Experimental investigation on the carbon isotope fractionation of methane during gas migration by diffusion through sedimentary rocks at elevated temperature and pressure

Molecular transport (diffusion) of methane in water-saturated sedimentary rocks results in carbon isotope fractionation. In order to quantify the diffusive isotope fractionation effect and its dependence on total organic carbon (TOC) content, experimental measurements have been performed on three natural shale samples with TOC values ranging from 0.3 to 5.74%. The experiments were conducted at 90°C and fluid pressures of 9 MPa (90 bar). Based on the instantaneous and cumulative composition of the diffused methane, effective diffusion coefficients of the ¹²CH₄ and ¹³CH₄ species, respectively, have been calculated.Compared with the carbon isotopic composition of the source methane (δ¹³C₁ = −39.1‰), a significant depletion of the heavier carbon isotope (¹³C) in the diffused methane was observed for all three shales. The degree of depletion is highest during the initial non-steady state of the diffusion process. It then gradually decreases and reaches a constant difference (Δ δ = δ¹³C_diff −δ¹³C_source) when approaching the steady-state. The degree of the isotopic fractionation of methane due to molecular diffusion increases with the TOC content of the shales. The carbon isotope fractionation of methane during molecular migration results practically exclusively from differences in molecular mobility (effective diffusion coefficients) of the ¹²CH₄ and ¹³CH₄ entities. No measurable solubility fractionation was observed.The experimental isotope-specific diffusion data were used in two hypothetical scenarios to illustrate the extent of isotopic fractionation to be expected as a result of molecular transport in geological systems with shales of different TOC contents. The first scenario considers the progression of a diffusion front from a constant source (gas reservoir) into a homogeneous “semi-infinite” shale caprock over a period of 10 Ma.In the second example, gas diffusion across a 100 m caprock sequence is analyzed in terms of absolute quantities and isotope fractionation effects. The examples demonstrate that methane losses by molecular diffusion are small in comparison with the contents of commercial size gas accumulations. The degree of isotopic fractionation is related inversely to the quantity of diffused gas so that strong fractionation effects are only observed for relatively small portions of gas.The experimental data can be readily used in numerical basin analysis to examine the effects of diffusion-related isotopic fractionation on the composition of natural gas reservoirs.     

Isotopic and molecular composition of coal-bed gas in the Amasra region (Zonguldak basin—western Black Sea)

Previous studies on the coal-bed methane potential of the Zonguldak basin have indicated that the gases are thermogenic and sourced by the coal-bearing Carboniferous units. In this earlier work, the origin of coal-bed gas was only defined according to the molecular composition of gases and to organic geochemical properties of the respective source rocks, since data on isotopic composition of gases were not available. Furthermore, in the western Black Sea region there also exist other source rocks, which may have contributed to the coal-bed gas accumulations. The aim of this study is to determine the origin of coal-bed gas and to try a gas-source rock correlation. For this purpose, the molecular and isotopic compositions of 13 headspace gases from coals and adjacent sediments of two wells in the Amasra region have been analyzed. Total organic carbon (TOC) measurements and Rock-Eval pyrolysis were performed in order to characterize the respective source rocks. Coals and sediments are bearing humic type organic matter, which have hydrogen indices (HI) of up to 300 mgHC/gTOC, indicating a certain content of liptinitic material. The stable carbon isotope ratios (δ¹³C) of the kerogen vary from −23.1 to −27.7‰. Air-free calculated gases contain hydrocarbons up to C₅, carbon dioxide (<1%) and a considerable amount of nitrogen (up to 38%). The gaseous hydrocarbons are dominated by methane (>98%). The stable carbon isotope ratios of methane, ethane and propane are defined as δ¹³C₁: −51.1 to −48.3‰, δ¹³C₂: −37.9 to −25.3‰, δ¹³C₃: −26.0 to −19.2 ‰, respectively. The δD₁ values of methane range from −190 to −178‰. According to its isotopic composition, methane is a mixture, partly generated bacterially, partly thermogenic. Molecular and isotopic composition of the gases and organic geochemical properties of possible source rocks indicate that the thermogenic gas generation took place in coals and organic rich shales of the Westphalian-A Kozlu formation. The bacterial input can be related to a primary bacterial methane generation during Carboniferous and/or to a recent secondary bacterial methane generation. However, some peculiarities of respective isotope values of headspace gases can also be related to the desorption process, which took place by sampling.     

