Alterations of Fractures in Carbonate Rocks by CO₂‑Acidified Brines

Fractures in geological formations may enable migration of environmentally relevant fluids, as in leakage of CO₂ through caprocks in geologic carbon sequestration. We investigated geochemically induced alterations of fracture geometry in Indiana Limestone specimens. Experiments were the first of their kind, with periodic high-resolution imaging using X-ray computed tomography (xCT) scanning while maintaining high pore pressure (100 bar). We studied two CO₂-acidified brines having the same pH (3.3) and comparable thermodynamic disequilibrium but different equilibrated pressures of CO₂ (<i>P</i>_CO₂ values of 12 and 77 bar). High-<i>P</i>_CO₂ brine has a faster calcite dissolution kinetic rate because of the accelerating effect of carbonic acid. Contrary to expectations, dissolution extents were comparable in the two experiments. However, progressive xCT images revealed extensive channelization for high <i>P</i>_CO₂, explained by strong positive feedback between ongoing flow and reaction. The pronounced channel increasingly directed flow to a small region of the fracture, which explains why the overall dissolution was lower than expected. Despite this, flow simulations revealed large increases in permeability in the high-<i>P</i>_CO₂ experiment. This study shows that the permeability evolution of dissolving fractures will be larger for faster-reacting fluids. The overall mechanism is not because more rock dissolves, as would be commonly assumed, but because of accelerated fracture channelization