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Carbon and hydrogen isotope compositions of CH 4 generated via methanogenesis in cultures of South Sumatra Basin (SSB) coalbed methane (CBM) formation waters grown on coal, acetate and H 2 + CO 2 were investigated. CH 4 production and molecular analysis confirmed the presence of active microbial communities that are able to convert coal into CH 4 using both acetoclastic and hydrogenotrophic pathways. The representative bacterial sequences were dominated by Bacteroidetes , Firmicutes and Deltaproteobacteria , while Methanosaeta and Methanosarcina were the most prevalent archaeal methanogens present in the cultures. CH 4 produced in this study's culturing experiments has δ 13 C values in the range of − 50 ‰ to − 20 ‰, with most values falling outside the current understanding of the carbon isotopic boundaries for biogenic CH 4 (− 110 ‰ to − 30 ‰). However, the corresponding apparent carbon isotopic α factor ( α c = 1.02 ± 0.006), and isotopic effect ( ε c = − 20.1 ‰ ± 15.3) showed that CH 4 in SSB cultures was predominantly produced by acetoclastic methanogenesis, which is consistent with the results of molecular DNA analysis. In addition, the calculated contribution of CO 2 reduction from the δ 13 C values of coal-treated cultures was overall < 50 %, further confirming the high contribution of the acetoclastic pathway to CH 4 production in the SSB cultures. The outcome of this experimental study also suggests that δ 2 H-CH 4 values may not provide a reliable basis for distinguishing methanogenic pathways, while apparent carbon isotopic fractionation factor ( α c ) and isotope effect ( ε c ) are considered more useful indicators of the methanogenic pathway. The high δ 13 C-CH 4 values (≥ 30 ‰) and the dominance of Methanosaeta over Methanosarcina indicate that methanogens within the SSB cultures were operating at low substrate concentrations. An unusually positive δ 13 C-CH 4 suggests a substrate depletion effect, which is thought to be related to a decrease in the relative abundance of key bacterial coal degraders with formation water inoculum storage time. Closer observation of δ 13 C-CH 4 values during the growth of cultures within a single experiment also showed a 13 C-enrichment trend over time. At log phase of growth, the CH 4 produced was 13 C-depleted when compared to the stationary phase that also indicates substrate depletion effects. Finally, the δ 13 C-CH 4 values encountered in this study (as high as − 20 ‰) highlight the possible positive extension of δ 13 C-CH 4 values of acetoclastic methanogenesis from those currently reported in the literature for natural and experimental samples (as high as − 30 ‰). [ABSTRACT FROM AUTHOR]

The end of the Late Palaeozoic Ice Age (LPIA) ushered in a period of significant change in Earth's carbon cycle, demonstrated by the widespread occurrence of coals worldwide. In this study, we present stratigraphically constrained organic stable carbon isotope (δ13Corg) data for Early Permian coals (312 vitrain samples) from the Moatize Basin, Mozambique, which record the transition from global icehouse to greenhouse conditions. These coals exhibit a three-stage evolution in atmospheric δ13C from the Artinskian to the Kungurian. Early Kungurian coals effectively record the presence of the short-lived Kungurian Carbon Isotopic Excursion (KCIE), associated with the proposed rapid release of methane clathrates during deglaciation at the terminus of the Late Palaeozoic Ice Age (LPIA), with no observed disruption to peat-forming and terrestrial plant communities. δ13Corg variations in coals from the Moatize Basin are cyclic in nature on the order of 103–105 years and reflect changes in δ13Corg of ~±1‰ during periods of stable peat accumulation, supporting observations from Palaeozoic coals elsewhere. These cyclic variations express palaeoenvironmental factors constraining peat growth and deposition, associated with changes in base level. This study also demonstrates the effectiveness of vitrain in coal as a geochemical tool for recording global atmospheric change during the Late Palaeozoic. [ABSTRACT FROM AUTHOR]

