Isotopic identification of the source of methane in subsurface sediments of an area surrounded by waste disposal facilities

The major source of methane (CH₄) in subsurface sediments on the property of a former hazardous waste treatment facility was determined using isotopic analyses measured on CH₄ and associated groundwater. The site, located on an earthen pier built into a shallow wetland lake, has had a history of waste disposal practices and is surrounded by landfills and other waste management facilities. Concentrations of CH₄ up to 70% were found in the headspace gases of several piezometers screened at 3 different depths (ranging from 8 to 17 m) in lacustrine and glacial till deposits. Possible sources of the CH₄ included a nearby landfill, organic wastes from previous impoundments and microbial gas derived from natural organic matter in the sediments.Isotopic analyses included δ¹³C, δD, ¹⁴C, and ³H on select CH₄ samples and δD and δ¹⁸O on groundwater samples. Methane from the deepest glacial till and intermediate lacustrine deposits had δ¹³C values from −79 to −82‰, typical of natural “drift gas” generated by microbial CO₂-reduction. The CH₄ from the shallow lacustrine deposits had δ¹³C values from −63 to −76‰, interpreted as a mixture between CH₄ generated by microbial fermentation and the CO₂-reduction processes within the subsurface sediments. The δD values of all the CH₄ samples were quite negative ranging from −272 to −299‰. Groundwater sampled from the deeper zones also showed quite negative δD values that explained the light δD observed for the CH₄. Radiocarbon analyses of the CH₄ showed decreasing ¹⁴C activity with depth, from a high of 58 pMC in the shallow sediments to 2 pMC in the deeper glacial till. The isotopic data indicated the majority of CH₄ detected in the till deposits of this site was microbial CH₄ generated from naturally buried organic matter within the subsurface sediments. However, the isotopic data of CH₄ from the shallow piezometers was more variable and the possibility of some mixing with oxidized landfill CH₄ could not be completely ruled out.     

Kinetic Model of Gaseous Alkanes Formed from Coal in a Confined System and Its Application to Gas Filling History in Kuqa Depression, Tarim Basin, Northwest China

Based on the pyrolysis products for the Jurassic low-mature coal under programmed temperature,and chemical and carbon isotopic compositions of natural gas from the Kuqa Depression, the genetic origin of natural gas was determined,and then a gas filling model was established,in combination with the geological background of the Kuqa Depression.The active energy of CH_4,C_2H_6 and C_3H_8 was gotten after the data of pyrolysis gas products under different heating rates(2℃/h and 20℃/h)were fitted by the Gas O...     

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.     

Origin,distribution and hydrogeochemical controls on methane occurrences in shallow aquifers,southwestern Ontario,Canada

Natural gas reservoirs in organic-rich shales in the Appalachian and Michigan basins in the United States are currently being produced via hydraulic fracturing. Stratigraphically-equivalent shales occur in the Canadian portion of the basins in southwestern Ontario with anecdotal evidence of gas shows, yet there has been no commercial shale gas production to date. To provide baseline data in the case of future environmental issues related to hydraulic fracturing and shale gas production, such as leakage of natural gas, saline water, and/or hydraulic fracturing fluids, and to evaluate hydrogeochemical controls on natural gas accumulations in shallow groundwater in general, this study investigates the origin and distribution of natural gas and brine in shallow aquifers across southwestern Ontario. An extensive geochemical database of major ion and trace metal chemistry and methane concentrations of 1010 groundwater samples from shallow, domestic wells in bedrock and overburden aquifers throughout southwestern Ontario was utilized. In addition, select wells (n = 36) were resampled for detailed dissolved gas composition, δ¹³C of CH₄, C₂, C₃, and CO₂, and δD of CH₄. Dissolved gases in groundwater from bedrock and overburden wells were composed primarily of CH₄ (29.7–98.6 mol% of total gas volume), N₂ (0.8–66.2 mol%), Ar + O₂ (0.2–3.4 mol%), and CO₂ (0–1.2 mol%). Ethane was detected, but only in low concentrations (<0.041 mol%), and no other higher chain hydrocarbons were present, except for one well in overburden overlying the Dundee Formation, which contained 0.81 mol% ethane and 0.21 mol% propane. The highest methane concentrations (30 to >100 in situ % saturation) were found in bedrock wells completed in the Upper Devonian Kettle Point Formation, Middle Devonian Hamilton Group and Dundee Formation, and in surficial aquifers overlying these organic-rich shale-bearing formations, indicating that bedrock geology is the primary control on methane occurrences. A few (n = 40) samples showed Na–Cl–Br evidence of brine mixing with dilute groundwater, however only one of these samples contained high (>60 in situ % saturation) CH₄. The relatively low δ¹³C values of CH₄ (−89.9‰ to −57.3‰), covariance of δD values of CH₄ and H₂O, positive correlation between δ¹³C values of CH₄ and CO₂, and lack of higher chain hydrocarbons (C₃₊) in all but one dissolved gas sample indicates that the methane in groundwater throughout the study area is primarily microbial in origin. The presence or absence of alternative electron acceptors (e.g. dissolved oxygen, Fe, NO₃, SO₄), in addition to organic substrates, controls the occurrence of microbial CH₄ in shallow aquifers. Microbial methane has likely been accumulating in the study area, since at least the Late Pleistocene to the present, as indicated by the co-variance and range of δD values of CH₄ (−314‰ to −263‰) and associated groundwater (−19‰ to −6‰ δD-H₂O).     