川东宣汉地区天然气地球化学特征及成因

依据10余口探井60多个气样的化学成份和碳同位素组成数据,结合烃源岩和储层沥青分析资料,系统剖析了四川盆地东部宣汉地区普光、毛坝场等构造带天然气地球化学特征,并探讨了其成因及来源。研究结果表明:这些构造带中飞仙关组—长兴组天然气为高含硫化氢的干气,天然气化学成份表现出古油藏原油裂解气的特点。其烃类气体中以甲烷为主(高于99.5%);富含非烃气体,CO₂和H₂S平均含量分别达5.32%和11.95%。甲烷碳同位素较重(-33‰～-29‰),表征高热演化性质;乙烷δ¹³C值主要分布在-33‰至-28‰范围,属油型气。这些天然气与川东邻近气田的同层位天然气具有同源性,而与石炭系气藏天然气在化学成份、碳同位素组成上有所不同,意味着有不同的气源。硫化物硫同位素和沥青元素组成证实高含量的H₂S是气藏发生TSR作用所致。δ³⁴S值表征层状沉积成因的硬石膏是TSR作用的反应物,而脉状硬石膏则是其残余物。储层的孔隙类型可能与TSR作用强度和H₂S含量高低有联系,裂缝型气层中H₂S少,孔洞型储层中H₂S丰富。乙烷、沥青和各层系烃源岩干酪根碳同位素对比表明研究区飞仙关组—长兴组气藏天然气主要来自二叠系烃源层。     

Origins of natural gases from marine strata in Northeastern Sichuan Basin (China) from carbon molecular moieties and isotopic data

To determine the origin, maturity, formation mechanism and secondary process of marine natural gases in Northeastern Sichuan area, molecular moieties and carbon isotopic data of the Carboniferous and Triassic gases have been analyzed. Typical samples of marine gas precursors including low-maturity kerogen, dispersed liquid hydrocarbons (DLHs) in source rocks, residual kerogen and oil have been examined in a closed system, and several published geochemical diagrams of gas origins have been calibrated by using laboratory data. Results show that both Carboniferous and Triassic gases in the study area have a thermogenic origin. Migration leads to stronger compositional and weak isotopic fractionation, and is path dependent. Carboniferous gases and low-H₂S gases are mainly formed by secondary cracking of oil, whereas high-H₂S gases are clearly related to the TSR (Thermal Sulfate Reduction) process. Gases in NE Sichuan show a mixture of heavy (¹³C-enriched) methane in comparison to the lower maturated ethane of Triassic gas samples, suggesting a similar source and maturity for ethane and propane of Carboniferous gases, and a mixture of heavy ethane to the propane for Triassic gases. Based on the data plotted in the diagram of Chung et al. (1988), the residual kerogen from Silurian marine shale and palaeo oil reservoirs are the main source for Carboniferous gases, and that the residual kerogen from Silurian and Permian marine rocks and Permian paleao oil reservoirs constitute the principal source of Triassic gases.     

Stable isotope geochemistry of coals, humic kerogens and related natural gases

Isotope systematics are well defined for conventional sapropelic, Type I/II kerogens and their associated bacterial and thermogenic natural-gas products. These geochemical tools are used to estimate source type, maturity and depositional environment, and as a correlation technique. In many cases the natural gas signatures in near-surface samples and drill cuttings can be used to classify or predict a deeper lying source rock or reservoir.Corresponding interpretative schemes for coals, Type III kerogens and their associated hydrocarbons are progressing quickly. The shift in attention to humic sources is driven primarily by depletion of conventional oil and gas resources and the economic and societal requirements of coal and coal-bed methane.Carbon, hydrogen and nitrogen stable isotope variations can be large between different coals and humic kerogens. These differences can often be recognized in their bulk δ¹³C_org, δD_org and δ¹⁵N_org values. Isotope signatures of coals can be diagnostic of several factors, including deposit age, type, geographic location, maturity and generation history. However, these characteristic isotopic variations are substantially better defined by the C-, H- and N-isotope ratios of the separate maceral groups, such as vitrinite, exinite and inertinite. This new application of stable isotopes, at the maceral and compound levels, have great potential to improve the interpretative precision over conventional whole coal or bulk techniques.Hydrocarbon gases, including coal gases, derived from coals and humic kerogens can be distinguished from Type I/II sources, based on their molecular rations, i.e., C₁/(C₂ + C₃) and by comparing their stable isotope compositions, especially δ¹³C_CH4 and δD_CH4. The δ¹³C_C2H6 can also be valuable, but ethane is generally present in small amount (<1 vol. %) and requires     

