Carbon Isotopic Composition Of Methane Research Articles

Tracing of natural gas migration by light hydrocarbons: A case study of the Dongsheng gas field in the Ordos Basin, NW China

Based on the analysis of light hydrocarbon compositions of natural gas and regional comparison in combination with the chemical components and carbon isotopic compositions of methane, the indication of geochemical characteristics of light hydrocarbons on the migration features, dissolution and escape of natural gas from the Dongsheng gas field in the Ordos Basin is revealed, and the effect of migration on specific light hydrocarbon indexes is further discussed. The study indicates that, natural gas from the Lower Shihezi Formation (P1x) in the Dongsheng gas field displays higher iso-C5−7 contents than n-C5−7 contents, and the C6−7 light hydrocarbons are composed of paraffins with extremely low aromatic contents (<0.4%), whereas the C7 light hydrocarbons are dominated by methylcyclohexane, suggesting the characteristics of coal-derived gas with the influence by secondary alterations such as dissolution. The natural gas from the Dongsheng gas field has experienced free-phase migration from south to north and different degrees of dissolution after charging, and the gas in the Shiguhao area to the north of the Borjianghaizi fault has experienced apparent diffusion loss after accumulation. Long-distance migration in free phase results in the decrease of the relative contents of the methylcyclohexane in C7 light hydrocarbons and the toluene/n-heptane ratio, as well as the increase of the n-heptane/methylcyclohexane ratio and heptane values. The dissolution causes the increase of isoheptane values of the light hydrocarbons, whereas the diffusion loss of natural gas in the Shiguhao area results in the increase of n-C5−7 contents compared to the iso-C5−7 contents.

РАСПРЕДЕЛЕНИЕ И ГЕНЕЗИС УГЛЕВОДОРОДНЫХ ГАЗОВ ДОННЫХ ОТЛОЖЕНИЙ ЛАПТЕВО-СИБИРОМОРСКОЙ ЗОНЫ ВОСТОЧНО-АРКТИЧЕСКОГО ШЕЛЬФА

Gases from bottom sediments of the Laptev–Siberian Sea zone contain methane (up to 8.3047 cm3/kg) and its homologues (down to and including pentane) totaling 0.0259 cm3/kg. The established values of the carbon isotope composition of methane (δ13С), the molecular weight of the hydrocarbon fraction, the weight concentrations of С1–С5 hydrocarbons and their ratios, the «wetness» and «transformation» coefficients of the hydrocarbons fraction, indicate the presence of various syngenetic and epigenetic gases in bottom sediments. Potential gas sources are modern sediments, peat, coal, gas and gas hydrate? deposits, solid bitumen, igneous rocks, and inferred oil and gas accumulations. It has been established that the distribution of hydrocarbon gases in sediments vertically and horizontally depends on the influence of a complex of geological factors – fold and fault tectonics, magmatism and seismic activity in the region, coal, oil and gas potential and bituminosity, organic saturation and lithological composition, hydrogeological, geocryological, and other conditions for accumulation of gases or their degassing.

Genesis and source of natural gas in Well Mitan-1 of Ordovician Majiagou Formation, middle-eastern Ordos Basin, China

The Well Mitan-1 has achieved a major breakthrough in the exploration of Ordovician subsalt natural gas in the mid-eastern Ordos Basin, demonstrating a high-yield industrial gas flow in fourth member of the Majiagou Formation of Ordovician (O1m4). Despite this success, there are ongoing disputes regarding the origin of the natural gas found in Well Mitan-1. Measured results show that the natural gas in Well Mitan-1 is mainly composed of alkane gas (95.18 %). The gas drying coefficient (C1/C1-5) is measured at 0.947, and the H2S content is 3.49 %, with a small amount of N2 and CO2 in the non-hydrocarbon gas. The carbon isotopic compositions of methane, ethane, and propane in the natural gas are −45.5 ‰, −26.4 ‰, and −24.3 ‰, respectively. Based on the regional geological background, the characteristics of potential source rocks and the geochemical characteristics of natural gas, it is considered that the natural gas in Well Mitan-1 is self-generated and self-accumulated oil-associated gas in Ordovician subsalt carbonate rocks. However, certain geochemical anomalies, such as the lighter methane carbon isotope value (δ13C1) and coal-type gas characteristics in ethane carbon isotope (δ13C2), raise questions. Further insights from thermal simulation experiments on hydrocarbon generation and the analysis of residual gas in rocks suggest a close relationship between the special geochemical characteristics of Well Mitan-1 and the presence of gypsum rocks. The ubiquitous gypsum rock serves a dual purpose: acting as an effective caprock, facilitating the retention of early-generated natural gas, and promoting the generation of heavy hydrocarbon gases (C2+) and H2S. The relatively low H2S content (less than 5 %) and higher C2+ content indicate that thermochemical sulfate reduction (TSR), if present, is not strong enough to significantly impact methane. The δ13C2 is identified as a potentially sensitive parameter for identifying TSR.

