Low‐temperature dunite hydration: evaluating CH4 and H2 production from H2O and CO2

Abiotic methane (CH₄) and hydrogen (H₂) produced after hydration of mafic/ultramafic rocks represent energy sources for microbes that may thrive in the deep subsurface regions of Earth and possibly on other planets. While H₂ is a direct product of serpentinization, CH₄ can form via Fischer–Tropsch Type (FTT) reactions (carbon reduction) that, due to potential H₂ migration, can be spatially and temporally detached from serpentinization. We tested an alternative process hypothesized by some scholars, in which CO₂ can be reduced through dunite hydration without initially added H₂, implying that CH₄ can form in the same serpentinized fluid–rock system. The experiment used natural dunite sand (Forsterite 92), CO₂ with δ¹³C ~ ?25‰ (VPDB), and a 1 mm dissolved SiO₂ solution mixed in 30 glass bottles (118 mL) stored for up to 8 months at low temperature (50°C) to simulate land‐based serpentinization systems. In addition, 30 control bottles without olivine were used as blanks. Trivial amounts of CH₄ (orders of 0.2–0.9 ppmv) were detected in both samples and blanks, likely representing analytical noise; essentially, no significant amount of CH₄ formed under the experimental conditions used in this work. Low amounts of H₂ (~2.55 ± 1.39 ppmv) were generated, with production yields that were one order of magnitude lower than in previously published experiments. Moderate concentrations of SiO₂ appeared to hinder low‐temperature H₂ production. Our experiment confirms that the low‐temperature reduction of CO₂ into CH₄ through direct olivine hydration, without initial H₂, is sluggish and not straightforward, which is consistent with previous studies. The presence of substantial amounts of H₂, as well as suitable metal catalysts, appears to be essential in the low‐temperature production of abiotic CH₄, as observed in published FTT experiments.     

The geochemical evolution of very dilute CO2‐rich water in Chungcheong Province,Korea: processes and pathways

A geochemical study was carried out on the CO₂‐rich water occurring in granite areas of Chungcheong Province, Korea. In this area, very dilute and acidic CO₂‐rich waters [62–242 mg l^?1 in total dissolved solid (TDS), 4.0–5.3 in pH; group I) occur together with normal CO₂‐rich waters (317–988 mg l^?1 in TDS, 5.5–6.0 in pH; group II). The concentration levels and ages of group I water are similar to those of recently recharged and low‐mineralized groundwater (group III). Calculation of reaction pathways suggests that group I waters are produced by direct influx of CO₂ gas into group III type waters. When the groundwater is injected with CO₂, it develops the capacity to accept dissolved solids and it can evolve into water with very high solute concentrations. Whether the water is open or closed to the CO₂ gases becomes less important in controlling the reaction pathway of the CO₂‐rich groundwater when the initial pco ₂ is high. Our data show that most of the solutes are dissolved in the CO₂‐rich groundwater at pH > 5 where the weathering rates of silicates are very slow or independent of pH. Thus, groundwater age is likely more important in developing high solute concentrations in the CO₂‐rich groundwaters than accelerated weathering kinetics because of acidic pH caused by high pco ₂.     

Migration of metamorphic CO2 into a coal seam: a natural analog study to assess the long‐term fate of CO2 in Coal Bed Carbon Capture,Utilization, and Storage Projects

This study assesses the displacement of coalbed methane by CO₂ migration along a fault into the coal seam in the Yaojie coalfield. Coal and gas samples were collected continuously at various distances in NO.2 coal seam from F19 fault. Vitrinite reflectance, maceral, and pore distributions and proximate analysis of fourteen coal samples were performed. Gas components, concentrations, carbon isotopes of 28 gas samples were determined. We examined the coal–gas trace characteristics of coalbed methane displaced away from the fault by CO₂ injection after geological ages. From east to west, away from the F19 fault, the CO₂ concentration decreased, whereas the CH₄ concentration increased gradually. The δ¹³C values for CO₂ varied between ?9.94‰ and 1.12‰, suggesting a metamorphic origin. A wider range of values (from ?9.94‰ to 20‰) was associated with the mixing of microbial carbon dioxide, isotopic fractionation during CO₂ migration through the microporous structures of coals, and/or carbon isotope fractionation during gas–water exchange and dissolution of CO₂. Away from the F19 fault, the volumes of micropores, mesopores and macropores decrease gradually. The Dubinin–Radushkevich (DR) micropore volume decreased from 0.0059 to 0.0037 cm³ g^‐1, and the mesopore and macropore volumes decreased from 0.066 to 0.026 cm³ g^‐1. The CO₂ injection can mobilize aromatic hydrocarbons and mineral matter from coal matrix, resulting in the decrease in the absorption peak intensity for coal samples after supercritical CO₂ treatment, which indicates that chemical reactions occur between coal and CO₂, not only physical adsorption.     