Fundamental studies on kinetic isotope effect (KIE) of hydrogen isotope fractionation in natural gas systems

Based on quantum chemistry calculations for normal octane homolytic cracking, a kinetic hydrogen isotope fractionation model for methane, ethane, and propane formation is proposed. The activation energy differences between D-substitute and non-substituted methane, ethane, and propane are 318.6, 281.7, and 280.2 cal/mol, respectively. In order to determine the effect of the entropy contribution for hydrogen isotopic substitution, a transition state for ethane bond rupture was determined based on density function theory (DFT) calculations. The kinetic isotope effect (KIE) associated with bond rupture in D and H substituted ethane results in a frequency factor ratio of 1.07. Based on the proposed mathematical model of hydrogen isotope fractionation, one can potentially quantify natural gas thermal maturity from measured hydrogen isotope values. Calculated gas maturity values determined by the proposed mathematical model using δD values in ethane from several basins in the world are in close agreement with similar predictions based on the δ¹³C composition of ethane. However, gas maturity values calculated from field data of methane and propane using both hydrogen and carbon kinetic isotopic models do not agree as closely. It is possible that δD values in methane may be affected by microbial mixing and that propane values might be more susceptible to hydrogen exchange with water or to analytical errors. Although the model used in this study is quite preliminary, the results demonstrate that kinetic isotope fractionation effects in hydrogen may be useful in quantitative models of natural gas generation, and that δD values in ethane might be more suitable for modeling than comparable values in methane and propane.     

Carbon and hydrogen isotope fractionation by moderately thermophilic methanogens

A series of laboratory studies were conducted to increase understanding of stable carbon (¹³C/¹²C) and hydrogen (D/H) isotope fractionation arising from methanogenesis by moderately thermophilic acetate- and hydrogen-consuming methanogens. Studies of the aceticlastic reaction were conducted with two closely related strains of Methanosaeta thermophila. Results demonstrate a carbon isotope fractionation of only 7‰ (α = 1.007) between the methyl position of acetate and the resulting methane. Methane formed by this process is enriched in ¹³C when compared with other natural sources of methane; the magnitude of this isotope effect raises the possibility that methane produced at elevated temperature by the aceticlastic reaction could be mistaken for thermogenic methane based on carbon isotopic content. Studies of H₂/CO₂ methanogenesis were conducted with Methanothermobacter marburgensis. The fractionation of carbon isotopes between CO₂ and CH₄ was found to range from 22 to 58‰ (1.023 ≤ α ≤ 1.064). Greater fractionation was associated with low levels of molecular hydrogen and steady-state metabolism. The fractionation of hydrogen isotopes between source H₂O and CH₄ was found to range from 127 to 275‰ (1.16 ≤ α ≤ 1.43). Fractionation was dependent on growth phase with greater fractionation associated with later growth stages. The maximum observed fractionation factor was 1.43, independent of the δD-H₂ supplied to the culture. Fractionation was positively correlated with temperature and/or metabolic rate. Results demonstrate significant variability in both hydrogen and carbon isotope fractionation during methanogenesis from H₂/CO₂. The relatively small fractionation associated with deuterium during H₂/CO₂ methanogenesis provides an explanation for the relatively enriched deuterium content of biogenic natural gas originating from a variety of thermal environments. Results from these experiments are used to develop a hypothesis that differential reversibility in the enzymatic steps of the H₂/CO₂ pathway gives rise to variability in the observed carbon isotope fractionation. Results are further used to constrain the overall efficiency of electron consumption by way of the hydrogenase system in M. marburgensis, which is calculated to be less than 55%.     

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.     

Isotopic signatures of CH4 and higher hydrocarbon gases from Precambrian Shield sites: A model for abiogenic polymerization of hydrocarbons

