Bisulfite enhances p-nitrophenol degradation by zero-valent iron under oxic conditions: Combination of indirect reduction by superoxide radical and direct reduction

Advanced oxidation processes based on the combination of zero-valent iron (ZVI) and S(IV) have been extensively investigated for oxidative degradation of organic pollutants, but little attention has been paid to their reducing capacities in the presence of oxygen. This work found bisulfite (BS) could greatly enhance the degradation of p-nitrophenol (PNP) by ZVI under oxic conditions and PNP was only reduced to p-aminophenol without further degradation. A combination of indirect reduction by superoxide radical (O 2 •– ) and direct reduction by ZVI was verified as the mechanism of PNP degradation. Highly oxidizing species, such as hydroxyl radical (HO • ) and sulfate radical (SO 4 •− ), were also produced in the ZVI/BS system under oxic conditions but did not contribute to pollutant degradation perhaps due to the rapid consumption by reducing substances like BS ions and the released Fe 2+ . BS concentration, ZVI dosage, initial solution pH and coexisting anions (CO 3 2– , PO 4 3– and Cl – ) affected the degradation of PNP. ZVI lost the reactivity after used for three times because of the production of goethite and lepidocrocite covered on its surface. This study will provide a new insight into degradation of organic pollutants in ZVI/BS system under oxic conditions.