Competitive kinetics of Ni(II)/Co(II) and Cr(VI)/P(V) adsorption and desorption on goethite: A unified thermodynamically based model

Abstract

Predicting the dynamic behavior of coexisting ions on mineral interface is essential to understanding their lability in soil matrix, but a mechanical kinetic model for predicting competitive adsorption is lacking. In this study, the thermodynamic and kinetic adsorption behaviors of Ni(II), Co(II), Cr(VI), and P(V) on goethite under various condition were investigated by batch and stirred-flow experiments, respectively. The equilibrium model CD-MUSIC was developed to describe their equilibrium behavior, followed by the development of a multi-rate kinetic model constrained by the equilibrium model to describe their kinetic behavior. Ni(II) and Co(II) exhibit similar adsorption affinities, while the adsorption of P(V) was stronger and faster than that of Cr(VI). The two surface species of Cr(VI) and P(V) differed in dynamic features, a finding confirmed by in-situ ATR-FTIR spectroscopy. The kinetic model was successfully used to predict the binary competitive adsorption of Ni(II)-Co(II) and Cr(VI)-P(V), and especially the overshooting of Cr(VI) induced by P(V). Our results showed that an integrated thermodynamic-kinetic model obtained from a single-ion experiment can be extended to describe complex multi-ion interactions, indicating the robustness and scalability of the model’s parameters. This approach can be used to construct more comprehensive equilibrium and dynamic models of the actual soil environment.