Previous studies of methane and higher hydrocarbon gases in Precambrian Shield rocks in Canada and the Witwatersrand Basin of South Africa identified two major gas types. Paleometeoric waters were dominated by hydrocarbon gases with compositional and isotopic characteristics consistent with production by methanogens utilizing the CO₂ reduction pathway. In contrast the deepest, most saline fracture waters contained gases that did not resemble the products of microbial methanogenesis and were dominated by both high concentrations of H₂ gas, and CH₄ and higher hydrocarbon gases with isotopic signatures attributed to abiogenic processes of water-rock reaction in these high rock/water ratio, hydrogeologically-isolated fracture waters. Based on new data obtained for the higher hydrocarbon gases in particular, a model is proposed to account for carbon isotope variation between CH₄ and the higher hydrocarbon gases (specifically ethane, propane, butane, and pentane) consistent with abiogenic polymerization. Values of δ¹³C for CH₄ and the higher hydrocarbon gases predicted by the model are shown to match proposed abiogenic hydrocarbon gas end-members identified at five field sites (two in Canada and three in South Africa) suggesting that the carbon isotope patterns between the hydrocarbon homologs reflect the reaction mechanism. In addition, the δ²H isotope data for these gases are shown to be out of isotopic equilibrium, suggesting the consistent apparent fractionation observed between the hydrocarbon homologs may also reflect reaction mechanisms involved in the formation of the gases. Recent experimental and field studies of proposed abiogenic hydrocarbons such as those found at mid-ocean spreading centers and off-axis hydrothermal fields such as Lost City have begun to focus not only on the origin of CH₄, but on the compositional and isotopic information contained in the higher hydrocarbon gases. The model explored in this paper suggests that while the extent of fractionation in the first step in the hydrocarbon synthesis reaction chain may vary as a function of different reaction parameters, δ¹³C values for the higher hydrocarbon gases may be predicted by a simple mass balance model from the δ¹³C values of the lower molecular weight precursors, consistent with abiogenic polymerization. Integration of isotopic data for the higher hydrocarbon gases in addition to CH₄ may be critical for delineation of the origin of the hydrocarbons and investigation of formation mechanisms.     

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.     

海相干酪根与原油裂解气甲烷生成及碳同位素分馏的差异研究

利用封闭金管高压釜体系对海相原油和成熟干酪根进行了热解生气实验,获取了两类裂解气的组分和甲烷碳同位素数据,对比研究了两类母质在生气机理上的差异,并借助碳同位素分馏动力学参数讨论了甲烷碳同位素分馏的异同点.结果表明,原油裂解气富含C2-5重烃,其后期裂解是甲烷的重要来源;而干酪根裂解气中C2-5的含量较低,其后期裂解对干酪根甲烷气的贡献较小.这是两类甲烷气体生成的最大差异之一.两类裂解气甲烷碳同位素都有随着热解温度增高,碳同位素值先变轻再变重的特点,但原油裂解气甲烷碳同位素的最小值对应的温度较高;在相同热解温度下,干酪根裂解气甲烷碳同位素值要重于原油裂解气甲烷碳同位素值,这与后者前系物经过多次碳同位素分馏有关.因此,生气机理的差异是造成同位素分馏差异的根本原因,两类甲烷气体碳同位素分馏动力学参数的差异也是有成因意义的.     

An experimental comparison of gas generation from three oil fractions: Implications for the chemical and stable carbon isotopic signatures of oil cracking gas

Although oil cracking has been documented as one of the important sources of gas in many overmature marine sedimentary basins, the chemical and carbon isotopic signatures of gases of this origin are still open to question. In this study a Cambrian crude oil from the central Tarim basin, along with its main separated fractions (saturates, aromatics and asphaltenes), were pyrolyzed in sealed gold tubes to investigate how generated gases vary in chemical and carbon isotopic composition and how this variation would influence the genetic interpretation of oil cracking gas. The results indicate that the gases from cracking of aromatics and asphaltenes are much drier and more enriched in ¹³C than the gases from the cracking of saturates and crude oil at the same level of thermal maturity. In the experimental run of 20 °C/h, the dryness index of the gases (defined as the volume percentage of C₁ in C_1–5) from the cracking of saturates ranges from 26.2–90.6% with the methane carbon isotope change ranging from −54.8‰ to −35.5‰, whereas the dryness index is never lower than 60.6% for the gases from the cracking of aromatics with methane carbon isotope ranging from −39.9‰ to −32.2‰. Correspondingly, experimental data for the four samples plot in different areas in diagrams designed to distinguish oil cracking gas from kerogen cracking gas, such as ln(C₂/C₃) vs. δ¹³C₂–δ¹³C₃ and δ¹³C₁ vs. δ¹³C₂–δ¹³C₃, indicating compositional variability of crude oil could assert an important influence in these diagrams. Therefore it is prudent to bring other geological constraints into consideration to avoid misinterpretation.The kinetic parameters for the bulk generation of C_1–5 gas and the methane carbon isotope fractionation extrapolated to geological conditions of 2 °C/Ma and an initial temperature of 50 °C show that the temperatures of C_1–5 gas generation from the aromatics and asphaltenes are lower than those from the saturates and crude oil due to their lower activation energies and frequency factors. Generation of C_1–5 gases from the aromatics is modeled to be initiated about 122 °C whereas the initiation temperature for the saturates sample is 176 °C. Below 189 °C (EasyRo = 1.8%), the yields of C_1–5 gases follow the order: aromatics > asphaltenes > crude oil > saturates. At similar thermal maturity levels, the methane carbon isotopic compositions are significantly different for the four samples, with an order of ¹³C enrichment: aromatics > asphaltenes > crude oil > saturates, however the difference in methane carbon isotopes becomes smaller with increasing temperature. This indicates that methane carbon isotopic values can be significantly different for gases cracked from oils that are compositionally diverse, especially in the early stage of methane generation.     

