Formation of cation bridges and its promoting mechanism for sorption of sulfamethoxazole by montmorillonite

The coexistence of metal cations is often accompanied by organic pollution and could affect the environmental fate of organics by mediating the formation of cation bridges. However, the environmental fate and risk of organics in cation co-existing environments are poorly understood due to the lack of accurate identification of cation bridge formation and stability. In this study, the sorption of sulfamethoxazole (SMX) on montmorillonite (MT) with the coexistence of three different valence metal cations (Na + , Ca 2+ , and Cr 3+ ) was investigated. Ca 2+ and Cr 3+ can significantly promote the sorption of SMX on MT for about 5∼10 times promotion, respectively, while Na + bridges displayed little effect on the sorption of SMX. The sorption binding energy of SMX with MT-Ca (−44.01 kcal/mol) and MT-Cr (−64.57 kcal/mol) bridges was significantly lower than that with MT-Na (−38.45 kcal/mol) and MT (−39.39 kcal/mol), indicating that the sorption affinity of SMX on Cr and Ca bridges was much stronger. The higher valence of the cations also resulted in a more stable adsorbed SMX with less desorption fluctuation. In addition, the relatively higher initial concentration of SMX and the valence of cations increased the bonding density of the cation bridges, thus promoting the apparent sorption of SMX on MT to a certain extent. This work reveals the formation and function of cation bridges in the sorption of SMX on MT. It lays a theoretical foundation for further understanding the environmental fate and risk of organics.