Self-Sourced Unconventional Tight Marlstone Reservoir Potential from Evaporative Lagoon of Triassic Leikoupo Formation in the Central Sichuan Basin

A breakthrough was made in tight marlstone reservoirs from an evaporative lagoon in the second sub-member of the third member of the Leikoupo Formation (Lei3-2) in the Central Sichuan Basin. The source rock characteristics, reservoir characteristics of the marlstone and geochemical parameters of the oil and natural gas were investigated to evaluate the unconventional hydrocarbon exploration potential of the tight marlstone from the evaporative lagoon. The results revealed that the source rocks were deposited in evaporative lagoon environments, and the average total organic carbon (TOC) content value for the samples was 0.75 wt%. The thermal maturity of the organic matter was relatively high, with a calculated vitrinite reflectance (Rc) of 1.7%. The characteristics of marlstones suggest that the potential source rocks had fair to good hydrocarbon generative potential. The condensate samples had low densities, low viscosities and high thermal maturity, with a Rc value of 1.7%. For the natural gas, the dry coefficient was around 0.90, and the carbon isotopic compositions of methane and ethane was −41.3‰ and −28.4‰, respectively. According to the carbon isotopic compositions, thermal maturity and geological background, the oil and natural gas from Lei3-2 are comparable with the marlstone of Lei3-2. Thus, the oil and natural gas is self-sourced and originates from the marlstone in the Lei3-2. Micropores and microfractures are often detected in the marlstone from Lei3-2, and a gypsum layer is conducive to the hydrocarbon preservation. These results suggest that the evaporative lagoon facies in Lei3-2 have large, self-sourced, unconventional, tight marlstone reservoir potential. This study also enhances the prospects for further oil and gas exploration of evaporative lagoon facies in other basins.

Zonation of the active methane-cycling community in deep subsurface sediments of the Peru trench.

The production and anaerobic oxidation of methane (AOM) by microorganisms is widespread in organic-rich deep subseafloor sediments. Yet, the organisms that carry out these processes remain largely unknown. Here we identify members of the methane-cycling microbial community in deep subsurface, hydrate-containing sediments of the Peru Trench by targeting functional genes of the alpha subunit of methyl coenzyme M reductase (mcrA). The mcrA profile reveals a distinct community zonation that partially matches the zonation of methane oxidizing and -producing activity inferred from sulfate and methane concentrations and carbon-isotopic compositions of methane and dissolved inorganic carbon (DIC). McrA appears absent from sulfate-rich sediments that are devoid of methane, but mcrA sequences belonging to putatively methane-oxidizing ANME-1a-b occur from the zone of methane oxidation to several meters into the methanogenesis zone. A sister group of ANME-1a-b, referred to as ANME-1d, and members of putatively aceticlastic Methanothrix (formerly Methanosaeta) occur throughout the remaining methanogenesis zone. Analyses of 16S rRNA and mcrA-mRNA indicate that the methane-cycling community is alive throughout (rRNA to 230 mbsf) and active in at least parts of the sediment column (mRNA at 44 mbsf). Carbon-isotopic depletions of methane relative to DIC (-80 to -86‰) suggest mostly methane production by CO2 reduction and thus seem at odds with the widespread detection of ANME-1 and Methanothrix. We explain this apparent contradiction based on recent insights into the metabolisms of both ANME-1 and Methanothricaceae, which indicate the potential for methanogenetic growth by CO2 reduction in both groups.

