Cerium(III)-induced structural transformation of hexagonal birnessite: Effect of mineral phase transition on arsenite transport and valence changes.

The widespread mining and application of rare earth elements (REEs) have led to their continuous accumulation in the environment, with increasing concentrations in soil. The interaction between the most abundant REEs, cerium (Ce), and the prevalent hexagonal birnessite (HB) in the environment is worth attention. HB is one of the most effective metal oxides for the oxidation of arsenite [As(III)] and subsequent adsorption, and thus for arsenic (As) immobilization. Therefore, in this study, we investigated the effect of the presence of Ce(III) ion on the HB formation process and the influence of generating minerals on the oxidation and removal of As(III). Research has found that the interfacial reactions of REEs in manganese (Mn) minerals not only affect their cycling but also alter the properties of the Mn minerals, thereby affecting the environmental fate of As. The results indicated that the presence of Ce ions affected the structure of HB during mineral synthesis and reduced the crystallinity of the conversion products. Their substitution for Mn(IV) in the lattice increased the specific surface area of minerals, reduced particle size, and produced more hydroxyl groups that were conducive to the immobilization of As(III). Meanwhile, Ce(III) was oxidized to Ce(IV) during the formation of Ce-bearing hexagonal birnessite (Ce-HB), and CeO nanoparticles were formed on the mineral surface and the removal rate of As(III) by Ce-HB was greatly improved. When the As concentration was lower than 6 mg·L, the removal effect of Ce-HB could reach the drinking water standard. However, the oxidation rate decreased due to the decrease in the proportion of Mn(IV). This study fundamentally reveals the behavior of HB coexisting with Ce in the migration and transformation of As(III) in the environment.