Combination of immobilized TiO2 and zero valent iron for efficient arsenic removal in aqueous solutions

Abstract

The photocatalytic removal of arsenic from aqueous solutions was investigated using titania (TiO2) immobilized on a glass support, both bare and combined with synthesized metallic iron nanoparticles (nZVI) or commercial microscale iron (ZVI). Three procedures, namely dip-coating, rotational coating, and sponge coating, were tested for achieving the immobilization of TiO2. The photocatalytic activity of the semiconductor films under UV-irradiation after cumulative coatings was evaluated for 10 mg L−1 aqueous As(III), which was entirely oxidized to As(V) with all settings within 90 and 180 min. Titania immobilized by dip-coating was found to be the most effective as it showed the faster kinetics. The reuse of immobilized TiO2 was also investigated, detecting no changes in the photocatalytic activity after five consecutive reactions. The addition of commercial ZVI particles to the immobilized TiO2 system did not bring about significant changes in the kinetics for As(III) oxidation at the three pH values investigated, i.e., 5, 7, and 9. By contrast, the addition of nZVI not only led to a faster depletion of As(III) compared to bare titania but also the removal of As(V) from the solution to concentrations below 10 μg L−1, the upper limit recommended by the World Health Organization for human consumption.

The role of iron species in the arsenic removal process with both [ZVI + immobilized-TiO2] and [nZVI + immobilized-TiO2] systems was further investigated by performing adsorption and irradiation experiments without titania. It was inferred that within the pH range evaluated, the minor corrosion of the ZVI surface, even under UV irradiation, restricts the production of reactive oxidizing species and the generation of sites for arsenic species adsorption. By contrast, adsorption should be the main process responsible for the overall diminution of As(III) and As(V) species in solution attained upon nZVI addition, promoted by the increase of the external oxides/hydroxides layer on iron nanoparticles. Nevertheless, it might be also considered a certain contribution of UV-generated oxidant species formed in nZVI to the photocatalytic oxidation performance of titania.