Experimental observations of CO₂-water-basaltic glass interaction in a large column reactor experiment at 50 °C

Mineralization of water dissolved carbon dioxide injected into basaltic rocks occurs within two years in field-scale settings. Here we present the results from a CO₂-water-basaltic glass laboratory experiment conducted at 50 °C and 80 bar pressure in a Ti high-pressure column flow reactor. We explore the possible sequence of saturation with Fe-Mg-Ca-carbonate minerals versus Fe-Mg-clay and Ca-zeolite saturation states, which all compete for divalent cations and pore space during injection of CO₂ into basaltic rocks. Pure water (initially with atmospheric CO₂) – basaltic glass reactions resulted in high pH (9–10) water saturated with respect to Mg-Fe-clays (saponites), Ca-zeolites, and Ca-carbonate. As CO₂-charged water (˜20 mM) entered the column and mixed with the high pH water, all the Fe-Mg-Ca-carbonates became temporarily supersaturated along with clays and zeolites. Injected waters with dissolved CO₂ reached carbonate mineral saturation within 12 h of fluid-rock interaction. Once the pH of the outflow water stabilized below 6, siderite was the only thermodynamically stable carbonate throughout the injection period, although no physical evidence of its precipitation was found. When CO₂ injection stopped while continuing to inject pure water, pH rose rapidly in the outflow and all carbonates became undersaturated, whereas zeolites became more saturated and Mg-Fe-saponites supersaturated. Resuming CO₂ injection lowered the pH from >8 to about 6, resulting in an undersaturation of the clays and Na-zeolites. These results along with geochemical modelling underscore the importance of initial pCO₂ and pH values to obtain a balance between the formation of carbonates versus clays and zeolites. Moreover, modelling indicates that pauses in CO₂ injection while still injecting water can result in enhanced large molar volume Ca-Na-zeolite and Mg-Fe-clay formation that consumes pore space within the rocks.