Characteristics of CO2‐driven cold‐water geyser,Crystal Geyser in Utah: experimental observation and mechanism analyses

Geologic carbon capture and storage (CCS) is an option for reducing CO₂ emissions, but leakage to the surface is a risk factor. Natural CO₂ reservoirs that erupt from abandoned oil and gas holes leak to the surface as spectacular cold geysers in the Colorado Plateau, United States. A better understanding of the mechanisms of CO₂‐driven cold‐water geysers will provide valuable insight about the potential modes of leakage from engineered CCS sites. A notable example of a CO₂‐driven cold‐water geyser is Crystal Geyser in central Utah. We investigated the fluid mechanics of this regularly erupting geyser by instrumenting its conduit with sensors and measuring pressure and temperature every 20 sec over a period of 17 days. Analyses of these measurements suggest that the timescale of a single‐eruption cycle is composed of four successive eruption types with two recharge periods ranging from 30 to 40 h. Current eruption patterns exhibit a bimodal distribution, but these patterns evolved during past 80 years. The field observation suggests that the geyser's eruptions are regular and predictable and reflect pressure and temperature changes resulting from Joule–Thomson cooling and endothermic CO₂ exsolution. The eruption interval between multiple small‐scale eruptions is a direct indicator of the subsequent large‐scale eruption.     

Experimental study of the effect of variation in in‐situ stress on capillary residual trapping during CO2 geo‐sequestration in sandstone reservoirs

During a geo‐sequestration process, CO₂ injection causes an increase in reservoir pore pressure, which in turn decreases the reservoir net effective stress. Changes in effective stress can change all the reservoir and cap‐rock properties including residual saturations. This article presents the results of an experimental work carried out to understand the potential change in the volumes of residually trapped CO₂, while the porous medium tested underwent change in the net effective stress under in‐situ reservoir conditions of pore pressure and temperature. The experimental results obtained show that an initial 1725 psi (11.9 MPa) decrease in the net effective pressure caused 1.4% reduction in the volumes of residually trapped CO₂, while another 1500 psi (10.3 MPa) reduction caused a further 3.2% drop in the residual saturation of CO₂.     

Organic–inorganic rock–fluid interactions in stylolitic micro‐environments of carbonate rocks: a FIB‐TEM study combined with a hydrogeochemical modelling approach

Stylolites and the interfaces to the host limestone have been investigated by means of a multidisciplinary analytical approach (thin section microscopy, FIB‐TEM, organic geochemistry and petrography). Carbonate dissolution assuming different boundary conditions was simulated by applying a generic hydrogeochemical modelling approach. It is the conceptual approach to characterize and quantify traceable organic–inorganic interactions in stylolites dependent on organic matter type and its thermal maturity, and to follow stylolite formation in carbonates as result of organic matter reactivity rather than pressure solution as a main control. The investigated stylolite samples are of Upper Permian (Lopingian, Zechstein), Middle Triassic (Muschelkalk) and Late Cretaceous (Maastrichtian) age and always contain marine organic matter. The thermal maturity of the organic matter ranges from the pre‐oil generation zone (0.4–0.5% R_r) to the stage of dry gas generation (>1.3% R_r). The results of the generic hydrogeochemical modelling indicate a sharp increase of calcite dissolution and the beginning of stylolite formation at approximately 40°C, which is equivalent to a depth of less than 800 m under hydrostatic conditions considering a geothermal gradient of 30°C and a surface mean temperature of 20°C. This temperature corresponds to the pre‐oil window when kerogens release an aqueous fluid enriched in carbon dioxide and organic acids. This aqueous fluid may change the existing pore water pH or alkalinity and causes dissolution of carbonate, feldspar and quartz, and clay mineral precipitation along the stylolite. Dissolution of limestone and dolostone leads to reprecipitation of calcite or dolomite opposite of the dissolution side, which indicates only localized mass redistribution. All these integrated hydrogeochemical processes are coupled to the generation of water during organic matter maturation. In all of the calculated hydrogeochemical scenarios, H₂O is a reaction product and its formation supports the suggested hypothesis.     

Bleached mudstone,iron concretions,and calcite veins: a natural analogue for the effects of reducing CO2‐bearing fluids on migration and mineralization of iron,sealing properties,and composition of mudstone cap rocks

This study investigates the Wangfu Depression of the Songliao Basin, China, as a natural analogue site for Fe migration (bleaching) and mineralization (formation of iron concretions) caused by reducing CO₂‐bearing fluids that leak along fractures after carbon capture, utilization, and storage. We also examined the origin of fracture‐filling calcite veins, the properties of self‐sealing fluids, the influence of fluids on the compositions of mudstone and established a bleaching model for the study area. Our results show that iron concretions are the oxidative products of precursor minerals (pyrite and siderite) during uplift and are linked to H₂S and CO₂ present in early stage fluids. The precipitation of calcite veins is the result of CO₂ degassing and is related to CO₂, CH₄, and minor heavy hydrocarbons in the main bleaching fluids. In our model, fluids preferentially enter high‐permeability fracture systems and result in the bleaching of surrounding rocks and precipitation of calcite veins. The infilling of calcite veins significantly decreases the permeability of fractures and forces the fluids to slowly enter and bleach the mudstone rocks. The Fe²⁺ released during bleaching migrates to elsewhere with the solutions or is reprecipitated in the calcite veins and iron concretions. The formation of calcite veins reduces the fracture space and effectively prevents fluid flow. The fluids have an insignificant effect on minerals within the mudstone. In terms of the chemistry of the mudstone, only the contents of Fe₂O₃, U, and Mo change significantly, with the content of U increasing in the mudstone and the contents of Fe₂O₃ and Mo decreasing during bleaching.