Zirconium-modified natural clays for phosphate removal: Effect of clay minerals

Excessive amount of phosphate entering water bodies may cause eutrophication and have detrimental effects on ecosystems. Clay-based materials have been drawing attractive attention in mitigating phosphate release to aquatic environment. In this study, we prepared a series of zirconium (Zr)-modified clays to investigate the effect of clay structure and expansion property on phosphate adsorption. Kaolinite, montmorillonite, and vermiculite were selected as three representative natural clays for Zr modification, and the resulting Zr-modified clays were characterized using various techniques that included powder X-ray diffraction, scanning electron microscopy, and zeta potential measurement. Different Zr-modified clays exhibited substantially different phosphate adsorption behaviors, which may be related to the distinct structural and expansion properties of each clay substrate. Particularly, Zr-modified montmorillonite had fastest phosphate adsorption kinetics and highest phosphate adsorption capacity among all Zr-modified clays, which may be attributed to the good expansion property of montmorillonite that favored the uniform intercalation of Zr species, making the adsorption sites easily accessible by phosphate. Furthermore, all Zr-modified clays showed robust performance for phosphate adsorption under various water chemistry conditions. Combined aqueous sorption and solid characterization analyses suggested that formation of inner-sphere surface complexes may be the primary mechanism for phosphate adsorption by Zr-modified clays.