Abstract
This research investigates the adsorption mechanisms of fluoride (F) on four clay minerals (kaolinite, montmorillonite, chlorite, and illite) under different F concentrations and reaction times by probing their fluoride superficial layer binding energies and element compositions using X-ray photoelectron spectroscopy (XPS). At high F concentrations ( = 5–1000 mg·L ), the amount of F adsorbed ( ), amount of hydroxide released by clay minerals, solution F concentration, and the pH increase with increasing . The increases are remarkable at >50 mg·L . The increases significantly by continuously modifying the pH level. At <5–100 mg·L , clay minerals adsorb H to protonate aluminum-bound surface-active hydroxyl sites in the superficial layers and induce F binding. As the increases, F , along with other cations, is adsorbed to form a quasi-cryolite structure. At >100 mg·L , new minerals precipitate and the product depends on the critical Al concentration. At [Al ]>10 mol·L , cryolite forms, while at [Al ]<10 mol·L , AlF is formed. At low (0.3–1.5 mg·L ), proton transfer occurs, and the F adsorption capabilities of the clay minerals increase with time.