Geochemical effects of elevated methane and carbon dioxide in near-surface sediments above an EOR/CCUS site

Carbon capture, utilization and storage (CCUS) aims to reduce CO₂ emissions by capturing CO₂ from sources and injecting it into geologic reservoirs for enhanced hydrocarbon recovery and storage. One concern is that unintentional CO₂ and reservoir gas release to the surface may occur through seepage pathways such as fractures and/or improperly plugged wells. We hypothesize that CO₂ and CH₄ migration into the vadose zone and subsequent O₂ dilution and Eh and pH changes could create an increased potential for metal mobilization, which could potentially contaminate ground and surface waters. This potential has not been addressed elsewhere. Goals of this study are to understand how the potential for metal mobilization through soil pore water may increase due to CO₂ and CH₄ and to assess potential impact to aquifers and/or the biosphere. The study was conducted at a CCUS site in Cranfield, MS, where localized seepage of CH₄ (45%) from depth reaches the surface and oxidizes to CO₂ (34%) in the vadose zone near a plugged well. Four sediment cores (4.5-9m long) were collected in a transect extending from a background site through the area of anomalously high soil gas CO₂ and CH₄ concentrations. Sediment samples were analyzed for Eh and pH using slurries (1:1 vol. with DI water) in the field and for occluded gas concentrations, metal (Ba, Co, Cr, Cu, Fe, Mn, Ni, Pb and Zn) concentrations, moisture content, organic carbon content, and grain size in the laboratory. Data from the background reference area (no gas anomaly: occluded gas ~21% O₂, <1% CO₂, 0% CH₄) showed oxidized conditions (Eh from 464-508mV) and neutral pH (7.0-7.8) whereas samples collected near the gas anomaly (13-21% O₂, 0.1-5% CO₂, <0.1% CH₄) were more reducing (Eh 133-566mV) and more acidic (pH = 5.3-8.0). Significant correlations were found between Eh and O₂ (r = 0.95), pH and CO₂ (r = -0.88), and between these parameters and acid-leachable metals in samples from within the soil gas anomaly. Correlations quickly weaken away from the anomaly. Statistically, total metal concentrations, except for Ba, are similar in all cores. Acid-mobile metal concentrations, above 5m, increase toward the gas anomaly. The percent of water-mobile metals is very low (<2%) for all metals in all cores, indicating freely-mobile metals are not affected by elevated CO₂/CH₄. Conclusions are: 1) oxidation of CH₄ to CO₂ depletes O₂ causing reducing conditions; 2) high CO₂ and low O₂ affect Eh and pH of sediments which in turn alters mineralogy and bond strength between sediments and adsorbed ions; 3) intrusion of strongly acidic fluids (pH of acid used was 0.39) into these sediments could potentially remove weakly bonded metals or dissolve minerals. Implications from this study are that Eh needs to be considered along with pH when analyzing contamination potential, and that exposure of sediments to reducing, followed by acidic conditions, increases the potential for metal mobilization in the vadose zone. More research is needed to determine the concentration of gases (CO₂, CH₄ and O₂) that will create Eh and pH levels that could affect the mineralogy and sorption mechanism potentially leading to metal mobilization. Methods for assessing potential metal mobilization may be useful for site characterization and risk assessment.