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。     

Composition and origin of coalbed gases in the Lower Silesian basin,southwest Poland

Coalbed gases in the Lower Silesian Coal Basin (LSCB) of Poland are highly variable in both their molecular and stable isotope compositions. Geochemical indices and stable isotope ratios vary within the following ranges: hydrocarbon (C_HC) index C_HC=CH₄/(C₂H₆₊ C₃H₈) from 1.1 to 5825, wet gas (C₂₊) index C₂₊=(C₂H₆₊ C₃H₈₊ C₄H₁₀₊ C₅H₁₂) / (CH₄₊ C₂H₆₊ C₃H₈₊ C₄H₁₀₊ C₅H₁₂) 100 (%) from 0.0 to 48.3%, CO₂–CH₄ (CDMI) index CDMI=CO₂/(CO₂₊ CH₄) 100 (%) from 0.1 to 99.9%, δ¹³C(CH₄) from −66.1 to −24.6‰, δD(CH₄) from −266 to −117‰, δ¹³C(C₂H₆) from −27.8 to −22.8‰, and δ¹³C(CO₂) from −26.6 to 16.8‰. Isotopic studies reveal the presence of 3 genetic types of natural gases: thermogenic (CH₄, higher gaseous hydrocarbons, and CO₂), endogenic CO₂, and microbial CH₄ and CO₂. Thermogenic gases resulted from coalification processes, which were probably completed by Late Carboniferous and Early Permian time. Endogenic CO₂ migrated along the deep-seated faults from upper mantle and/or magma chambers. Minor volumes of microbial CH₄ and CO₂ occur at shallow depths close to the abandoned mine workings. “Late-stage” microbial processes have commenced in the Upper Cretaceous and are probably active at present. However, depth-related isotopic fractionation which has resulted from physical and physicochemical (e.g. diffusion and adsorption/desorption) processes during gas migration cannot be neglected. The strongest rock and gas outbursts occur only in those parts of coal deposits of the LSCB which are dominated by large amounts of endogenic CO₂.     

Application of sulfur and carbon isotopes to oil–source rock correlation: A case study from the Tazhong area,Tarim Basin,China