Biogeochemical Activity of Methane-Related Microbial Communities in Bottom Sediments of Cold Seeps of the Laptev Sea

Bottom sediments at methane discharge sites of the Laptev Sea shelf were investigated. The rates of microbial methanogenesis and methane oxidation were measured, and the communities responsible for these processes were analyzed. Methane content in the sediments varied from 0.9 to 37 µmol CH4 dm-3. Methane carbon isotopic composition (δ13C-CH4) varied from -98.9 to -77.6‱, indicating its biogenic origin. The rates of hydrogenotrophic methanogenesis were low (0.4-5.0 nmol dm-3 day-1). Methane oxidation rates varied from 0.4 to 1.2 µmol dm-3 day-1 at the seep stations. Four lineages of anaerobic methanotrophic archaea (ANME) (1, 2a-2b, 2c, and 3) were found in the deeper sediments at the seep stations along with sulfate-reducing Desulfobacteriota. The ANME-2a-2b clade was predominant among ANME. Aerobic ammonium-oxidizing Crenarchaeota (family Nitrosopumilaceae) predominated in the upper sediments along with heterotrophic Actinobacteriota and Bacteroidota, and mehtanotrophs of the classes Alphaproteobacteria (Methyloceanibacter) and Gammaproteobacteria (families Methylophilaceae and Methylomonadaceae). Members of the genera Sulfurovum and Sulfurimonas occurred in the sediments of the seep stations. Mehtanotrophs of the classes Alphaproteobacteria (Methyloceanibacter) and Gammaproteobacteria (families Methylophilaceae and Methylomonadaceae) occurred in the sediments of all stations. The microbial community composition was similar to that of methane seep sediments from geographically remote areas of the global ocean.

Contribution of soluble organic matter to hydrocarbon generation in saline lacustrine source rocks: Evidence from thermal simulation experiments

Soluble organic matter generally exists in the source rocks of saline lacustrine basins. In this paper, we quantified the contribution of soluble organic matter to hydrocarbon generation based on thermal simulation experiments using a saline lacustrine source rock from the Qaidam Basin. Our results show that the yields of gaseous and liquid hydrocarbons in the thermal simulation products are greatly improved in the presence of soluble organic matter. As a comparison, the maximum yields of gaseous and liquid hydrocarbons in series C (without soluble organic matter) were 270 mg/gTOC and 329.78 mg/gTOC, respectively, while in series A (with soluble organic matter) they were 364 and 602.98 mg/gTOC, respectively. The proportion of isoprenoids and n-alkanes in the products also increased from approximately 3%–40%. Meanwhile, the presence of soluble organic matter reduced the temperature corresponding to the hydrocarbon generation peak from 375 to 250°C. Moreover, the presence of soluble organic matter also had a remarkable change on the stable carbon isotope composition of methane, resulting in more 12C enrichment with a range of 2.24‰–5.25‰. The combined evidence indicates that soluble organic matter can promote the formation of immature‒low maturity oil in source rocks.

Generation and geochemical signatures of natural gas from solid bitumen: Implications from closed and stepwise semi-open pyrolysis experiments

Solid bitumen has been acknowledged as an important source of overmature shale gas. However, the gas generation potential, chemical signatures and carbon isotopic compositions of natural gas derived from solid bitumen in an overmature hydrocarbon system are not well-understood with respect to various geological conditions. In this study, a relatively low-maturity solid bitumen from Cambrian reservoirs in the northwest Sichuan Basin was pyrolyzed in both closed and stepwise, semi-open systems. In the closed system, methane generated in the overmature thermal stage is dominated by the secondary cracking of wet gas and cumulative methane carbon isotopic values that are 4.4‰–14.8‰ lighter than the carbon isotope composition of the original solid bitumen. In semi-open systems, the gas is predominantly generated from residual solid bitumen and has wetness (i.e., C2–C5/C1–C5 by volume) values of generally less than 1%. At the same thermal maturity levels, the carbon isotope composition of methane in various semi-open systems is 4.4‰–10.0‰ heavier than those in the closed system and may also be isotopically heavier than the carbon isotope value of the original solid bitumen. The present study also illustrates that the calculated gas yields and methane carbon isotopes within a certain thermal maturity range in the closed system cannot be compared with those from residual solid bitumen as measured in the corresponding semi-open systems. This highlights the need to conduct specific semi-open pyrolysis experiments to investigate the late gas generation potential and geochemical signatures of natural gas from solid bitumen when the geological system is not a closed system. By comparing the above-mentioned results with the geochemical characteristics of Wufeng-Longmaxi shale gas from the Changning and Jiaoshiba gas fields of the Sichuan Basin, southwest China, it is suggested that the shale gas examined in this study is most likely generated in semi-open systems rather than in a closed system. In other words, the early-generated gas has been expelled from the shales, leaving the late-generated gas from residual solid bitumen and/or kerogen as the main gas source in the present hydrocarbon system.

