Dissolution behavior of mixed calcium‑cobalt carbonates at 25 °C in contact with different gas phases

Abstract

The potential immobilization of cobalt in various environments can be achieved through the incorporation of Co into carbonate minerals, forming solid solutions of (Ca_1-xCo_x)CO₃. However, the thermodynamic properties of these minerals are not well-understood due to conflicting data from natural observations and experiments. In this work, a series of mixed calcium‑cobalt carbonates were prepared and their interaction with aqueous solution was investigated. Depending on the Co/(Ca + Co) mol ratio (X_Co) of the mixed solution, ranging from 0.00 to 1.00, pure calcite, Co-bearing calcite, Co-bearing aragonite, Ca-bearing spherocobaltite and pure spherocobaltite were successively synthesized using a precipitation method. Upon dissolution of the Co-bearing solids (X_Co = 0.10–1.00) in N₂-degassed water (NW) and air-saturated water (AW), the Co concentration of the aqueous solutions increased gradually to a stable state of 0.017–0.191 and 0.018–0.186 mmol/L after 240–360 d dissolution, respectively. When the dissolution occurred in CO₂-saturated water (CW), the Co concentration initially spiked to 0.372–2.258 mmol/L within 6 h ∼ 15 d and then decreased to a stable range of 0.030–0.559 mmol/L after 240–360 d. The Co/(Ca + Co) mol ratio in the aqueous solution (X_Co2+,AS) was significantly lower than the Co/(Ca + Co) atomic ratio in the solids (X_Co,SS), particularly when dissolved in NW and AW. During these dissolution processes in NW, AW and CW at 25 °C, the average log IAP values at the final stable state were determined as follows: for calcite (CaCO₃), the values were −8.25 ± 0.03 in NW, −8.34 ± 0.11 in AW, and −8.10 ± 0.08 in CW; for spherocobaltite (CoCO₃), they were −9.24 ± 0.26 in NW, −9.39 ± 0.23 in AW, and −9.38 ± 0.09 in CW. Furthermore, the log IAP values increased from those typical for calcite to −7.89 ± 0.01 ∼ −7.84 ± 0.10 for the solid with X_Co,SS = 0.187 as X_Co,SS increased, eventually aligning with those typical of spherocobaltite. Lippmann diagrams, constructed using the Guggenheim parameters a₀ = 2.30 and a₁ = 0.265 for the “subregular” calcite-spherocobaltite solid solutions [(Ca_1-xCo_x)CO₃] with a miscibility gap ranging from X_Co,SS = 0.251 to 0.858, highlighted the “peritectic” point at X_Co2+,AS = 0.0538 on the solutus. This analysis revealed that the solids dissolved non-stoichiometrically in water. Consequently, the Co-poor aqueous solution would reach equilibrium with the Co-rich calcite-structure phase at the solid surface.