Coal bed methane (CBM) has recently been produced from sub-bituminous to high volatile bituminous low rank coals (vitrinite reflectance 0.39 to 0.53%) from the Paleocene Cuervos Formation in the Cesar Sub-basin, Colombia. Understanding CBM gas origin is vital for designing exploration and production strategies, in order to target either shallow economic accumulations of microbial gas or deeper and thermally mature coal seams. In this context, this study aims to determine whether thermogenic gas, biogenic gas, or a mixture of both gas types have contributed to gas yield in the Cesar Sub-basin; it also discusses the relationship between gas origin and tectonics. For the first time, co-produced waters and gas samples from CBM multi-seam production wells and shallow aquifer water-wells were collected in the Boqueron compartment (Cesar Sub-basin) and were analysed via stable isotope composition and molecular geochemistry. Structural compartmentalisation in the Sub-basin as a result of interplate shortening during the Mid-Paleogene has resulted in slightly different coal ranks, saturation, and gas contents between compartments of the Paleocene Cuervos Formation. This event could have interrupted early thermogenesis and allowed the introduction of meteoric waters carrying bacteria consortia responsible for biogenesis. The produced waters from the CBM wells were HCO 3 > Na+ > Cl− type, and ranged in TDS (Total dissolved solids) from 2268 to 6602 mg/L (avg. 3887 mg/L). Recently revised genetic diagrams of δ13C-CH 4 versus δ2H-CH 4 and additional parameters, such as gas dryness ratio and water chemistry, corroborated biogenesis as the main gas origin. Carbon isotopic differences between carbon dioxide and methane (Δ13C H2O–CH4), as well as those of hydrogen isotopes in water and methane (Δ2H H2O–CH4), also indicated a typical microbial CO 2 reduction pathway. The positive carbon isotope composition of dissolved inorganic carbon (δ13C-DIC) not only showed a clear differentiation between waters from CBM wells and those from shallow aquifers, but also confirmed the occurrence of methanogenesis when paired with high alkalinity. In addition, the water quality analysis showed increasing sodium and bicarbonate concentrations with depth, which is typical of CBM production basins. Although biogenic gas was identified, tectonic settings do not seem to explain gas origin occurrence, since secondary biogenesis was expected in an uplifted basin such as Cesar Rancheria. Isotopic data was not decisive in differentiating primary versus secondary biogenesis, since the gas isotope compositions plot close to the boundary between the primary and secondary biogenic gas fields. Further studies on isotopic chemistry are required to refine this interpretation and confirm gas generation in the other two compartments. [ABSTRACT FROM AUTHOR]

Abstract: Carbonaceous matter (CM) from ca. 3.5Ga hydrothermal black cherts of the Pilbara Craton of Western Australia and the Barberton Greenstone Belt of South Africa yielded transmission electron microscopy (TEM) images that are suggestive of microbial remains and possible remnants of microbial cell walls. These are compared to a potential modern analogue, the hyperthermophilic Methanocaldococcus jannaschii, derived from an active seafloor hydrothermal environment and cultured under similar conditions. A striking resemblance to the early Archaean forms was evident in wall structure and thermal degradation mode. Cell disintegration of the cultures occurred at 100°C marking the limits of life. Complete disintegration, deformation and shrinkage occurred at 132°C. A multidisciplinary approach to the characterisation of the CM was undertaken using organic petrology, TEM coupled with electron dispersive spectral analysis (EDS), high resolution TEM (HRTEM) to determine molecular ordering, and elemental and carbon isotope geochemistry. Reflectance measurements of the CM to determine thermal stress yielded a range of values corresponding to several populations, and pointing to different sources and processes. The δ13C values of Dresser Formation CM (−36.5 to −32.1‰) are negatively correlated with TOC (0.13–0.75%) and positively correlated with C/N ratio (134–569), which is interpreted to reflect the relative abundance of high R o/oxidised/recycled CM and preferential loss of 12C and N during thermal maturation. TEM observations, inferred carbon isotopic heterogeneity and isotope fractionations of −27 to −32‰ are consistent with the activity of chemosynthetic microbes in a seafloor hydrothermal system where rapid silicification at relatively low temperature preserved the CM. [Copyright &y& Elsevier]

