ( $\delta D_{H_2 O} $=−58‰), and seawater ( $\delta D_{H_2 O} $=−4.8‰) added, respectively. The experimental results show that the productivities of H and CO obviously increased under hydrous conditions and that the productivity of CH also remarkably increased in the high-evolution phase of hydrous experiments. Water was involved in the chemical reaction of hydrocarbon generation, and then the hydrogen isotopic composition of methane was affected. There is a linear correlation between the hydrogen isotopic composition of methane and its productivity, as reflected in the three series of experiments. In the case of the same CH productivity, the hydrogen isotopic composition of the methane produced in anhydrous experiments was the heaviest, that of the methane produced in seawater-adding experiments came second, and that of the methane produced in deionized water-adding experiments was the lightest. The hydrogen isotopic composition of natural gas/methane is affected by the following factors: 1) the characteristics of hydrogen isotopic composition of organic matter in source rocks, 2) the thermal evolution extent of organic matter, and 3) fossil-water media in the natural gas-generation period. The experimental results show that the influence of the fossil-water medium in the natural gas-generation period was lower than that of the other factors. [ABSTRACT FROM AUTHOR]

The total organic carbon (TOC) in the marine source rock of the Ordos Basin mostly ranges from 0.2% to 0.5%. The industrial standard commonly states that the TOC value has to be no less than 0.5% (0.4% for high mature or over-mature source rock) to form large petroleum reservoirs. However, gas source correlation indicates that the natural gas in the Jingbian gas field does receive contribution from marine source rocks. In order to determine the effect of carboxylate salts (or called as organic acid salts) on TOC in highly mature source rocks with low TOC value, we sampled the Ordovician marine source rock and the Permian transitional facies source rock in one drilled well in the southern Ordos Basin and performed infrared and GC-MS analysis. It is found that both kerogen-derived organic acids and carboxylate salt-conversed organic acids exist in both marine and transitional facies source rocks. The carboxylate salt-conversed organic acids mainly come from the complete acidification of carboxylate salts, which confirms the presence of carboxylate salts in the marine source rocks. Although the C 16:O peak is the main peak for the organic acids both before and after acidification, the carboxylate salt-conversed organic acids have much less relative abundance ahead of C 16:O compared with that of the kerogen-based and free organic acids. This observation suggests that the kerogen-based and free organic acids mainly decarboxylate to form lower carboxylic acids, whereas the carboxylate salt-conversed organic acids mainly break down into paraffins. By using calcium hexadecanoate as the reference to quantify the kerogen-derived and carboxylate salt-conversed organic acids, the high TOC (>2.0%) marine source rocks have low carboxylate salt content and the low TOC (0.2%–0.5%) marine source rocks contain high content of carboxylate salt. Therefore, for the marine source rocks with 0.2%–0.5% TOC, the carboxylate salts may be a potential gas source at high maturity stage. [ABSTRACT FROM AUTHOR]