Comparative study of the adsorption of tetracycline on clay minerals with various nanostructures: allophane, halloysite, and montmorillonite

With the over-use of tetracycline (TC) and its ultimate accumulation in aquatic systems, the demand for TC removal from contaminated water is increasing due to its severe threat to public health. Clay minerals have attracted great attention as low-cost adsorbents for controlling water pollution. The objective of the present study was to measure the adsorption behavior and mechanisms of TC on allophane, a nanosized clay mineral with a hollow spherical structure; to highlight the advantage of the allophane nanostructure, a further objective was to compare allophane with halloysite and montmorillonite, which have nanostructures that differ from allophane. Structural features and surface physicochemical properties were characterized by transmission electron microscopy (TEM), Fourier-transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), zeta potential, N₂-physisorption, and acid–base titration. The adsorption data showed that TC adsorption followed the pseudo-second order and Langmuir models. The adsorption was pH dependent, as all three clay minerals performed better under neutral to weakly alkaline conditions and maintained high adsorption performance in the presence of co-existing Na⁺/K⁺/Ca²⁺/Mg²⁺ cations. Regeneration of the adsorbent was excellent, with efficiencies exceeding 75% after five recycles. By comparison, allophane always exhibited the greatest adsorption capacity, up to 796 mg g^–1 at ~pH 9. The TC adsorption on allophane and halloysite was dominated by inner-sphere complexation, together with a small amount of electrostatic adsorption, while that on montmorillonite involved mainly interlayer cation exchange. The findings provide insights into the effects of nanostructures of clay minerals on their TC adsorption performance and highlight the huge potential of allophane as an efficient and inexpensive adsorbent for TC removal.