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.     

Kinetic-simulating experiment combined with GC-IRMS analysis: application to identification and assessment of coal-derived methane from Zhongba Gas Field (Sichuan Basin, China)

The main purpose of this study is to model the δ¹³C values of methane derived from coal by combining kinetic-simulating experiment with the gas chromatography-isotope ratio mass spectrum (GC-IRMS) analysis. The stable carbon isotopic variation of methane in pyrolysates with heating temperature indicates that the assumptions for both a constant kinetic isotope effect (α) and a uniform initial isotopic composition (δ¹³C_o) are impractical for explaining the carbon isotopic fractionation during coalification. For purposes of simplification, two approaches are used in this paper to deal with the heterogeneity of terrestrial organic matter. One is that, assuming a uniform initial isotopic composition (i.e., δ¹³C_{i, o}=δ¹³C_o) for all methane-generating precursors in coal, the isotopic variation of methane is fitted by adjusting ΔE_{a, i} (E_{a¹³C, i}−E_{a¹²C, i}) for each hypothetical reaction. The other is that, assuming a constant kinetic isotope effect during the whole gas formation, that is all ΔE_{a, i} values are identical, the modeling of methane isotopic composition is achieved by changing the ¹³CH₄ generation potential of each reaction (f_{i, ¹³C}), namely, by adjusting the initial δ¹³C value (δ¹³C_{i, o}) for each methane-generating precursor. Results of the kinetic calculation shows that the two simulating methods can yield a similar result at a geological heating rate of 2 °C/My, which further demonstrates that those natural gases with methane δ¹³C value being approximately −36‰ are possibly sourced from the upper Triassic coal measure strata in the Northwestern Sichuan Basin.     

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%.     

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.     

Geochemical characteristics and possible origin of natural gas in the Taibei Depression,Turpan-Hami Basin,China

292 chemical composition data and 82 isotopic composition data of gas samples collected from the Taibei Depression of the Turpan-Hami Basin, West China, were used in the study of their origin. Non-hydrocarbon gas is poor in most samples whereas abundant nitrogen in some samples is positively correlated with δ13C1. Although methane is the main constituent, higher molecular gaseous hydrocarbons, from ethane to pentane, are detected in most samples, in accordance with the distribution of oil reservoirs. The stable carbon isotope ratios of methane, eth-ane and propane are defined as d13C1: -45.5‰ to -33.5‰, d13C2: -30.2‰ to -10.5‰, and d13C3: 27.6‰ to -11.2‰, respectively. According to the distribution of carbon isotope ratios, 2 families of gas can be grouped, most showing normal distribution of carbon isotopes, and others having obvious heavier carbon isotopes and being of abnormal distribution. Based on the isotopic composition, the disagreement between the relationship of Δ(d13C1-d13C2) and d13C2 and that of Δ(d13C1-d13C2) and d13C2, and the calculated Ro, there are oil-associated gas, coal-derived gas and mixture of them. Other samples with obviously heavier isotopic compositions from the Yanmuxi oilfield of the Taibei Depression have been degraded by organisms.     

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.     

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

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

New Approaches and Markers for Identifying Secondary Biogenic Coalbed Gas

According to the adsorption-desorption characteristics of coalbed gas and analysis of various experimental data, this paper proposes that the generation of secondary biogenic gas (SBG) and its mixing of with the residual thermogenic gas at an early stage inevitably lead to secondary changes of the thermogenic gas and various geochemical additive effects. Experimental results also show that the fractionation of the carbon isotope of methane of coal core desorption gas changes very little; the δ13C1 value of the mixed gas of biogenic and thermogenic gases is between the δ13C1 values of the two “original” gases, and the value is determined by the carbon isotopic compositions and mixing proportions of the two “original” methanes. Therefore this paper proposes that the study on the secondary changes of the thermogenic gas and various additive effects is a new effective way to study and identify SBG. Herein, a systematic example of research on the coalbed gas (Huainan coalbed gas) is further conducted, revealing a series of secondary changes and additive effects, the main characteristics and markers of which are: (1) the contents of CO2 and heavy-hydrocarbons decrease significantly; (2) the content of CH4 increases and the gas becomes drier; (3) the δ13C and δD values of methane decrease significantly and tend to have biogenetic characteristics; and (4) the values of δ13C2 and δ13CCO2 grow higher. These isotopic values also change with the degradation degrees by microbes and mixing proportions of the two kinds of gases in different locations. There exists a negative correlation between the δ13C1 vs δ13CCO2 values. The △δ13CC2–C1 values obviously become higher. The distributions of the △δ13CCO2–C1 values are within certain limits and show regularity. There exist a positive correlation between the N2 versus Ar contents, and a negative correlation between the N2 versus CH4 contents, indicating the down forward infiltration of the surface water containing air. These are important markers of the generation and existence of SBG.     