Abstract: The emplacement of calcite-filled veins perpendicular to the Dead Sea Fault Zone in northern Israel reflects strain partitioning during transpression. We present structural, geochemical, and U–Th geochronological data that constrain the mechanism, conditions and timing of vein formation. Vein walls are strongly brecciated and commonly cemented with coarsely crystalline calcite, whereas calcite-filled veins are composed of wall-parallel bands of calcite crystals. Elongated blocky and fibrous calcite crystals grew perpendicular to the vein walls and are characterised by a truncate sealing-hiatus morphology, indicating episodes of partial or complete sealing of the fractures during calcite precipitation. Stable isotope and rare-earth element and yttrium (REY) analyses indicate that calcite-filled veins precipitated by karst processes, involving meteoric water and limited fluid-rock interactions. U–Th dating results show a prolonged history of vein growth. While some veins initiated prior to 500 ka, the majority of the veins were active between 358 and 17 ka. Age constraints on vein activity correspond to an ∼E–W regional shortening phase in this sector of the Dead Sea Fault Zone, associated with an increased component of convergence during the late-Pleistocene. [Copyright &y& Elsevier]

Coupling carbon and nitrogen isotopes and petrography of coals and related intra-seam carbonaceous mudstone partings from basins in northern China provides insight into regional palaeoenvironments and palaeoclimate during the late Carboniferous–early Permian. The carbon isotopic composition (δ 13C coal , VPDB) of coal samples from the Taiyuan and Shanxi formations of Qinshui and North China-Bohaiwan basins ranges from −25.3‰ to −22.7‰, with an average of −23.7‰. The average δ 13C coal value is −23.6‰ in the late Carboniferous, −23.4‰ in the early Permian and −23.5‰ in the mid–early Permian. By contrast, equivalent early Permian coals in the southern North China-Bohaiwan Basin to the east were found to be significantly more negative at −25.2‰, likely as a function of regional aridity changes. Related δ 15N in coal seams ranges from +2.3‰ to +4.7‰, with an average of +3.7‰. Within the thick, economically important #15coal seam of the Qinshui Basin, δ 15N coal is significantly more negative than δ 15N in mudstone partings (avg. +7.1‰), implying that the coals underwent a stronger degree of microbial degradation during peat formation. δ 15N of mudstone partings varies stratigraphically, with significantly more positive δ 15N (+8.1‰, +8.3‰) for the lower partings and lower δ 15N (+4.8‰) for the upper parting. This may reflect varying degrees of microbial activity, but could reflect higher thermal maturity in the upper part of the seam as indicated in the coal rank profile. δ 13C coal in this region was used to calculate the carbon isotopic composition of atmospheric CO 2 (δ 13C a). Calculated δ 13C a ranges from −6.0‰ to −3.4‰, with an average of −4.5‰, which is more positive than the δ 13C a of modern atmospheric CO 2 (−8.5‰, Graven et al., 2017). Two δ 13C a excursions are noted: a positive one (magnitude 3.7‰) in the late Carboniferous and a tentative negative excursion (magnitude 6.0‰) in the mid–early Permian. The positive shift coincided with a sea-level transgression in the Qinshui Basin. The rise in sea level may have led to the burial of more terrestrial plant debris that decreased photosynthesis and enriched atmospheric CO 2 in 13C. More data are needed to understand mid-early Permian variation in δ 13C, as this could reflect a regional aridity or humidity effect rather than a global signal. Unlabelled Image • C and N isotope analysis of major coal seams in the Taiyuan and Shanxi formations. • Results compared with the existing terrestrial δ 13C org curve for northern China. • δ 13N coal offers insights on short-term environmental changes and microbial activity. [ABSTRACT FROM AUTHOR]