UC Berkeley

The dissolution of CO2 in water leads to a pH decrease and a carbonate content increase in affected groundwater, which in turn can drive the mobilization of metals from sediments. The mechanisms of metal release postulated in various field and laboratory studies often differ. Drawing primarily on previously published results, we examine contrasting metal mobilization behaviors at two field tests and in one laboratory study, to investigate whether the same mechanisms could explain metal releases in these different experiments. Numerical modeling of the two field tests reveals that fast Ca-driven cation exchange (from calcite dissolution) can explain the release of most major and trace metal cations at both sites, and their parallel concentration trends. The dissolution of other minerals reacting more slowly (superimposed on cation exchange) also contributes to metal release over longer time frames, but can be masked by fast ambient groundwater velocities. Therefore, the magnitude and extent of mobilization depends not only on metal-mineral associations and sediment pH buffering characteristics, but also on groundwater flow rates, thus on the residence time of CO2-impacted groundwater relative to the rates of metal-release reactions. Sequential leaching laboratory tests modeled using the same metal-release concept as postulated from field experiments show that both field and laboratory data can be explained by the same processes. The reversibility of metal release upon CO2 degassing by de-pressurization is also explored using simple geochemical models, and shows that the sequestration of metals by resorption and re-precipitation upon CO2 exsolution is quite plausible and may warrant further attention.