塔里木盆地西部阿克莫木气田形成初探

塔里木盆地西部阿克莫木气田天然气为非烃组份含量较高的干气,干燥系数高达99.7%;天然气δ¹³C₁和δ¹³C₂值明显偏重,δ¹³C₁为- 25.2‰～-21.9,δ¹³C₂为-21.2～-20.2‰,如果按传统的观点该天然气应为过成熟煤成气。但是综合气源对比研究表明阿克莫木气田天然气主要源自石炭系Ⅱ型烃源岩,成藏过程研究表明该气田主要聚集了石炭系烃源岩在Ro为1.5%～1.8%之后生成的天然气,具有晚期阶段聚气的特征,这是造成阿克1井天然气组份很“干”、碳同位素很重的主要原因。     

Stable carbon isotope composition and concentrations of CO2 and CH4 in the deep catotelm of a peat bog

Vertical profiles of concentration and C-isotopic composition of dissolved methane and carbon dioxide were observed over 26 months in the catotelm of a deep (6.5 m) peat bog in Switzerland. The dissolved concentrations of these gases increase with depth while CO₂ predominates over CH₄ (CO₂ ca. 5 times CH₄). This pattern can be reproduced by a reaction-advection-ebullition model, where CO₂ and CH₄ are formed in a ratio of 1:1. The less soluble methane is preferentially lost via outgassing (bubbles). The isotopic fractionation between CO₂ and CH₄ also increases with depth, with α_C values ranging from 1.045 to 1.075. The isotopic composition of the gases traces the passage of respiration-derived CO₂ (from the near surface) through a shallow zone with methanogenesis of low isotopic fractionation (splitting of fermentation-derived acetate). This solution then moves through the catotelm, where methanogenesis occurs by CO₂ reduction (large isotopic fractionation). In the upper part of the catotelm the C-13-depleted respiration-derived CO₂ pool buffers the isotopic composition of CO₂; the δ¹³C of CO₂ increases only slowly. At the same time strongly depleted CH₄ is formed as CO₂ reduction consumes the depleted CO₂. In the lower part of the catotelm, the respiration-derived CO₂ and shallow CH₄ become less important and CO₂ reduction is the dominant source of CO₂ and CH₄. Now, the δ¹³C values of both gases increase until equilibrium is reached with respect to the isotopic composition of the substrate. Thus, the δ¹³C values of methane reach a minimum at intermediate depth, and the deep methane has δ¹³C values comparable to shallow methane. A simple mixing model for the isotopic evolution is suggested. Only minor changes of the observed patterns of methanogenesis (in terms of concentration and isotopic composition) occur over the seasons. The most pronounced of these is a slightly higher rate of acetate splitting in spring.     

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

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

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.     

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.     

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.     

