Mechanisms of arsenate and cadmium co-immobilized on ferrihydrite inferred from ternary surface configuration

Abstract

Elucidating the interfacial interactions of arsenate (AsO43-) and cadmium (Cd) on minerals can better reveal their environmental behavior under various geological settings. Herein, the adsorption of Cd on ferrihydrite (Fh) in the presence of arsenate was investigated through batch experiments, surface complexation, and spectroscopic techniques. We determined the concentration-dependent interactions of Cd (II) and As (V) on each other’s behavior on Fh. Cadmium and arsenate tended to co-precipitate at high Cd/As ratios, whereas adsorption dominated at low Cd/As ratios. Compared with the single-ion system, the coexistence of Cd(II) and As on Fh significantly reduces the respective mobility of Cd(II) and As(V). The results of in situ attenuated total reflection–Fourier-transform infrared spectroscopy and charge distribution multisite complexation modeling revealed that the synergistic effects originated from electrostatic interactions and the formation of a ternary complex. The curve fitting of the spectra revealed three deconvolution peaks at ~ 765 cm−1, ~813 cm−1, and ~ 870 cm−1, which were assigned to As–OX (X = H+, cations, and H2O), As–O–Fe, and As–Oumcomplexed, respectively. After the addition of Cd(II), the intensity of As–OX increased at different pH values, indicating the formation of an As–O–Cd ternary complexes. We infer that two types of surface complex were assembled on the surface of Fh: namely anion-bridged Fe–As–Cd and cation-bridged Fe–Cd–As. These results contribute to our understanding of the behavior of multiple contaminates in an iron-rich environment and are helpful for the development of the corresponding restoration technology.