Carbon isotopic composition of methane and its origin in natural gas from the Petišovci-Dolina oil and gas field (Pannonian Basin System, NE Slovenia) – a preliminary study

The carbon isotopic composition of methane (δ13CCH4) in natural gas from the Petišovci-Dolina oil and gas field (NE Slovenia) was measured for the first time in August and September 2021. The gas samples from different depths were taken from three wells: Dolina-deep (Pg-6) from the depth interval 3102–3104 m, Petišovci-deep (Pg-5) from the depth interval 2772–2795 m, and Petišovci-shallow (D-5) from the depth interval 1212–1250 m. According to the available composition dataset of gas, available from the Petrol Geo d.o.o. documentation, the “deep” gases sampled from the Pg-6 and Pg-5 wells consist of 85 % methane (C1), 11 % hydrocarbons heavier than methane (C2–C6) and 4 % CO2. The “shallow” gas from well D-5 contains more than 89 % methane, up to 11 % C2–C6 gases, while the CO2 content is negligible. The “deep« gas from the Pg-6 and Pg-5 wells has δ13CCH4 -36.7 ‰ and -36.6 ‰, respectively, while the “shallow” gas from the D-5 well has the δ13CCH4 of -38.6 ‰. The methane from the “shallow” gas is slightly enriched in the lighter 12C isotope. δ13CCH4 in the range from -38.6 to -36.6 ‰ clearly indicates the thermogenic origin of methane formed during the catagenesis phase of gas formation.

The 13C-depleted methane in terrigenous shale gas: A case study in the Triassic Yanchang Formation, Ordos Basin

The methane carbon isotopic composition (δ13C1) of some shale gas, and of some conventional gas in shale gas regions, is more depleted in 13CH4 than can be predicted from vitrinite reflectance (Ro) using the δ13C1-Ro equation. This is also often the case for coal bed methane. There is currently no convincing explanation for this phenomenon primarily because wellhead gas or core desorption cannot represent the original, in-situ state of the shale gas, owing to problems of desorption fractionation, lost gas, and residual gas. In this paper, we focus on shale gas in the Yanchang Formation of the Ordos Basin. To avoid the above-mentioned problems and obtain the shale gas in-situ, two shale samples, obtained from pressure coring, were used for parallel experiments. The gas desorption experiment was carried out under normal temperature and heating conditions, the core residual gas was obtained by crushing, and the components and carbon isotopic composition of desorption gas and residual gas were analyzed. The δ13C1 values for the two shale (Ro = 1.2%) desorption gas samples were −50.7‰ and −50.8‰, about 10‰ lighter than the value of −40.6‰ predicted by the empirical δ13C1-Ro formula. The δ13C1 values for the small amount of core residual gas in the two samples were −47.0‰ and −47.6‰, indicating that δ13C1 of Yanchang Formation in-situ shale gas is about 10‰ lighter than the δ13C1-Ro empirical formula predicts. This difference may be related to gas adsorption onto organic matter and clay minerals in shale. The negative δ13C1 is due to the retention of pre-biogas and early thermogenic gas. Dynamic adsorption experiments with activated carbon and a 5 Å molecular sieve show that early methane molecules preferentially occupy adsorption sites with relatively low pore radii and are likely to be replaced by late methane molecules, due to the high adsorption energy. The pore size distribution characteristics of shale in the Yanchang Formation are generally consistent with this pattern. In general, the δ13C1 of shale gas is related to adsorption, and the degree to which it is negative is related to the adsorption intensity and pore structure of the source rock.

Hydrocarbon gas seepage along the Gydratny Fault (Lake Baikal)

The Gydratny Fault, extending in SW-NE over 60 km, is situated in the central basin of Lake Baikal. This fault governs a distribution of hydrocarbon gas discharge zones on the lake bottom, many of them are hydrate-bearing. During the Class@Baikal-2019 expedition gas samples were obtained from bottom sediments along the fault zone, molecular and isotopic properties of the gases were studied. It is concluded that the fault zone is permeable for hydrocarbons and serves as an important fluid flow conduit from deep sources to the surface. The most intensive gas seepage was determined along the central and north-eastern segments of the fault zone where it is associated with the MSU hydrate-bearing structure and the Novosibirsk and Ukhan mud volcanoes. Within these structures the highest concentrations of methane and C2+ components were detected, the heaviest isotopic composition of methane carbon (–57‰ VPDB) were identified and near-surface gas hydrate accumulations were observed. The south-western segment of the fault is characterized by the lowest concentrations of gases in sediments with light carbon isotopic composition of methane (–76‰ VPDB).A dominant gas migration mechanism (advection or diffusion) in the upper part of the basin sedimentary section conditions the registered concentrations of methane and its homologues in sediments and their carbon isotopic composition. Diffusion and dispersion of migrated thermogenic gases and significant portion of microbial methane in seeping gases are characteristic for the areas where the fault is buried under relatively thick modern sediments. Focused gas migration followed by its focused discharge are specific for the areas where the fault propagates to the lake floor and is well-expressed in a bottom relief. Two models of hydrocarbon gases migration to the surface explaining the observed gas-geochemical characteristics of bottom sediments are described and discussed. Obtained results can help in enhancing interpretation of data of gas geochemical prospecting for offshore oil and gas.

