Impact of crystalline and amorphous iron- and aluminum hydroxides on mechanisms of phosphate adsorption and desorption
Stella Gypser , Florian Hirsch , Anja M. Schleicher , Dirk Freese
DOI:10.1016/j.jes.2017.12.001
Received May 29, 2017,Revised , Accepted December 01, 2017, Available online December 12, 2017
Volume 30,2018,Pages 175-189
Fourier-transform infrared (FT-IR) spectroscopic experiments were carried out during phosphate adsorption on highly crystalline gibbsite, poorly crystalline 2-line-ferrihydrite and amorphous iron–aluminum–hydroxide mixtures in the molar ratio 1:0, 10:1, 5:1, 1:1, 1:5, 1:10 and 0:1. The OH stretching vibrational bands were utilized to analyze changes in structural and surface OH groups during adsorption, because the position of characteristic P
O vibrational bands can shift depending on reaction conditions, pH or adsorbed phosphate content. Adsorption and desorption kinetics were studied at pH 6 and different initial phosphate concentrations to achieve varying phosphate coverage on the mineral surfaces. For gibbsite the formation of AlHPO4 and Al2HPO4 can be assumed, while for ferrihydrite, a FeHPO4 or Fe2PO4 complex and the precipitation of FePO4 with longer equilibration time were proposed. Fe2HPO4 or a Fe2PO4 surface complex was deduced for Fe-hydroxides, an AlH2PO4 surface complex was identified for Al-hydroxide, and both displayed either hydrogen bonds to neighboring hydroxyl groups or hydrogen bonds to outer-sphere complexes. Fe:Al-hydroxide mixtures with high Al ratios showed a low phosphate desorption rate, while ferrihydrite and the Fe:Al-hydroxide mixtures with high Fe ratios had almost negligible desorption rates. It was concluded that within the weakly associated amorphous FeO(OH) materials, FePO4 precipitated, which was bound by outer-sphere hydrogen bonds. With high Al ratios, desorption increased, which indicated weaker phosphate binding of both inner-sphere and outer-sphere complexes and hence, either no or minor quantities of precipitate. Ferrihydrite showed a more rigid structure and a lower extent of precipitation compared to amorphous Fe-hydroxide.
