Tunable Manipulation of Mineral Carbonation Kinetics in Nanoscale Water Films via Citrate Additives

We explored the influence of a model organic ligand on mineral carbonation in nanoscale interfacial water films by conducting five time-resolved in situ X-ray diffraction (XRD) experiments at 50 °C. Forsterite was exposed to water-saturated supercritical carbon dioxide (90 bar) that had been equilibrated with 0–0.5 m citrate (C6H5O7–3) solutions. The experimental results demonstrated that greater concentrations of citrate in the nanoscale interfacial water film promoted the precipitation of magnesite (MgCO3) relative to nesquehonite (MgCO3·3H2O). At the highest concentrations tested, magnesite nucleation and growth were inhibited, lowering the carbonation rate constant from 9.1 × 10–6 to 3.6 × 10–6 s–1. These impacts of citrate were due to partial dehydration of Mg2+(aq) and the adsorption of citrate onto nuclei and magnesite surfaces. This type of information may be used to predict and tailor subsurface mineralization rates and pathways.