The hydrogeochemical characteristics of coalbed-produced water can provide insights into the sources of ions and water, the groundwater environments, hydrodynamic conditions, and water-rock interactions of depositional basins. To study the water-rock reaction process and reveal whether there is a microbial activity in the groundwater, a case of the Dafosi biogenic gas field was chosen by testing the ionic concentrations and hydrogen and oxygen isotopic compositions of coalbed-produced water and employing R-type cluster and principal component analyses. The results showed that Na⁺, , and HCO₃^- are the principal ions in the coalbed-produced water, while the water type is mainly a Na–Cl. Due to the hydrolysis of HCO₃^-, the pH in this region was controlled primarily by HCO₃^-. As the main cation in water, Na⁺ contributed substantially to the total dissolved solids. Na⁺ is also related to the exchange between rock-bound Na⁺ and Ca²⁺ and Mg²⁺ in water or surrounding rocks. The coalbed-produced water’s oxygen isotopes displayed a characteristic ¹⁸O drift and enrichment, indicating that the ¹⁶O isotope in the water was preferentially exchanged with the coal organic matter. Early evaporation is also contributed to the enrichment of TDS (total dissolved solids) and ¹⁸O in the water. The central part of the study area, including the Qijia anticline, was affected by the Yanshanian uplift and denudation and subsequently developed a water-conducting fissure zone and was recharged atmospheric precipitation; these conditions were conducive to the formation of secondary biogenic gas.

Investigations into the connectivity and complexity of pore systems in shales are essential for understanding the flow of shale gas and the capacities of the associated reservoirs. In the present study, eight shale samples from the Wufeng-Longmaxi (WF-LMX) Formation that were collected from Well Yucan-6 in the southeast of the Sichuan Basin were analyzed for microstructural, pore network, and pore connectivity characteristics. The measurement results of low-pressure nitrogen adsorption illustrated that all shale samples contain micropores, mesopores, and macropores. Micropores and mesopores account for a high proportion of the total pores, and the dominant pore throat size is in the range of 2–6 nm. High-pressure mercury injection tests reveal that the porosity, total pore volume, and total specific surface area of pores for samples from the WF Formation are higher than those for samples from the LMX Formation. In spontaneous absorption experiments, the slopes of the absorption curves of n-decane (oil-wetting) and deionized water (water-wetting) in the WF and LMX Formations varied from 0.254 to 0.428 and from 0.258 to 0.317, respectively. These results indicate that shales in both formations exhibit mixed wettability characteristics, but lipophilic pores are better connected relative to hydrophilic pores. The total organic carbon and silica contents are the main factors controlling the pore connectivity in these shales, while the effects of other minerals are not significant. The findings of this work can improve our understanding of the pore structure characteristics of black shale.

Marine redox conditions and their dynamic changes were a major factor that controlled the formation of black shale and caused the late Ordovician marine extinction in the Upper Yangtze Basin (South China). However, the spatiotemporal variation and potential controlling factors of marine redox conditions in this area remain unclear. We analyzed whole-rock geochemistry and pyrite sulfur isotopes (δ³⁴S_py) of 47 shale samples from the Late Katian to Rhuddanian in a shelf-to-slope (Qianjiang Shaba section and Wc-1 well) region of northeastern Upper Yangtze Basin, and reconstructed water column redox conditions during the Late Ordovician–Early Silurian Transition. The geochemical characteristics of shale, including the ratio of elements, discriminant function and ternary diagram location in the study area suggest a passive continental margin sedimentary environment, wherein the terrigenous detritus is mainly derived from felsic igneous rocks in the upper crust, showing characteristics of near-source deposition. The redox indices (Fe speciation, C_org/P, U_EF, and Mo_EF) showed that the development of anoxic water, especially euxinia, has obvious spatiotemporal heterogeneity. Under conditions of high availability of active organic carbon and limited sulfate supply, high active Fe input and strong biological irrigation in the shallow water area may effectively remove H₂S produced by microbial sulfate reduction, conducive to the prevalence of ferruginous water columns. However, for this deep water area, the rapid accumulation rate of organic matter, decrease in dissolved Fe (caused by upwelling in the open sea), and seawater stratification (caused by the rising of sea level) promoted the development of a euxinic water column. This inference is supported by the covariant relationship between organic carbon accumulation rate, chemical index of alteration, Co × Mn, and δ³⁴S_py. Our study highlights the potential control effects of sea level change, continental weathering and upwelling on the development of euxinic water columns.

The distribution characteristics and formation of marine anoxic conditions through the Late Ordovician–Early Silurian (O–S) remain poorly resolved despite their importance in the preservation of sedimentary organic matter and the formation of black shale. In this study, the major, trace, and pyrite δ³⁴S (δ³⁴S_py) contents of 36 shale samples at the edge of the southwest depocenter of the Upper Yangtze Basin (Tianlin and Changhebian sections) were analyzed to understand the redox conditions, terrigenous clastic inputs, and primary productivity changes. The iron speciation and enrichment factor of U and Mo show that the range of anoxic conditions gradually expanded from the sedimentation center to the edge during the late Katian stage, peaked in the early Hirnantian stage followed by a rapid decrease, and expanded again during the early Rhuddanian stage. Comprehensive index analysis showed that the increase of terrigenous clastic input and the relative decrease of primary productivity due to tectonism and sea level change controlled the transformation of the water column from anoxic, especially euxinic, to suboxic-oxic conditions. This is reflected in the correlation between paleo-salinity, δ³⁴S_py, chemical index of alteration, and the organic carbon accumulation rate. This work emphasizes the control of terrigenous clastic input and sulfate availability on the transformation of marine redox conditions during the O-S period in semi-restricted basins.

The biological reduction of Fe (III) is common in underground environments. This process not only affects the biogeochemical cycle of iron but also influences the migration and transformation of pollutants. Humic substances are considered effective strategies for improving the migration and transformation of toxic substances and enhancing the bioavailability of Fe (III). In this study, the electron shuttle anthraquinone-2-sulfonate (AQS) significantly promoted the bio-reduction of Fe (III). On this basis, different concentrations of aniline were added. The research results indicate that at an aniline concentration of 3 μM, the production of Fe (II) in the reaction system was 2.51 times higher compared to the microbial reaction group alone. Furthermore, the degradation of aniline was most effective in this group. The increased consumption of sodium lactate suggests that aniline, under the mediation of AQS, promoted the metabolism of Shewanella oneidensis MR-1 cells and facilitated the involvement of more electrons in the reduction process. After the reaction, the solid mineral Fe (II)-O content increased to 41.32%. This study provides insights into the reduction mechanism of Fe (III) in the complex environment of microorganisms, iron minerals, electron shuttles, and pollutants. It aims to offer a theoretical basis for the biodegradation of aromatic hydrocarbon pollutants.