Diffusive Leakage of scCO2 in Shaly Caprocks: Effect of Geochemical Reactivity and Anisotropy

Supercritical carbon dioxide (scCO2) trapping mechanisms within carbon geostorage (CGS) primarily hinge on the upper caprock system, with shales being favored for their fine-grained nature and geological abundance. Experimental assessments of CO2 reactivity in brine-saturated shales reveal microstructural changes, raising concerns about long-term CO2 leakage risks. Existing models of scCO2 transport through caprocks lack consideration for shale anisotropy. This study addresses these gaps by investigating the diffusive properties and propagation of geochemical reactivity in shaly caprocks, accounting for anisotropy. Horizontal and vertical core samples from three shale formations with varying petrophysical characteristics underwent mineralogical, total organic carbon (TOC), porosity, and velocity measurements. scCO2 treatment for up to 3 weeks at 150°F and 3,000 psi was conducted. The propagation of geochemical reactivity was monitored by multiple surface X-ray fluorescence (XRF) measurements and fine polishing. A nuclear magnetic resonance (NMR)-based H2O-D2O fluid exchange protocol was used to quantify effective diffusivities and tortuosities parallel and perpendicular to bedding. Results indicate preferential surface reactivity toward carbonate minerals; however, the apparent reaction diffusivity of the shaly caprock is notably slow (~10−15 m2/s). This aligns with previous experimental and reactive transport modeling studies, emphasizing long timescales for carbonate dissolution reactions to influence shale caprock properties. Shale-effective diffusivities display anisotropy increasing with clay content, where diffusivities parallel to bedding exceed those perpendicular by at least three times. Faster horizontal diffusion in shaly confining zones should be considered when estimating diffusive leakage along faults penetrating these zones, a significant risk in CGS. Post-scCO2 treatment, diffusivity changes vary among samples, increasing within the same order of magnitude in the clay-rich sample. Nonsteady-state modeling of scCO2 diffusion suggests limited caprock penetration over 100 years, with a minimal increase from 5 m to 7 m post-scCO2 treatment for the clay-rich sample. This study extends existing literature observations on the slow molecular diffusion of scCO2 within shaly caprocks, integrating the roles of geochemical reactions and shale anisotropy under the examined conditions.