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 (C 6 H 5 O 7 -3 ) solutions. The experimental results demonstrated that greater concentrations of citrate in the nanoscale interfacial water film promoted the precipitation of magnesite (MgCO 3 ) relative to nesquehonite (MgCO 3 ·3H 2 O). At the highest concentrations tested, magnesite nucleation and growth were inhibited, lowering the carbonation rate constant from 9.1 × 10 -6 o 3.6 × 10 -6 s -1 . These impacts of citrate were due to partial dehydration of Mg 2+ (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.