Plagioclase dissolution during CO₂-SO₂ cosequestration: effects of sulfate

Geologic CO2 sequestration (GCS) is one of the most promising methods to mitigate the adverse impacts of global climate change. The performance of GCS can be affected by mineral dissolution and precipitation induced by injected CO2. Cosequestration with acidic gas such as SO2 can reduce the high cost of GCS, but it will increase the sulfate's concentration in GCS sites, where sulfate can potentially affect plagioclase dissolution/precipitation. This work investigated the effects of 0.05 M sulfate on plagioclase (anorthite) dissolution and subsequent mineral precipitation at 90 °C, 100 atm CO2, and 1 M NaCl, conditions relevant to GCS sites. The adsorption of sulfate on anorthite, a Ca-rich plagioclase, was examined using attenuated total reflectance Fourier-transform infrared spectroscopy and then simulated using density functional theory calculations. We found that the dissolution rate of anorthite was enhanced by a factor of 1.36 by the formation of inner-sphere monodentate complexes between sulfate and the aluminum sites on anorthite surfaces. However, this effect was almost completely suppressed in the presence of 0.01 M oxalate, an organic ligand that can exist in GCS sites. Interestingly, sulfate also inhibited the formation of secondary mineral precipitation through the formation of aluminum-sulfate complexes in the aqueous phase. This work, for the first time, reports the surface complexation between sulfate and plagioclase that can occur in GCS sites. The results provide new insights for obtaining scientific guidelines for the proper amount of SO2 coinjection and finally for evaluating the economic efficiency and environmental safety of GCS operations.