Molecular and isotopic compositions of hydrocarbon gases generated from anomalously 13C-enriched sapropelic sedimentary organic matter in lacustrine basins

For lacustrine basins, the enrichment of 13C in sedimentary organic matter is closely related to the growth of plankton biological productivity. Consequently, there are many cases where the sapropelic organic matter is more 13C-enriched than the humic organic matter. However, the geochemical characteristics of the pyrolysis products produced by 13C-enriched lacustrine sapropelic organic matter are less discussed. Herein, two lacustrine sapropelic kerogen samples with remarkably different carbon isotopic ratios (–23.2‰ and –28.4‰) and a coal sample (–25.6‰) were performed by a closed and dry pyrolysis system at temperatures ranging from 300 °C to 600 °C. The results indicated that the carbon isotopic compositions of hydrocarbon gas products were significantly affected by the initial carbon isotopic composition of their sources. At similar simulated temperatures, the carbon isotopic compositions of methane generated from the 13C-enriched sapropelic sample and the coal sample were more consistent. However, owing to the difference in their gas-generation mechanism, the natural gas generated from the coal sample had a more 13C-enriched isotopic composition of ethane (δ13C2) and a higher dryness, particularly at higher maturity levels. The hydrogen isotopic composition of methane (δ2HC1) was markedly enriched in deuterium as the thermal maturity increased and may have been independent of the genetic type and salinity. Therefore, we used the “Dryness vs. δ2HC1” and “δ13C2 vs. δ2HC1” diagrams to confirm the genetic type of natural gas in lacustrine basins.

A novel isotopic approach to distinguish primary microbial and thermogenic gases in shallow subsurface environments

The stable carbon isotopic compositions of methane and ethane have been used for several decades to characterize petroleum gas in the subsurface. However, difficulties have frequently remained in determining the exact origin of natural gas samples derived from microbial activity, thermal degradation of organic matter (e.g. thermogenic gas), and mixtures of both components. To further refine this approach, we represent the carbon isotope difference between methane and ethane, or Δ13CC1–C2, plotted versus the individual δ13C values of methane and ethane as a new graphical tool for a refined assessment of natural gas origins and their mixtures. In addition, a new mathematical notation using the δ13C values of methane and ethane is also proposed for discrimination of the origin of natural gas samples. This parameter has been termed isotope factor O(C1/C2) and is defined as the ratio [(δ13CC1*1000)/(δ13CC2)3]. When this factor is represented against the δ13C values of methane and ethane, an improved distinction between primary microbial and thermogenic gases is achieved. Our study does not propose mechanisms for microbial generation of ethane, but the data suggest that the isotopic composition of ethane should be taken into account for the characterization of the origin of natural gas samples from shallow subsurface environments. For primary microbial and thermogenic gases with similar δ13C values of methane, the primary microbial gas will be characterized by lower O(C1/C2) values (<1.5) compared to the thermogenic gas (>2), and will have a Δ13CC1–C2 value 10–20‰ more positive than that of thermogenic gas. Gas mixtures have intermediate O(C1/C2) and Δ13CC1–C2 values and are graphically identifiable using the here presented classification tools. The effectiveness of the new graphical tools is demonstrated using natural gas samples from Canadian groundwater wells, low-permeability petroleum reservoirs (including coalbed methane plays) in Canada and the USA, Quaternary primary microbial gas accumulations in China, and secondary microbial gases from Northern Africa and China.

