Formation of Cd precipitates on Γ-Al₂O₃: Implications for Cd sequestration in the environment

Apart from surface complexation, precipitation of minerals also plays an important role in reducing the mobility and transport of heavy metals in the environment. In this study, Cd(II) sorption species on surfaces of γ-Al₂O₃ at pH 7.5 were characterized using multiple techniques. Results show that in addition to adsorption complexes, Cd hydroxide phases (Cd(OH)₂ precipitates and Cd_x(OH)_y polynuclear complexes) were formed at the initial stages of Cd(II) sorption and gradually transformed to CdCO₃ with time. In addition, Cd(II) formed Cd[sbnd]Al layered double hydroxide (LDH) on γ-Al₂O₃ under various conditions, independent of temperature and Cd loadings. The formation of Cd hydroxide phases and Cd[sbnd]Al LDH could be ascribed to surface-induced precipitation because the bulk solution was undersaturated with respect to hydroxides. Cd[sbnd]Al LDH formation on the Al-bearing mineral here is rather surprising because typically this occurs with elements of ionic radii similar to that of Al³⁺; this formation is unknown for metals such as Cd(II) with a much larger ionic radius. The thermodynamic feasibility of Cd[sbnd]Al LDH formation was further confirmed by laboratory synthesis of Cd[sbnd]Al LDH and density function theory (DFT) calculations. These results suggest that Cd precipitation on Al-bearing minerals can be an important mechanism for Cd immobilization in the natural environment. Additionally, the finding of Cd[sbnd]Al LDH formation on Al-bearing minerals and the thermodynamic stability of Cd[sbnd]Al LDH provides new insights into the remediation of Cd-polluted soils and aquatic systems.