Up until now, it has been assumed that oil in the Palaeozoic reservoirs of the Tazhong Uplift was derived from Upper Ordovician source rocks. Oils recently produced from the Middle and Lower Cambrian in wells ZS1 and ZS5 provide clues concerning the source rocks of the oils in the Tazhong Uplift, Tarim Basin, China. For this study, molecular composition, bulk and individual n-alkane δ¹³C and individual alkyl-dibenzothiophene δ³⁴S values were determined for the potential source rocks and for oils from Cambrian and Ordovician reservoirs to determine the sources of the oils and to address whether δ¹³C and δ³⁴S values can be used effectively for oil–source rock correlation purposes. The ZS1 and ZS5 Cambrian oils, and six other oils from Ordovician reservoirs, were not significantly altered by TSR. The ZS1 oils and most of the other oils, have a “V” shape in the distribution of C₂₇–C₂₉ steranes, bulk and individual n-alkane δ¹³C values predominantly between −31‰ to −35‰ VPDB, and bulk and individual alkyldibenzothiophene δ³⁴S values between 15‰ to 23‰ VCDT. These characteristics are similar to those for some Cambrian source rocks with kerogen δ¹³C values between −34.1‰ and −35.3‰ and δ³⁴S values between 10.4‰ and 21.6‰. The oil produced from the Lower Ordovician in well YM2 has similar features to the ZS1 Cambrian oils. These new lines of evidence indicate that most of the oils in the Tazhong Uplift, contrary to previous interpretations, were probably derived from the Cambrian source rocks, and not from the Upper Ordovician. Conversely, the δ¹³C and δ³⁴S values of ZS1C Cambrian oils have been shown to shift to more positive values due to thermochemical sulfate reduction (TSR). Thus, δ¹³C and δ³⁴S values can be used as effective tools to demonstrate oil–source rock correlation, but only because there has been little or no TSR in this part of the section.     

Abiotic methane seepage in the Ronda peridotite massif,southern Spain

Abiotic methane in serpentinized peridotites (MSP) has implications for energy resource exploration, planetary geology, subsurface microbiology and astrobiology. Once considered a rare occurrence on Earth, reports of MSP are increasing for numerous localities worldwide in low temperature, land-based springs and seeps. We report the discovery of six methane-rich water springs and two ponds with active gas bubbling in the Ronda peridotite massif, in southern Spain. Water is hyperalkaline with typical hydrochemical features of active serpentinization (pH: 10.7 to 11.7, T: 17.1 to 21.5 °C, Ca–OH facies). Dissolved CH₄ concentrations range from 0.1 to 3.2 mg/L. The methane stable C and H isotope ratios in the natural spring and bubbling sites (δ¹³C_CH4: −12.3 to −37‰ VPDB; δ²H_CH4: −280 to −333‰ VSMOW) indicate a predominant abiotic origin. In contrast, springs with manmade water systems, i.e., pipes or fountains, appear to have mixed biotic-abiotic origin (δ¹³C_CH4: −44 to −69‰; δ²H_CH4: −180 to −319‰). Radiocarbon (¹⁴C) analyses show that methane C in a natural spring is older than ca. 50,000 y BP, whereas dissolved inorganic carbon (DIC) analysed in all springs has an apparent ¹⁴C age ranging from modern to 2334 y BP. Therefore most, if not all, of the CH₄ is allochthonous, i.e., not generated from the carbon in the hyperalkaline water. Methane is also released as bubbles in natural ponds and as diffuse seepages (∼10¹–10² mg CH₄ m⁻²d⁻¹) from the ground up to several tens of metres from the seeps and springs, albeit with no overt visual evidence. These data suggest that the gas follows independent migration pathways, potentially along faults or fracture systems, physically isolated from the hyperalkaline springs. Methane does not seem to be genetically related to the hyperalkaline water, which may only act as a carrier of the gas. Gas-bearing springs, vents and invisible microseepage in land-based peridotites are more common than previously thought. In addition to other geological sources, MSP is potentially a natural source of methane for the troposphere and requires more worldwide flux measurements.     

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.     

Chemical and isotope compositions of shallow groundwater in areas impacted by hydraulic fracturing and surface mining in the Central Appalachian Basin,Eastern United States