Carbon isotope composition of sedimentary rocks in the southern Siberian Platform and surrounding fold systems

Organic carbon isotope composition was studied in the sedimentary cover of the southern Siberian Platform and its surrounding fold systems. The rocks experienced catagenesis, metamorphism, and metasomatism. The chloroform bitumoid (CB) has a stable carbon isotope composition within a wide range of postsedimentation transformations. The average values of δ¹³C in CB of the sedimentary cover are ?29.5‰. Metamorphism and, especially, ore metasomatism, at the Sukhoi Log deposit caused a 2‰ increase in the heavy carbon isotope concentration of CB as compared to that of the platform deposits. The narrow variations in carbon isotope composition of the bitumoid are defined by their derivation from lipids, whose components are almost insusceptible to changes in the PT conditions. Kerogen from platform deposits is more strongly depleted than CB in the heavy carbon isotope (δ¹³C_av ? 32.2‰). The insoluble carbonaceous matter (ICM) of the metamorphic shales is significantly enriched in the heavy carbon isotope (δ¹³C_av ? 21.9‰). The highest changes in carbon isotope composition were found in concentrates of ICM from metasomatically altered rocks of the Sukhoi Log deposit (δ¹³C_av ? 17.5‰). The heavier carbon isotope composition caused by metamorphism and metasomatism is evidently defined by isotopic exchange between the carbonate carbon and CO₂ of metasomatic solutions, on one hand, and ICM of shales, on the other.     

Formation and abundance of doubly-substituted methane isotopologues (CH3D) in natural gas systems

Formation of the Carbon-13 (¹³C) and deuterium (D) doubly-substituted methane isotopologues (¹³CH₃D) in natural gases is studied utilizing both first-principle quantum mechanism molecular calculation and direct FTIR laboratorial measurements of specifically synthesized high isotope concentration methane gas. For ¹³CH₃D, the symmetrically breathing mode A₀ emerges as IR-detectable attributed to the molecular symmetry lowering to C_3v from T_d of the non-isotopic methane (CH₄), along with a large vibrational frequency shift from ∼3000 to ∼2250 cm⁻¹. Our studies also indicate that the concentration of ¹³CH₃D is dependent on the environmental temperature through isotope exchanges among methane isotopologues; and the Gibbs’ Free Energy difference due to Quantum Mechanics Zero-Point vibrational motions has the major contribution to this temperature dependency. Potential geologic applications of the ¹³CH₃D measurement to natural gas exploration and assessments are also discussed. In order to detect the ¹³CH₃D concentration change of each 50 °C in the natural gas system, a 10⁻⁹ resolution is desirable. Such a measurement could provide important add-on information to distinguish natural gas origin and distribution.     

Quantification of carbon flow from stable isotope fractionation in rice field soils with different organic matter content

Rice fields are an important source for the greenhouse gas methane produced by acetoclastic and hydrogenotrophic methanogenesis. Fractionation of ¹³C/¹²C can in principle be used to quantify the relative contribution of these pathways, but our knowledge of isotopic fractionation during reduction of CO₂ and turnover of acetate in different methanogenic environments is still scarce. We therefore measured δ¹³C signatures in two types of anoxic Italian rice field soils, one with high and one with low degradable organic matter (OM) content. Both soils were incubated in the presence and absence of methyl fluoride, a specific inhibitor of acetoclastic methanogenesis. Optimization of methyl fluoride concentration resulted in complete inhibition of acetoclastic methanogenesis. CH₄ was then exclusively produced by hydrogenotrophic methanogenesis, allowing determination of the isotopic signatures and fractionation factors specific for this methanogenic pathway. Acetate, which was then no longer consumed, accumulated and was used for determination of the isotopic signature of the fermentatively produced acetate (both total acetate and methyl carbon of acetate). Hence, all isotopic signatures, including fractionation factors were determined for the methanogenic soil. These data, were then used for computation of the relative contribution of the two methanogenic pathways. In the high OM soil, the contribution of acetoclastic methanogenesis to total CH₄ production increased simultaneously with decreasing acetate concentration. In the low OM soil, methanogenesis from H₂/CO₂ was clearly greater than theoretically expected. Furthermore, isotope fractionation of hydrogenotrophic methanogenesis indicated that the in situ energy status of methanogens strongly depended on the availability of organic carbon in the rice field soil system. Collectively, our data show that the study of isotopic fractionation in methanogenic environments allows a deeper insight into the ongoing processes, which may be quite different in the same ecosystem with different content of degradable OM.     