Indication of methane movement from petroleum reservoir to surface, Löningen oilfield, NW-Germany

An existing method of detecting microgas seeps was applied in a free soil gas investigation above the Löningen oilfield, NW-Germany. Simple gas surveying was combined with sampling of soil gases for gas-chromatographic treatment and examination of the carbon isotopic composition. A zone of biological gas formation and an area of thermocatalytic methane were discovered, the latter probably caused by migration from the subsurface petroleum accumulation.The methane in the reservoir differs in isotopic composition depending on its origin: gas from gascap or petroleum. Methane dissolved from petroleum is depleted in ¹²C by about 5 ppt compared to methane from the gascap. In relation to the reservoir a general ¹³C-enrichment between 2.5 and 4.6 ppt is observed in the soil gas methanes which is supposedly due to isotopic fractionation during migration. The two species of reservoir methane are still distinguishable on the surface by their different composition. Gaseous hydrocarbons from C₂ to C₄ seem to be restricted by migration. Bacterial oxidation appears not to affect the isotopic composition of the thermocatalytic methane seriously.     

Comparison of fluid geochemistry and microbiology of multiple organic-rich reservoirs in the Illinois Basin, USA: Evidence for controls on methanogenesis and microbial transport

Microbial methane in sedimentary basins comprises approximately 20% of global natural gas resources, yet little is known about the environmental requirements and metabolic rates of these subsurface microbial communities. The Illinois Basin, located in the midcontinent of the United States, is an ideal location to investigate hydrogeochemical factors controlling methanogenesis as microbial methane accumulations occur: (1) in three organic-rich reservoirs of different geologic ages and organic matter types - Upper Devonian New Albany Shale (up to 900 m depth), Pennsylvanian coals (up to 600 m depth), and Quaternary glacial sediments (shallow aquifers); (2) across steep salinity gradients; and (3) with variable concentrations of . For all three organic-rich reservoirs aqueous geochemical conditions are favorable for microbial methanogenesis, with near neutral pH, concentrations <2 mM, and Cl⁻ concentrations <3 M. Also, carbon isotopic fractionation of CH₄, CO₂, and DIC is consistent with microbial methanogenesis, and increased carbon isotopic fractionation with average reservoir depth corresponds to a decrease of groundwater flushing rates with average depth of reservoir. Plots of stable isotopes of water and Cl⁻ show mixing between a brine endmember and freshwater, suggesting that meteoric groundwater recharge has affected all microbial methanogenic systems. Additionally, similar methanogenic communities are present in all three reservoirs with comparable cell counts (8.69E3-2.58E6 cells/mL). TRFLP results show low numbers of archaea species with only two dominant groups of base pairs in coals, shale, and limestone aquifers. These results compare favorably with other methanogen-containing deep subsurface environments. Individual hydrogeochemical parameters that have a Spearman correlation coefficient greater than 0.3 to variations in methanogenic species include stable isotopes of water (δ¹⁸O and δD), type of substrate (i.e. coals versus shale), pH, and Cl⁻ concentration. The matching of variations between methanogenic TRFLP data and conservative tracers suggests that deep circulation of meteoric waters influenced archaeal communities in the Illinois Basin. In addition, coalification and burial estimates suggest that in the study area, coals and shale reservoirs were previously sterilized (>80 °C in nutrient poor environments), necessitating the re-introduction of microbes into the subsurface via groundwater transport.     