Hydraulic fracturing of shale deposits has greatly increased the productivity of the natural gas industry by allowing it to exploit previously inaccessible reservoirs. Previous research has demonstrated that this practice has the potential to contaminate shallow aquifers with methane (CH₄) from deeper formations. This study compares concentrations and isotopic compositions of CH₄ sampled from domestic groundwater wells in Letcher County, Eastern Kentucky in order to characterize its occurrence and origins in relation to both neighboring hydraulically fractured natural gas wells and surface coal mines. The studied groundwater showed concentrations of CH₄ ranging from 0.05 mg/L to 10 mg/L, thus, no immediate remediation is required. The δ¹³C values of CH₄ ranged from −66‰ to −16‰, and δ²H values ranged from −286‰ to −86‰, suggesting an immature thermogenic and mixed biogenic/thermogenic origin. The occurrence of CH₄ was not correlated with proximity to hydraulically fractured natural gas wells. Generally, CH₄ occurrence corresponded with groundwater abundant in Na⁺, Cl⁻, and HCO₃⁻, and with low concentrations of SO₄²⁻. The CH₄ and SO₄²⁻concentrations were best predicted by the oxidation/reduction potential of the studied groundwater. CH₄ was abundant in more reducing waters, and SO₄²⁻ was abundant in more oxidizing waters. Additionally, groundwater in greater proximity to surface mining was more likely to be oxidized. This, in turn, might have increased the likelihood of CH₄ oxidation in shallow groundwater.     

Geochemical characteristics of methane from sediments of the underwater high Posolskaya Bank (Lake Baikal)

The component and carbon isotope compositions were studied in the hydrocabon gases from sediments of the underwater high Posolskaya Bank (Lake Baikal). It was established that sediments of this Baikal area contain methane of microbial (C₁/C₂ >16000; δ¹³C 70 ± 3‰) and thermocatalytic (C₁/C₂ <100; δ¹³C–46 ± 3‰) origin. Some samples represent a gas mixture of thermocatalytic and microbial origin. This gas is characterized by δ¹³C of methane varying from–60 to–70‰ and contains a significant amount of ethane. The main homolog of methane in the thermocatalytic and mixed gas is ethane. Owing to biodegradation, propane and butanes are present in trace amounts.     

Gas genetic type and origin of hydrogen sulfide in the Zhongba gas field of the western Sichuan Basin, China

Natural gases and associated condensate oils from the Zhongba gas field in the western Sichuan Basin, China were investigated for gas genetic types and origin of H₂S by integrating gaseous and light hydrocarbon geochemistry, formation water compositions, S isotopes (δ³⁴S) and geological data. There are two types of natural gas accumulations in the studied area. Gases from the third member of the Middle Triassic Leikoupo Formation (T₂l³) are reservoired in a marine carbonate sequence and are characterized by high gas dryness, high H₂S and CO₂ contents, slightly heavy C isotopic values of CH₄ and widely variable C isotopic values of wet gases. They are highly mature thermogenic gases mainly derived from the Permian type II kerogens mixed with a small proportion of the Triassic coal-type gases. Gases from the second member of the Upper Triassic Xujiahe Formation (T₃x²) are reservoired in continental sandstones and characterized by low gas dryness, free of H₂S, slightly light C isotopic values of CH₄, and heavy and less variable C isotopic values of wet gases. They are coal-type gases derived from coal in the Triassic Xujiahe Formation.The H₂S from the Leikoupo Formation is most likely formed by thermochemical SO₄ reduction (TSR) even though other possibilities cannot be fully ruled out. The proposed TSR origin of H₂S is supported by geochemical compositions and geological interpretations. The reservoir in the Leikoupo Formation is dolomite dominated carbonate that contains gypsum and anhydrite. Petroleum compounds dissolved in water react with aqueous SO₄ species, which are derived from the dissolution of anhydrite. Burial history analysis reveals that from the temperature at which TSR occurred it was in the Late Jurassic to Early Cretaceous and TSR ceased due to uplift and cooling thereafter. TSR alteration is incomplete and mainly occurs in wet gas components as indicated by near constant CH₄ δ¹³C values, wide range variations of ethane, propane and butane δ¹³C values, and moderately high gas dryness. The δ³⁴S values in SO₄, elemental S and H₂S fall within the fractionation scope of TSR-derived H₂S. High organo-S compound concentrations together with the occurrence of 2-thiaadamantanes in the T₂l reservoir provide supplementary evidence for TSR related alteration.     

