Enhanced immobilization of phosphate by ferrihydrite during the photoreductive dissolution process

The surface interactions of iron (hydr)oxides with various environmental chemicals play a vital role in controlling their environmental transport and fate. As a bioessential element, phosphorus and its biogeochemical cycling are usually controlled by its adsorption on iron (hydr)oxides. Photoreductive dissolution of iron (hydr)oxides can change their surface structure and properties, but its influence on the adsorption of phosphate remains unknown. Here, an enhanced removal of phosphate during the photoreductive dissolution of ferrihydrite (Fh) was investigated. The K_d value of phosphate adsorption on Fh under light irradiation is evidently larger than that in the dark (21 vs 13 L/g). Zeta potential determination in combination with X-ray photoelectron spectroscopy analysis suggested that the released Fe²⁺ from Fh surface during photoreductive dissolution can be oxidized to Fe³⁺, which then co-adsorb with phosphate back to Fh surface, enhancing the immobilization of phosphate on Fh. In situ ATR-FTIR results disclosed that light irradiation could further facilitate the formation of ternary complexes and surface precipitation on Fh, even after the increment of phosphate adsorption becoming negligible in the dark, and the relative content of surface precipitation increased evidently. The desorption ratio of phosphate from the irradiated Fh sample was reduced, which should be attributed to a high content of surface precipitation that can tightly bind phosphate on Fh. The findings of this study highlight an important yet previously unappreciated pathway that light irradiation can enhance the immobilization of phosphate on iron (hydr)oxides.