Iodide-mediated photooxidation of arsenite under 254 nm irradiation

The preoxidation of As(III) to As(V) is a desirable process to increase the removal efficiency of arsenic in water treatment In this work, the photooxidation of As(III) under 254 nm irradiation was investigated in the concentration range of 1-1000 microM in the presence of potassium iodide (typically 100 microM). Although the direct photooxidation of As(III) in water was negligible, the presence of iodide dramatically enhanced the oxidation rate. The quantitative conversion of As(III) to As(V) was achieved. The quantum yields of As(III) photooxidation ranged from 0.08 to 0.6, depending on the concentration of iodide and As(III). The excitation of iodides under 254 nm irradiation led to the generation of iodine atoms and triiodides, which seem to be involved in the oxidation process of As(III). Because the efficiency of iodine atom generation is highly dependent on the presence of suitable electron acceptors,the photooxidation of As(III) was efficient in an air- or N2O-saturated solution but markedly reduced in the N2-saturated solution. The production of H2O2 was also accompanied by the generation of As(V). The addition of excess methanol (OH radical scavenger) did not reduce the photooxidation rate at all, which ruled out the possibility of hydroxyl radical involvement. It was found that the in situ photogenerated triiodides oxidize As(III) with regenerating iodides by completing a cycle. The proposed UV254/KI/As(III) process is essentially an iodide-mediated photocatalysis.