Carbon and hydrogen isotopic compositions of products of open-system catalytic hydrogenation of CO2: Implications for abiogenic hydrocarbons in Earth’s crust

This paper reports the isotope effects in an open-system Fischer-Tropsch type (FTT) synthesis, with implications for the origin of natural abiogenic hydrocarbons. The starting form of carbon was CO₂, with carbon and hydrogen isotopic compositions measured for products of catalytic hydrogenation of CO₂ on iron and cobalt catalysts (FTCO₂-Fe and FTCO₂-Co) at 350 and 245 °C, respectively, and 10 MPa. The carbon isotopic composition of the resulting saturated hydrocarbons (alkanes) as a function of carbon number shows a positive trend for both FTCO₂-Fe and FTCO₂-Co, with a fractionation of 2-4‰ and 3-6‰ between CH₄ and C₂H₆ over the Fe and Co catalysts, respectively. The unsaturated hydrocarbons (alkenes) do not show any trend. A strong kinetic isotope fractionation (>40‰) occurred between CO₂ and CH₄ in both experiments. The hydrogen isotope fractionation between alkanes appeared to be similar to that found in natural (thermogenic and biogenic) gases, with enrichment in deuterium of longer hydrocarbon chains; the dominant H/D fractionation occurred between CH₄ and C₂H₆. Alkenes in the products of the FTCO₂-Fe reaction are enriched in deuterium (∼50‰) and do not show any trend versus carbon number. We suggest that other than FTT reactions or a simple mixing are responsible for the occurrence of the inverse isotopic trends in both δ¹³C and δD found in light hydrocarbons in some terrestrial environments and meteorites.     

Natural gas potential of Neoproterozoic and lower Palaeozoic marine shales in the Upper Yangtze Platform,South China: geological and organic geochemical characterization

In this article, we describe the geological features of the Ediacaran (upper Sinian), lower Cambrian and lower Silurian shale intervals in the Upper Yangtze Platform, South China, and report on the gas potential of 53 samples from these major marine shale formations. Reflected light microscopy, total organic carbon (TOC) measurement, Rock-Eval, carbon isotope ratio analysis, thermovaporization gas chromatography (Tvap-GC), and open pyrolysis gas chromatography (open py-GC) were used to characterize the organic matter. Measured TOC in this research is normally >2% and averages 5%. TOC contents are roughly positively correlated with increasing geological age, i.e. lower Silurian shales exhibit generally lower TOC contents than lower Cambrian shales, which in turn commonly have lower TOC contents than Ediacaran shales. Kerogen has evolved to the metagenesis stage, which was demonstrated by the abundant pyrobitumen on microphotographs, the high calculated vitrinite reflectance (R_o = 3%) via bitumen reflectance (R_b), as well as δ¹³ C of gas (methane) inclusions. Pyrolysates from Tvap-GC and open py-GC are quantitatively low and only light hydrocarbons were detected. The lower Silurian shale generally exhibits higher generation of hydrocarbon than the lower Cambrian and Ediacaran shale. Cooles’ method and Claypool’s equations were used to reconstruct the original TOC and Rock-Eval parameters of these overmature samples. Excellent original hydrocarbon generation was revealed in that the original TOC (TOC_o) is between 5% and 23%, and original S1+S2 (S1_o+S2_o) is ranging from 29 to 215 mg HC/g rock.     

Mathematical simulation of the carbon isotopic fractionation between huminitic coals and related methane

In order to estimate the isotope fractionation effect between coals and methane during coalification a maturity-related fractionation model has been developed for coals and reservoir gases of NW Germany which is based on empirical data. Assuming that observed isotope shifts of the convertible carbon of coals of different maturities are related to a loss of methane during coalification and that this shift can be described by a Rayleigh distillation process, functions with preselected fractionation factors were fitted to measured isotope data of the convertible carbon of coals. The best approximation of theoretical and measured data was achieved with a low fractionation factor (α_c= 1.003). Using this model theoretical methane carbon isotope data were determined and compared to the isotopic composition of reservoir methanes of NW Germany. Although the methane isotope data of reservoir gases and the related maturity of the coals show a slight scatter, the theoretical data plot within the same range and follow the increase of the ¹³C concentration of reservoir gases with increasing maturity of the coals.