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Doubly-substituted methane isotopologues (13CH3D and 12CH2D2) can provide unique information to resolve the origin, transport, and conversion of environmental methane. We used a high-resolution mass spectrometer (Thermo Fisher Scientific 253 Ultra) to precisely determine Δ13CH3D and Δ12CH2D2 (precision and accuracy of ∼0.35‰ and ∼1.35‰ (1σ), respectively) in this study. The impacts of temperature, humidity, and slit quality are found to be critical for the reproducibility of the results, while the fragmentation rate and bellows effects on the clumped isotope results were negligible. A heating equilibrium experiment performed at 500 °C, 400 °C and 300 °C (n = 19) calibrates the results to an absolute reference. A pretreatment system that can extract methane having concentrations from ∼15% to ∼99.8% is proposed, while the fractionation produced throughout the pretreatment is negligible within precision (Δ13CH3D = +0.16 ± 0.32‰ and Δ12CH2D2 = +0.14 ± 1.12‰ (n = 16)). Analyses of natural gases from shale basins and variable methane-rich gases emitted from artificial lakes validate the capability of the current pretreatment and spectrometer systems to determine methane clumped isotopes in a wide range of natural environmental samples. [ABSTRACT FROM AUTHOR]

Methane is an economic energy resource and potent greenhouse gas. Distinguishing secondary microbial methane from thermogenic gas is important for natural gas exploration and consideration of subsurface microbial activity in the global carbon cycle, but remains challenging. To understand controls on methane origins in natural gas systems, we investigated the methane clumped isotopologue distributions in the Qinshui Basin high-thermal maturity coal bed methane (CBM) reservoir. Here, near-equilibrium clumped isotopologues distribution (Δ13CH 3 D and Δ12CH 2 D 2) inferred a temperature interval of 21.6–252.3 °C. The high-temperature thermodynamic equilibrium most likely represents original thermogenic CBM characteristics during coalification. The low-temperature equilibrium clumped isotopologue distributions suggest microbial alteration to CH 4 isotopic bond ordering by increased enzymatically catalyzed isotopic exchange. The independent constraints from clumped isotopes, integrated with other geochemical and genomic evidence, confirm notable secondary microbial methane from biodegradation in the highly mature reservoir. Thus, methane clumped isotopes can be used as unequivocal tracers to distinguish secondary microbial methane from thermogenic gases and hence provide the ability to incorporate them separately into global methane budgets. [ABSTRACT FROM AUTHOR]

[Display omitted] • Coal and amendments significantly increase methane production in incubation. • Machine learning help predict missing biogenic Δ12CH 2 D 2 data. • Clumped isotopes indicate differential reversibility and combinatorial effects. • Coal bioavailability rather than coal thermal maturity determine CH 4 production. Biogenic (microbial) methane is an imperative natural gas resource and plays an important role in the global carbon cycle. Determining isotope systematics in microbially enhanced coal bed methane (MECBM) informs methane biogeochemical processes and environmental impacts. Here, we conduct laboratory MECBM experiments using coal samples of differing maturities (from lignite to anthracite) and report analytical results of methane production, bulk and clumped isotopes (δ13C, δD, Δ13CH 3 D and Δ12CH 2 D 2). We reproduce the differential reversibility in methanogenic reactions, which exhibits a correlation with kinetic clumped isotope fractionation (Δ13CH 3 D from +0.17 ‰ to +4.04 ‰). The exogenous combinatorial effects play a greater role in determining the negative Δ12CH 2 D 2 (<–30 ‰). In the microcosm of MECBM, coal and amendments are suggested to significantly increase methane production (from 82.4 ± 17.1 to 344.6 ± 22.8 μmol CH 4 /g coal), with effects controlled by substrate coal bioavailability rather than coal thermal maturity. This suggests the possibility of MECBM attempts to utilize high thermal maturity coal. We perform machine learning models and improve the accuracy of biogenic 12CH 2 D 2 predictions, which help understand the mechanism of methane formation, and further provide new insights into clumped isotope effects among different biogenic methane sources. Our incubation experimental and compiled dataset (n = 275) better constrain biological participation in the methane formation process and potentially be used for methane sources tracing. [ABSTRACT FROM AUTHOR]

• δ13C of coalbed gases measured from 5 Qinshui Basin blocks with different maturity. • Secondary microbial methane from the biodegradation of overmature coals detected. • The mutual conversion between CH 4 and CO 2 occurred in shallow buried coals. • Overmature coals hold high potential in stimulating microbial methane generation. Understanding the generation of secondary microbial methane (SMM) is important for the evaluation of natural gas resources and instructive for the stimulation of methane production. Coal seams are popular targets for extracting in situ preserved methane and studying microbe-stimulated methane yield. However, few studies have been done on overmature coals. Here we collected gas samples from coals varying from bituminous to meta-anthracite in the Qinshui Basin, North China, and analysed the molecular and stable isotopic compositions to systematically evaluate the influence of biodegradation in high-rank coals in geological settings. The stable isotope signatures (δ13C and δD) of methane are dominated by the thermal decomposition of organic matter in deep coals but inconsistent with the maturity rank of shallow burial coals. The decoupling of coal maturity with C 1 /C 2+ ratios and δ13C-CH 4 values, and positive δ13C-CO 2 values (−9.2 to +24.4 ‰) suggest biodegradation of light wet gases (C 2+ components) and CO 2 reduction. Negative trends between δ13C-CO 2 and CH 4 /CO 2 in shallow burial coal seams reveal the mutual conversion of CH 4 and CO 2 and carbon isotope exchange, driven by microorganisms. The calculated isotopic temperatures (33–328 °C) based on the carbon isotope fractionation factors between CH 4 and CO 2 (1.024–1.069) demonstrate that carbon isotope exchange is prevalent in high-rank coals. It also reveals that the burial depth is an imperative factor in controlling microbial environments and thus the biodegradation process. This study implicates the potential of high-rank coals as the target for microbial-enhanced methane recovery and also implies that microorganisms are widely involved in reservoir carbon cycling. [ABSTRACT FROM AUTHOR]