Carbon Mineralization in CO₂-Seawater-Basalt Systems: Reactive Transport Dynamics and Vesicular Pore Architecture...

Carbon mineralization in basaltic rocks offers a promising pathway for rapid, permanent CO₂ storage, yet fundamental controls on reactive transport, precipitation patterns, and permeability evolution under seawater conditions remain poorly constrained. This study integrates flow-through column experiments at 80 °C with CO₂-acidified seawater, geochemical modeling, and multiscale pore imaging (SEM-EDS and micro-CT) to elucidate mineralization dynamics in basaltic glass. Results demonstrate that carbonate precipitation is nucleation-limited and kinetically controlled rather than thermodynamically driven or growth-dominated, forming discrete patchy accumulations despite sustained supersaturation. An order-of-magnitude reduction in flow rate (0.05 to 0.005 mL/min) was required to achieve visible precipitation, highlighting residence time as the primary control. Postexperiment characterization identified calcium carbonate and inferred smectite-like clays, with dissolution-induced surface roughening and localized precipitation evident across the column. Seawater chemistry further complicates mineralization kinetics and efficiency relative to freshwater systems. Micro-CT analysis of three vesicular basalt facies revealed low coordination numbers (modal = 2) and serial connectivity, contrasting sharply with higher-coordination sandstone networks. The connected porosity (1.3-32%) differs significantly from the total segmented porosity (18-42%), demonstrating that network topology, rather than total porosity, controls permeability. Pore-scale observations thus indicate that precipitation may render basalts inherently more vulnerable to permeability impairment from modest, distributed precipitation. We explore end-member precipitation-induced clogging scenarios in which small, distributed precipitates cause disproportionately severe permeability loss compared to large, isolated masses. These findings underscore the need for probabilistic reactive transport frameworks that incorporate realistic pore topologies and nucleation barriers, which are fundamentally different from conventional CCS in sedimentary reservoirs, to improve predictions of injectivity and long-term carbon mineralization performance in mafic formations.