Carbon capture, utilization, and storage, one proposed method of reducing anthropogenic emissions of CO 2 , relies on low permeability formations, such as shales, above injection formations to prevent upward migration of the injected CO 2. Porosity in caprocks evaluated for sealing capacity before injection can be altered by geochemical reactions induced by dissolution of injected CO 2 into pore fluids, impacting long-term sealing capacity. Therefore, long-term performance of CO 2 sequestration sites may be dependent on both initial distribution and connectivity of pores in caprocks, and on changes induced by geochemical reaction after injection of CO 2 , which are currently poorly understood. This article presents results from an experimental study of changes to caprock porosity and pore network geometry in two caprock formations under conditions relevant to CO 2 sequestration. Pore connectivity and total porosity increased in the Gothic Shale; while total porosity increased but pore connectivity decreased in the Marine Tuscaloosa. Gothic Shale is a carbonate mudstone that contains volumetrically more carbonate minerals than Marine Tuscaloosa. Carbonate minerals dissolved to a greater extent than silicate minerals in Gothic Shale under high CO 2 conditions, leading to increased porosity at length scales <*200 nm that contributed to increased pore connectivity. In contrast, silicate minerals dissolved to a greater extent than carbonate minerals in Marine Tuscaloosa leading to increased porosity at all length scales, and specifically an increase in the number of pores >*1 lm. Mineral reactions also contributed to a decrease in pore connectivity, possibly as a result of precipitation in pore throats or hydration of the high percentage of clays. This study highlights the role that mineralogy of the caprock can play in geochemical response to CO 2 injection and resulting changes in sealing capacity in longterm CO 2 storage projects.

Laboratory experiments evaluated two shale caprock formations, the Gothic Shale and Marine Tuscaloosa Formation, at conditions relevant to carbon dioxide (CO 2) sequestration. Both rocks were exposed to CO 2saturated brines at 160°C and 15 MPa for *45 days. Baseline experiments for both rocks were pressurized with argon to 15 MPa for *35 days. Varying concentrations of iron, aqueous silica, sulfate, and initial pH decreases coincide with enhanced carbonate and silicate dissolution due to reaction between CO 2-saturated brine and shale. Saturation indices were calculated and activity diagrams were constructed to gain insights into sulfate, silicate, and carbonate mineral stabilities. Upon exposure to CO 2-saturated brines, the Marine Tuscaloosa Formation appeared to be more reactive than the Gothic Shale. Evolution of aqueous geochemistry in the experiments is consistent with mineral precipitation and dissolution reactions that affect porosity. This study highlights the importance of tracking fluid chemistry to clarify downhole physicochemical responses to CO 2 injection and subsequent changes in sealing capacity in CO 2 storage and utilization projects.