Methanogenesis in the Eocene Tharad lignite deposits of Sanchor Sub-Basin, Gujarat, India: Insights from gas molecular ratio and stable carbon isotopic compositions

The present study investigates the molecular ratio and stable carbon isotopic compositions of gas samples from the Lower to Middle Eocene lignite deposits of the Lower to Middle Tharad Formation in the Sanchor Sub-Basin, Gujarat, India, which were understudied, hitherto. The stable carbon isotopic composition of methane (−69.30 to −57.20‰ in BK-5 and from −67.40 to −64.50‰ in BK-7 well) may imply the generation of primary microbial gas through the hydrogenotrophic methanogenesis, which was mixed with the early mature thermogenic gas, and this is a novel finding from this study area. The relation between the gas molecular ratio [methane/(ethane + propane)] and the stable carbon isotopic composition of methane confirms the mixing trend (~90–~40%) of the primary microbial methane with the early mature thermogenic gas sourced from hydrogen-rich macerals either in situ or at a higher depth that subsequently migrated upwards. Further, the studied gas samples comprise a large amount of carbon dioxide (16.95–32.32 vol.% and from 18.91 to 28.60 vol.% in BK-5 and BK-7 wells, respectively). The relation between the carbon dioxide content and its stable carbon isotopic composition (−21.30 to −11.80‰ and from −11.20 to −9.40‰ in BK-5 and BK-7 wells, respectively) may suggest the origin of carbon dioxide from volcanic degassing from the Deccan Trap basaltic magma as well as from coalification through decarboxylation and decarbonylation reactions. So, the mixed origins of carbon dioxide (inorganic + organic) and methane (primary microbial and early mature thermogenic) would have influenced the carbon isotopic difference between carbon dioxide and methane as well as the isotopic discrimination factor, which is also reported for the first time from this investigation. Finally, the relation between the gas molecular ratio and the carbon isotopic difference between carbon dioxide and methane compliments the gas mixing effects. Hence, the novelty of this investigation lies in elucidating the influences of the early mature thermogenic gas on the gas molecular and stable carbon isotopic signatures of primary microbial gas originated through the hydrogenotrophic pathway as depicted by the gas molecular ratio and stable carbon isotopic compositions of methane and carbon dioxide.

Surface geochemical survey in the vicinity of decommissioned coal mine shafts.

Methane observed in soil atmosphere above active and abandoned bituminous coal mines has a thermogenic (coalbed) and/or microbial (produced by anaerobic bacteria or resulted from in situ coal biodegradation) origin or it may be a mixture of gases generated from various sources. Identification of the origin of methane may support or refute the thesis on the uncontrolled migration of mine gases in rock formations followed by their emission to the atmosphere at coal extraction sites. Surface geochemical surveys were carried out in the vicinity of the decommissioned mine shafts at the Murcki-Staszic Coal Mine, located in the Upper Silesian Coal Basin (southern Poland). Over a 3-month period, measurements were carried out cyclically at 2 locations. Totally, 43 fixed geochemical probes were installed in the area of the Murcki II "Stanisław" Shaft, in which measurements were carried out in six sessions. Next 29 probes were installed in the area of the Staszic III Shaft, where measurements were taken twice. Each measurement included concentrations of 5 components (methane, non-methane volatile organic compounds, total hydrocarbons, carbon dioxide and oxygen), which provided a total number of 1405 individual analytical determinations. For measurements, portable EcoProbe 5 instrument was used. The stable carbon isotope composition of methane and carbon dioxide was analyzed in selected 10 samples. The isotopic composition of hydrogen in methane was also measured in one sample. The comparative material consisted of eight samples of soil gases and two samples of mine gases, which were used as reference 'soil' gases. The isotopic analyses were conducted using a mass spectrometry method. Based on the results of our analyses, it is stated that both the Murcki II "Stanisław" and the Staszic III shafts were properly decommissioned. The successful sealing of mine shafts prevented mine gases from migration through the shaft into the atmosphere. However, at a single geochemical probe located more than 100m from the former shaft center, methane concentration in soil gases reached over 1vol%. This confirms the general observation that mine gas migrates from coal seams and/or gobs through crushed rocks into the atmosphere. The stable carbon isotope analysis of methane and carbon dioxide as well as stable hydrogen isotope analysis of methane suggest that methane in the soil atmosphere is of thermogenic origin with minor contribution of microbial component.

New equation to decipher the relationship between carbon isotopic composition of methane and maturity of gas source rocks

The identification of the origin and source of natural gas is always a difficult and hot issue. Hereinto, the maturity identification is one of the most important scientific problems. Many empirical equations have been established to decipher the relationship between the maturity of gas source rocks and the carbon isotopic composition of natural gas. However, these equations proposed often fail to identify the maturity of the source rocks correctly, which in turn prevents the identification of genetic types and source rocks of the natural gas because the petroliferous sedimentary basins in China are complex and diverse, with multiple sets of source rocks and different thermal history. In this paper, the oil-associated gas from the Permian lacustrine source rocks and the coal-derived gas from the Jurassic source rocks in Junggar and Turpan-Hami basins have been investigated to decipher the relationship between the maturity (vitrinite reflectance) of gas source rocks and the carbon isotopic composition of methane. The equations established are δ13C1=25lgRo−42.5 for oil-associated gas, and δ13C1=25lgRo−37.5 for coal-derived gas. These new equations are suitable for the maturity identification of source rocks in most petroliferous basins, and favorable for the identification of the genetic type and source of natural gas, which is very important to improve the geological theory of natural gas.