Geochemistry and origins of natural gases in the central Junggar Basin,northwest China

The petroliferous central Junggar Basin in northwest China is predominantly an oil exploration region. However, its gas exploration also might have good prospects. Thus to assist in gas exploration, the geochemistry and origins of gases are discussed in this paper based on relatively comprehensive analyses of compositions, carbon isotopes and light hydrocarbons of gases. Based on the results, the gas genetic types are grouped into families and combined with the geological setting (e.g., biomarkers of retrograde condensates and source rock characteristics). We show that there are four representative genetic types of gases. The first consists of gases derived from Permian lacustrine mudstones with type I–II kerogen and type III kerogen sources in the Penyijingxi sag. Their representative geochemical feature is δ¹³C₂ ranging from −31.4‰ to −24.7‰. The second is gas sourced from Carboniferous tufaceous mudstones of type III kerogen in the Dishuiquan sag, whose representative geochemical feature is the heaviest values of δ¹³C₁ in the studied samples, ranging from −32.0‰ to −30.4‰. The third consists of gases sourced from Jurassic coals and mudstones in the Shawan–Fukang sag. The light hydrocarbon fingerprints of these gases are similar to those of gases and oils typically derived from Jurassic source rocks in the southern Junggar Basin. The fourth is gas most likely generated from the degradation of crude oil. It is mainly found in the Luliang area and has dryness values as much as 0.999 and δ¹³C₁ ranging from −54.8‰ to −43.2‰. Among these four types of gases, the first (mainly sourced from the Permian lacustrine mudstones in the Penyijingxi sag) is the predominant type.     

Carbon-Isotope Characteristics of CO2 and CH4 in Geothermal Springs from the Central Andes

Carbon stable-isotope compositions of coexisting carbon dioxide and methane from geothermal springs across the Central Andes of northern Chile and Bolivia are reported. A total of 60 samples were analyzed for δ¹³C_CO2 and, of these, 10 were selected for δ¹³C_CH4 analyses. The Central Andes are characterized by an active volcanic arc and an unusually thick (up to 75 km) continental crust behind the arc, beneath the high plateau region of the Altiplano. Furthermore, helium-isotope evidence suggests active mantle degassing in a 350-km-wide zone beneath the thick continental crust in the Central Andes (Hoke et al., 1994).

The present results show a wide range of δ¹³C_CO2 (-14.9 to -0.6‰) and a surprisingly heavy δ¹³C_CH4 (?20.9 to ?12.3‰). The difference between δ¹³C_CO2 and δ¹³C_CH4 (δ¹³C_CO2-CH4 ) for individual samples varies between 1.5‰ and 13.5‰. The δ¹³C_CO2 results show wide and overlapping ranges in the samples collected from the Precordillera, the Volcanic Arc (or Western Cordillera), the Altiplano, and the Eastern Cordillera. The widest ranges occur in the Eastern Cordillera (?15.0 to ?4.8‰) and the Altiplano (?20 to ?6‰). The δ¹³C_CO2 results for geothermal samples from the Volcanic Arc range between ?8.0‰ (Surire) and ?0.6‰ (Abra de Nappa), whereas δ¹³C_CO2 measured in gases collected from geothermal springs in the Precordillera range from ?10 to ?5‰.

The relationships between 3He/4He, δ¹³C_CO2 , and δ¹³C_CH4 are used to distinguish between crustal and mantle origins. The wide (21‰) range in the is interpreted to reflect contributions from different CO₂ sources that include organic and inorganic crustal and mantle carbon. Assuming isotopic equilibrium between coexisting methane and carbon dioxide, Δ¹³C_CO2-CH4 suggests very high equilibrium temperatures, in excess of 530°C, for some geothermal systems that also are characterized by a high (up to 63%) mantle-derived helium component.

δ¹³C_CH4 results suggest that methane has not formed by bacteriogenic processes or by thermal decomposition of organic matter, but rather abiogenically through the high-temperature reaction between H₂ and CO₂. The δ¹³C_CH4 results for the samples from the Volcanic Arc and from two CO₂-rich geothermal springs in the Altiplano (Coipasa-2 and Belen de Andamarca) are similar to those reported from hydrothermal fluids emitted from the East Pacific Rise (Welhan, 1988) and White Island, New Zealand (Hulston and McCabe, 1962), suggesting a mantle-derived carbon component in the methane.     

