The role of fluoroaluminate complexes on the adsorption of fluoride onto hydrous alumina in aqueous solutions

Abstract

Activated alumina (AA) has been extensively applied in the defluorination of industrial wastewaters and groundwater. Although the dissolution of AA due to formation of fluoroaluminate complexes (AlFx3-x), especially in acidic condition, has been observed, its role on fluoride uptake by alumina has not been discussed in any previous literature, most of which consider F- as the sole adsorbed species. The present study described the effect of fluoroaluminate complexes on fluoride adsorption onto alumina. Results indicated that fluoroaluminate complexes, major fluoride species at pH < 6, were responsible for total fluoride adsorbed. Free fluoride ions were adsorbed mainly in the alkaline pH region, e.g., pH > 6. The dissolution of AA during defluorination was measured and analyzed by the thermodynamic solubility model. The surface concentration of F- and AlFx3-x were calculated considering electrostatic interactions. Characterization of fluoride-laden AA by XPS revealed that the fraction of surface Al-F species decreased with pH, which suggested the transition of the surface fluorinated species to that of free fluoride ions. The stability constants of four surface complexes, namely, AIOH-FAl2+, AlOH-F2Al+, AlOH2(+)(F)-F-, and AIOH-F-, were 10(6.88), 10(5.36), 10(2.72) and 10(2.36), respectively. Obviously fluoroaluminate complexes exhibited stronger chemical bonds with the surface hydroxy species than free fluoride. (C) 2019 Published by Elsevier Inc.