Dissolved methane in the water column of the Saguenay Fjord

Near-shore environments are a significant source of atmospheric methane but the size of this source is poorly constrained, particularly for fjords and fjards. This study investigated the methane emission rates and the drivers controlling the dynamics of dissolved methane in the Saguenay Fjord, a deep, stratified, and well‑oxygenated subarctic fjord system in eastern Canada. Dissolved methane concentrations ([CH4]) in the water column were measured in October 2016 and June, October, and November 2017, with stable carbon isotope composition of methane (δ13CCH4) analyzed during the November 2017 survey. Surface-water [CH4] ranged from 16 to 184 nmol L−1 and decreased with increasing salinity in a bi-segment linear manner, inferring a temporally constant marine endmember but a freshwater discharge-dependent river endmember. The multi-cruises dataset yields a mean [CH4] saturation ratio of 12.7 (range: 4.5–48.7) and a mean emission rate of 53.4 μmol m−2 d−1 (range: 16.4–256.9 μmol m−2 d−1). [CH4] was generally higher in surface water than in deep water. However, sill-induced mixing could homogenize [CH4] near the mouth of the fjord and sedimentary input of biogenic methane (δ13CCH4: −57.660‰) in the fjord's head region increased [CH4] in the overlying bottom water up to 459 nmol L−1. The longitudinal pattern of [CH4] below the surface layer was primarily controlled by deep-water renewal events. Deep-water [CH4] declined with rising apparent oxygen utilization, suggestive of aerobic microbial methane oxidation at rates estimated to be <0.1 nmol L−1 d−1. The δ13CCH4 data yields a carbon isotopic fractionation factor of 1.08 in both the surface and deep waters that points to microbial oxidation dictating the carbon isotopic fractionation of methane in the fjord. Mass-balance budgeting reveals that river runoff accounts for 81% of the total methane input to the fjord (12.13 × 106 mol year−1) and that microbial oxidation of methane (4.45 × 106 mol year−1) is comparable to emission to the atmosphere (4.27 × 106 mol year−1). This study demonstrates the important roles of river runoff and deep-water renewal in controlling the dynamics of [CH4], δ13CCH4, and methane emission to air in fjords receiving large terrestrial freshwater discharges and experiencing frequent deep-water renewals. The areal methane emission rates for deep fjords obtained by this and earlier studies are one to two orders of magnitude higher than the mean flux estimate for global coastal oceans, placing fjords and fjards as a potentially significant contributor to coastal methane emission.

Биогеохимические характеристики мелководных струйных метановых газовыделений в прибрежных районах Крыма в сравнении с глубоководными сипами Чёрного моря

Струйные метановые газовыделения (сипы) — широко распространённый феномен в Мировом океане, в том числе в бассейне Чёрного моря. Актуальность исследований метановых сипов обусловлена их важной ролью в качестве источника метана как парникового и средообразующего газа для водной толщи и атмосферы. В работе представлен сравнительный анализ данных собственных биогеохимических исследований мелководных сипов Крымского полуострова, охватывающих последние десять лет, и материалов, посвящённых глубоководным газовыделениям Чёрного моря. В этот период были проведены поисковые гидроакустические исследования, выявлен компонентный состав пузырькового газа, измерен изотопный состав углерода метана, а также молекулярно-биологическими методами определена структура микробного сообщества бактериальных матов, покрывающих площадки газовыделений, и выполнена оценка газовых потоков от отдельных сипов. В течение многолетнего мониторинга обнаружено и описано 14 отдельных газовыделяющих площадок в прибрежных районах Крыма, которые располагались от мыса Тарханкут на западе полуострова до бухты Двуякорная на юго-востоке. Превалирующая часть прибрежных сипов Крыма имела биогенную природу и сезонный характер газовыделений. К глубинному газу термокаталитического генезиса отнесены сипы в бухте Ласпи. Наблюдался значительный разброс величин изотопного состава углерода метана δ13C-CH4 пузырькового газа прибрежных мелководных районов (−94…−34 ‰), что указывает на разные условия его генерации и созревания в донных отложениях. Так же, как и глубоководным сипам, прибрежным струйным газовыделениям сопутствовали бактериальные маты разной структуры с различными доминирующими видами. Показано, что для формирования устойчивой бактериальной биомассы, основу которой составляли, как правило, сульфид- и сероокисляющие бактерии, необходим флюидный поток восстановленных растворённых газов, тогда как точечная разгрузка пузырькового газа не обеспечивает достаточных градиентов концентрации и может механически разрушать структуру образующегося сообщества. Различными методами сделаны оценки размерных спектров пузырьков и потоков от отдельных струй. Диапазон значений газового потока варьировал от 1,8 л·сут−1 (бухта Мартынова) до 40 л·сут−1 (бухта Ласпи). Проанализированы средообразующие эффекты, связанные с выделением пузырькового газа в прибрежных районах: влияние сипов на кислородный режим в донных осадках и в толще воды́ над точками газовыделений; вертикальное перемешивание вод за счёт газлифтового эффекта; флюидная разгрузка на площадках струйных газовыделений.