Determining the origin of carbon dioxide and methane in the gaseous emissions of the San Vittorino plain (Central Italy) by means of stable isotopes and noble gas analysis

The chemistry and isotope ratios of He, C (δ¹³C) and H (δD) of free gases collected in the San Vittorino plain, an intramontane depression of tectonic origin, were determined to shed light on mantle degassing in central Italy. The C isotopic composition of CO₂ (δ¹³C–CO₂ −2.0‰ to −3.8‰) and He isotope ratios (R/R_A 0.12–0.27) were used to calculate the fraction of CO₂ originating from mantle degassing vs. sedimentary sources. The results show that CO₂ predominantly (average of 75%) derives from the thermo-metamorphic reaction of limestone. Between 6% and 22% of the CO₂ in the samples derives from organic-rich sedimentary sources. The mantle source accounts for 0–6% of the total CO₂; however, in two samples, located in proximity to the most important faults of the plain, the mantle accounts for 24% and 42%. The presence of faults and fractures allows upward gas migration from a deep source to the Earth’s surface, not only in the peri-Tyrrhenian sector, as generally reported by studies on natural gas emissions in central Italy, but also in the pre-Apennine and Apennine belts. Isotope ratios of CH₄ (δ¹³C–CH₄ −6.1‰ to −22.7‰; δD–CH₄ −9‰ to −129‰) show that CH₄ does not appear to be related to mantle or magma degassing, but it is the product of thermal degradation of organic matter (i.e. thermogenic origin) and/or the reduction of CO₂ (i.e. geothermal origin). Most of the samples appear to be affected by secondary microbial oxidation processes.     

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.     

Helium and carbon isotope systematics of natural gases from Taranaki Basin,New Zealand

The chemical and isotopic compositions of gases from hydrocarbon systems of the Taranaki Basin of New Zealand (both offshore and onshore) show wide variation. The most striking difference between the western and south-eastern groups of gases is the helium content and its isotopic ratio. In the west, the Maui gas is over an order of magnitude higher in helium concentration (up to 190 μmol mol⁻¹) and its ³He/⁴He ratio of 3.8 R_A (where R_A=the air ³He/⁴He ratio of 1.4×10⁻⁶) is approximately half that of upper mantle helium issuing from volcanic vents of the Taupo Volcanic Zone. In the SE, the Kupe South and most Kapuni natural gases have only a minor mantle helium input of 0.03–0.32 R_A and low total helium concentrations of 10–19 μmol mol⁻¹. The ³He/C ratio (where C represents the total carbon in the gas phase) of the samples measured including those from a recent study of on-shore Taranaki natural gases are generally high at locations where the surface heat flow is high. The ³He/CO₂ ratio of the Maui gases of 5 to 18×10⁻⁹ is higher than the MORB value of 0.2 to 0.5×10⁻⁹, a feature found in other continental basins such as the Pannonian and Vienna basins and in many high helium wells in the USA. Extrapolation to zero CO₂/³He and CO₂/C indicates δ¹³C(CO₂) values between −7 and −5‰ close to that of MORB CO₂. The remaining CO₂ would appear to be mostly organically-influenced with δ¹³C(CO₂) c.−15‰. There is some evidence of marine carbonate CO₂ in the gases from the New Plymouth field. The radiogenic ⁴He content (He_rad) varies across the Taranaki Basin with the highest He_rad/C ratios occurring in the Maui field. δ¹³C(CH₄) becomes more enriched in ¹³C with increasing He_rad and hydrocarbon maturity. Because ³He/⁴He is related to the ratio of mantle to radiogenic crustal helium and ³He/C is virtually constant in the Maui field, there is a correlation between R_C/R_A (where R_C=air-corrected ³He/⁴He) and δ¹³C(CH₄) in the Maui and New Plymouth fields, with the more negative δ¹³C(CH₄) values corresponding to high ³He/⁴He ratios. A correlation between ³He/⁴He and δ¹³C(CO₂) was also observed in the Maui field. In the fields adjacent to Mt Taranaki (2518 m andesitic volcano), correlations of some parameters, particularly CO₂/CH₄, C₂H₆/CH₄ and δ¹³C(CH₄), are present with increasing depth of the gas reservoir and with distance from the volcanic cone.     

