Cd(II) adsorption on earth-abundant serpentine in aqueous environment: Role of interfacial ion specificity

Adsorption of heavy metal ions (e.g., Cd(II)) on clay minerals significantly affects their transport and fate in natural and engineered waterbodies. To date, the role of interfacial ion specificity in the adsorption of Cd(II) on earth-abundant serpentine remains elusive. In this work, the adsorption of Cd(II) on serpentine at typical environment conditions (pH 4.5–5.0), particularly under the complex influence of common environmental anions (e.g., NO3−, SO42−) and cations (e.g., K+, Ca2+, Fe3+, Al3+) was systemically investigated. It was found that the adsorption of Cd(II) on serpentine surface due to the inner-sphere complexation could be negligibly affected by the anion type, yet the cations specifically modulated the Cd(II) adsorption. The presence of mono- and divalent cations moderately enhanced the Cd(II) adsorption by weakening the electrostatic double layer (EDL) repulsion between Cd(II) and Mg–O plane of serpentine, while trivalent cations significantly suppressed the adsorption of Cd(II) due to the competitive adsorption. Based on the spectroscopy analysis, Fe3+ and Al3+ were found to robustly bind the surface active sites of serpentine, thereby preventing the inner-sphere adsorption of Cd(II). The density functional theory (DFT) calculation indicated that Fe(III) and Al(III) exhibited the larger adsorption energy (Ead = −146.1 and −516.1 kcal mol−1, respectively) and stronger electron transfer capacity with serpentine compared to Cd(II) (Ead = −118.1 kcal mol−1), thus resulting in the formation of more stable Fe(III)–O and Al(III)–O inner-sphere complexes. This study provides valuable insights into the influence of interfacial ion specificity on the Cd(II) adsorption in terrestrial and aquatic environments.