天然气甲烷碳同位素动力学模型与地质应用新进展

天然气甲烷碳同位素动力学模拟是在热模拟实验的基础上对甲烷碳同位素值进行数字模拟的一种研究方法。它在石油、天然气地球化学中具有广阔的应用前景：模拟甲烷碳同位素的整个演化趋势，模拟天然气成藏，进行精确的气源对比。分析了国外几个典型的甲烷碳同位素动力学模型，对各模型的特点和优缺点进行了简要的评述，并认识到Cramer 3是目前对实验数据模拟效果最好、适用范围最宽的一个模型。在此基础上，结合一些研究实例，探讨了天然气甲烷碳同位素动力学研究的发展方向。     

热成因甲烷碳同位素分布的形成机制

很多学者从不同的角度用不同的方法模拟了从有机母质 (包括煤和干酪根等气源 )形成天然气 (甲烷 )时的碳同位素分馏效应 ,建立了碳同位素分馏效应的很多模型 ,同时也讨论了催化作用和成烃后作用对天然气碳同位素的影响。但这些理论模型和模拟实验结果都还不能完全地拟合自然界中热成因甲烷碳同位素的分布 ,也未能从本质上完全阐明其碳同位素的分馏机制。其原因是各种模型的前提假设都未能完全满足复杂的自然界条件。今后工作的重点应放在用化学动力学的方法建立更完善的模型上 ,同时也应当重点考虑催化作用和成烃后作用对天然气同位素的影响。     

Carbon and oxygen isotope fractionation in scleractinian corals: a review

The present theories on the fractionation of stable isotopes in scleractinian corals are critically discussed in the light of data available on primary productivity, respiration and stable isotope chemistry. These data support a model of fractionation in which the carbon and oxygen isotopes are decoupled. Calcification occurs from a reservoir of carbon dioxide derived from both organic and inorganic sources. Photosynthesis preferentially fixes¹³C and thereby leaves behind¹³C. Increases in the rate of photosynthesis therefore also enrich the carbon isotope ratio of the skeleton. From theoretical considerations, photosynthesis has little effect on the oxygen isotope ratio of the skeleton, a fact confirmed by available data. The process of respiration adds depleted carbon and oxygen to the calcification reservoirs. The varying correlations between carbon and oxygen isotopes seen in hermatypic corals are caused by changes in the relationship between photosynthesis and respiration at different geographical localities. The isotopic compositions in the skeletons of non-zooxanthellate corals, which show a consistent positive correlation, can also be explained by the above scenario.     

Origin of light hydrocarbon gases from the Matsukawa geothermal area in Japan

Light hydrocarbon and isotope compositions of methane were analyzed in well steam samples from the Matsukawa vapour-dominated type geothermal system. Alkanes (C₁-C₄) and alkene (C₂) were detected in all samples. Light hydrocarbon contents of CO₂-type steam are slightly higher than those of CO₂-H₂S-type steam. The isotope composition of methane and the relationship between methane/ethane ratio and δ¹³C-value of methane suggest that these light hydrocarbon gases are mixtures of thermogenic and abiogenic components. The abiogenic hydrocarbon may be attributed to magmatic hydrocarbon gases equilibrated with carbon dioxide at f_o2 defined by the fayalite-magnetite-quartz buffer (FMQ).     

Origin and Accumulation of Natural Gases in the Upper Paleozoic Strata of the Ordos Basin in Central China

The natural gases in the Upper Paleozoic strata of the Ordos basin are characterized by relatively heavy C isotope of gaseous alkanes with δ 13C1 and δ13C2 values ranging mainly from ?35‰ to ?30‰ and ?27‰ to ?22‰, respectively, high δ13C excursions (round 10) between ethane and methane and predominant methane in hydrocarbon gases with most C1/(C1-C5) ratios in excess of 0.95, suggesting an origin of coal-derived gas. The gases exhibit different carbon isotopic profiles for C1-C4 alkanes with those of the natural gases found in the Lower Paleozoic of this basin, and believed to be originated from Carboniferous-Permian coal measures. The occurrence of regionally pervasive gas accumulation is distinct in the gently southward-dipping Shanbei slope of the central basin. It is noted that molecular and isotopic composition changes of the gases in various gas reservoirs are associated with the thermal maturities of gas source rocks. The abundances and δ13C values of methane generally decline northwards and from the basin center to its margins, and the effects of hydrocarbon migration on compositional modification seem insignificant. However, C isotopes of autogenetic calcites in the vertical and lateral section of reservoirs show a regular variation, and are as a whole depleted upwards and towards basin margins. Combination with gas maturity gradient, the analysis could be considered to be a useful tool for gas migration.