Fluctuations in methane and carbon dioxide concentrations in the near-surface zone and their genetic characterization in abandoned and active coal mines in the SW part of the Upper Silesian Coal Basin, Poland

The objective of this paper is to determine the origin and variability of methane and carbon dioxide concentrations in the near-surface zone and of coalbed methane in the SW part of the Chwałowice Trough and adjacent areas of the Main Syncline of the Upper Silesian Coal Basin (USCB). For this purpose soil-gas samples were taken at 202 measuring points, arranged along 5 profiles located in the mining area of the abandoned 1 Maja mine and directly adjacent areas as well as in the vicinity of four abandoned and remediated mining shafts. The maximum methane and carbon dioxide concentrations in the gas samples measured exceeds 22 and 9 vol%, respectively. The carbon isotope composition of methane and carbon dioxide was determined in samples in which elevated concentrations of these gases were found. Moreover, seven coalbed gas samples and bituminous coals were collected from coal seams exclusively from virgin parts of the Anna, Marcel, Jastrzębie, and Zofiówka mines. These data were supplemented with results of archival research for genetic interpretation of coalbed gases.Research reveals that typical humic low- and medium-volatile bituminous coals occur in Mississippian and Pennsylvanian coal-bearing strata in the study area. Fluctuations in methane and carbon dioxide concentration in the near-surface zone are related to the lithostratigraphy and tectonics of the area as well as to complicated methane depth distribution. Faults may play an important role in the microseepage of gases from deep to the near-surface zone. The connection of near-surface gases with subsurface gases was confirmed by similar stable carbon isotope composition in the methane recorded in the soil-gas samples and in the gas samples from the coal seams and sandstones of the Carboniferous formations. Distribution of anomalous methane concentrations recorded in soil-gas samples taken from profiles may indicate natural gas accumulations in the top zone of the Pennsylvanian coal-bearing formations. One example of this kind of accumulation is the Marklowice natural gas field, located within the mining area of the Marcel coal mine. Relatively high methane concentrations measured in soil gas in the vicinity of shafts I and III indicate that the degassing systems of closed and remediated mining shafts are not fully effective. Increases in carbon dioxide concentrations in the surface zone and frequent associated decreases in methane concentration were most often the result of microbial methane oxidation.

Temperature-depth control of petroleum occurrence in the sedimentary section of the South Caspian basin

This study analyses the temperature and depth control of well productivity (oil and gas), density of hydrocarbons (HC) and gas/liquid HC ratio (GLR) of petroleum fields in the South Caspian Basin (SCB). The database includes more than 700 field data from 54 onshore and offshore fields, which were processed to provide graphical and statistical analysis using standard computer programs. It was established that the peak of initial production and proven oil reserves falls in the temperature range 50–70 °C. The oils of this interval are characterized by medium (about 890 kg/m3) and light (about 806 kg/m3) density. The maximum condensate and gas production are in the temperature range 100–120 oС, associated with the discovery and operation of large gas condensate fields in the deepwater part of the SCB. Liquid HC are represented in this temperature interval by “volatile” oils and condensates with an average density of 777–802 kg/m3. Low values of GLR are typical for temperatures below 70 °C, associated both with poor gas conservation conditions and relatively high volumes of oil production. The carbon isotope composition of methane indicates an exclusively catagenetic (thermal) origin at temperatures >50 °C and both catagenetic and mixed (microbiological-catagenetic) at temperatures <50 °C. Based on the results, a forecast is provided for the discovery of new commercial HC accumulations.