Photoinduced transformation of ferrihydrite in the presence of aqueous sulfite and its influence on the repartitioning of Cd.

The photoinduced transformation of ferrihydrite is an important process that can predict the geochemical cycle of Fe in anoxic environments as well as the fate of trace elements bonded to Fe minerals. We report that the photooxidation of sulfite by UV irradiation produces hydrated electrons (super-reductants), which significantly promote ferrihydrite reduction to Fe(II), and SO3•- (a moderate oxidant), enabling its further oxidation to more crystalline Fe(III) products. The experimental results show that the concentration of sulfite was key in influencing the rate and extent of surface-bound Fe(II) formation, which ultimately determined the distribution of individual products. For example, fitting of the Mössbauer spectroscopy data revealed that the relative abundances of mineral species after 8 h of treatment in the UV/sulfite systems were 41.9% lepidocrocite and 58.1% ferrihydrite at 2 mM SO32-; 41.8% goethite, 28.2% lepidocrocite, and 29.1% ferrihydrite at 5 mM SO32-; and 100% goethite at 10 mM SO32-. The combined results of the chemical speciation analysis and the Cd K-edge EXAFS characterization provided compelling evidence that Cd was firmly incorporated into the structure of newly formed minerals, particularly at high sulfite concentrations. These findings provide an understanding of the role of UV/sulfite in facilitating ferrihydrite transformation and promoting Cd stabilization in oxygen-deficit soils and aquatic environments.

Facile ammonium oxidation to nitrogen gas in acid wastewater by in situ photogenerated chlorine radicals.

The treatment of low-concentration ammonium (e.g., <50 mg L-1) in highly acidic wastewaters through traditional biological nitrification, physical separation, or chemical stripping remains a huge challenge. Herein, we report that photocatalytic ammonium oxidation using bismuth oxychloride (BiOCl) can successfully occur in Cl--laden solutions within a pH range of 1.0-6.0. All reactions follow pseudo-zero-order kinetics (with rate constants of 0.27-0.32 mg L-1 min-1 at pH 2.0-6.0 and 0.14 mg L-1 min-1 at pH 1.0), indicating the saturation of reactive species by the reactants. The interlayer is self-oxidized by the valence band holes (VB h+), resulting in the formation of Cl• and subsequently HClO, which is excited upon UV irradiation to provoke consecutive photoreactions for chlorine radical generation. Compared to the free chlorine, HO•, Cl•, and Cl2•-, the ClO• produced using the UV/BiOCl system plays a predominant role in oxidizing ammonium under acidic conditions. BiOCl exhibits good stability because of the compensation of Cl- from solution and maintains high activity under different conditions (i.e., different cations and co-existing anions, temperatures, and initial substrate concentrations). The successful removal of ammonium from real wastewater using the UV/BiOCl system suggests that this is a promising method for treating diluted ammonium under highly acidic conditions.