Origin of hydrogen-nitrogen gas seeps,Oman

Six gas samples were collected from five thermal springs in the Semail Nappe ophiolite and the calcareous (calcite and dolomite) Hajar Formation, northern Oman. The³He/⁴He,⁴He/²⁰Ne,⁴⁰Ar/³⁶Ar and³⁸Ar/³⁶Ar ratios, chemical compositions (H₂, N₂, CO₂, CH₄, O₂, Ar and He), and stable isotope compositions (δD_H2, δD_H2O, δ¹³C_CO2, δ¹³C_CH4, and δ¹⁵N_N2) are reported. Samples from the ophiolite region are significantly anoxic with major constituents of H₂, CH₄ and N₂, while those from calcite and dolomite regions are ordinary gas seeps, consisting of N₂, CO₂ and/or O₂. The former H₂-rich gas is characterized by relatively high³He/⁴He ratio (0.4–0.8 R_atm) with low He content (<5 ppm), atmospheric⁴⁰Ar/³⁶Ar ratio, low N₂/Ar ratio (<55) and high δ¹⁵N_N2 value (∼1 ‰). On the other hand, the latter N₂-rich gas shows relatively low³He/⁴He ratio (0.1–0.4 R_atm) with high He concentration (>300 ppm), slight radiogenic⁴⁰Ar/³⁶Ar ratio, high N₂/Ar ratio (77–97) and low δ¹⁵N_N2 value (<0‰). Observed δD_H2 value of −536‰ in H₂-rich gas is distinguished from the literature value of −699‰ in the ophiolite region, giving discrepant isotope formation temperatures.     

The carbon isotopic composition of catalytic gas: a comparative analysis with natural gas

The idea that natural gas is the thermal product of organic decomposition has persisted for over half a century. Crude oil is thought to be an important source of gas, cracking to wet gas above 150°C, and dry gas above 200°C. But there is little evidence to support this view. For example, crude oil is proving to be more stable than previously thought and projected to remain intact over geologic time at typical reservoir temperatures. Moreover, when oil does crack, the products do not resemble natural gas. Oil to gas could be catalytic, however, promoted by the transition metals in carbonaceous sediments. This would explain the low temperatures at which natural gas forms, and the high amounts of methane. This idea gained support recently when the natural progression of oil to dry gas was duplicated in the laboratory catalytically. We report here the isotopic composition of catalytic gas generated from crude oil and pure hydrocarbons between 150 and 200°C. δ¹³C for C₁ through C₅ was linear with 1/n (n = carbon number) in accordance with theory and typically seen in natural gases. Over extended reaction, isobutane and isopentane remained lighter than their respective normal isomers and the isotopic differentials were constant as all isomers became heavier over time. Catalytic methane, initially −51.87‰ (oil = −22.5‰), progressed to a final composition of −26.94‰, similar to the maturity trend seen in natural gases: −50‰ to −20‰. Catalytic gas is thus identical to natural gas in molecular and isotopic composition adding further support to the view that catalysis by transition metals may be a significant source of natural gas.     

川东北飞仙关组甲烷为主的TSR及其同位素分馏作用

川东北开江-梁平陆棚东北侧飞仙关组多孔鲕粒白云岩中发生了以甲烷为主的热化学硫酸盐还原作用(TSR),产生高达20%的H₂S;而西南侧鲕粒灰岩以低孔、低H₂S天然气为特征。东北侧白云岩主要发育白云石粒间溶孔或粒间扩大溶孔,这些溶孔可与方解石(δ¹³C=-10‰~-19‰)、储层沥青、元素硫、黄铁矿和石英紧密共生,可分布于片状储层沥青与白云石晶体之间,说明白云石溶解作用发生在沥青形成以后。白云石的溶解作用导致现今天然气以无机CO₂为主,δ¹³C_CO2主要介于-2‰~+2‰之间。这种溶解作用是在酸性条件下,硬石膏或天青石参与下发生的,可能先产生MgSO₄配对离子,而后MgSO₄又与甲烷反应产生H₂S,净增大了孔隙。研究还发现,普光气田及以东天然气的来源不同于河坝和元坝天然气;对普光气田及以东天然气分析显示,甲烷δ¹³C值与残余烃含量 之间存在对数相关关系。这表明TSR过程中,甲烷同位素分馏作用遵从封闭体系下瑞利分馏原理。据此计算显示,渡4井约有15%甲烷被氧化了。