Efficient Fluoride Removal by a Fixed-Bed Column of Self-Assembled Zr(IV)-, Fe(III)-, Cu(II)-Complexed Polyvinyl Alcohol Hydrogel Beads.

Fixed-bed column adsorption studies are performed with metal-complexed polyvinyl alcohol (PVA) hydrogel beads to remove fluoride from groundwater. The fixed-bed column (bed height = 8 ± 0.2 cm) of copper-zirconium-PVA (PCZH), zirconium-PVA (PZH), and iron-zirconium-PVA (PFZH) hydrogel beads have equilibrium fluoride removal capacities of 17.26 ± 0.05, 31.67 ± 0.05, and 11.84 ± 0.05 mg g from a 10 ± 0.20 mg L fluoride solution of pH 6.5 maintained at a flow rate of 1 ± 0.01 mL min. The breakthrough curves for fluoride adsorption are analyzed by non-linear empirical models of Thomas, Bohart-Adams, Yoon-Nelson, and semi-empirical bed depth service time models. The maximum fluoride adsorption capacities obtained from the Thomas model are 25.66 ± 0.05, 38.17 ± 0.05, and 13.75 ± 0.05 mg g for PCZH, PZH, and PFZH. Moreover, the column of PZH (bed height = 4 ± 0.2 cm) removes about 1.67 ± 0.05 mg g of fluoride from the alkaline groundwater sample with high total dissolved solids containing 2.84 ± 0.20 mg L fluoride maintained at a flow rate of 0.5 ± 0.01 mL min. The fluoride removal efficiency decreases marginally (<1 ± 0.02%) in the presence of interfering ions such as chlorides, sulfates, phosphates, bicarbonates, and nitrates. Furthermore, the fixed-bed column (bed height = 4 ± 0.2 cm) of PCZH, PZH, and PFZH remove 7.40 ± 0.05, 14.85 ± 0.05, and 6.53 ± 0.05 mg g fluoride, respectively, even after the third regeneration cycle. Additionally, the hydrogel beads are effective in the removal of arsenate (≤90 ± 0.02%) and chromate ions (≤96 ± 0.02%) from 100 ± 0.20 mg L solution in batch adsorption studies. Therefore, the hydrogel beads could be used as potent filters for the removal of fluoride, chromate, and arsenate ions from water.