Impact of humic acid on the photoreductive degradation of perfluorooctane sulfonate (PFOS) by UV/Iodide process

Abstract

Iodide photolysis under UV illumination affords an effective method to produce hydrated electrons (eaq–) in aqueous solution. Therefore, UV/Iodide photolysis can be utilized for the reductive degradation of many recalcitrant pollutants. However, the effect of naturally occurring organic matter (NOM) such as humic and fulvic acids (HA/FA), which may impact the efficiency of UV/Iodide photoreduction, is poorly understood. In this study, the UV photoreductive degradation of perfluorooctane sulfonate (PFOS) in the presence of I− and HA is studied. PFOS undergoes a relatively slow direct photoreduction in pure water, a moderate level of degradation via UV/Iodide, but a rapid degradation via UV/Iodide/HA photolysis. After 1.5 h of photolysis, 86.0% of the initial [PFOS] was degraded in the presence of both I− and HA with a corresponding defluorination ratio of 55.6%, whereas only 51.7% of PFOS was degraded with a defluorination ratio of 4.4% via UV/Iodide illumination in the absence of HA. The relative enhancement in the presence of HA in the photodegradation of PFOS can be attributed to several factors: a) HA enhances the effective generation of eaq– due to the reduction of I2, HOI, IO3− and I3− back to I−; b) certain functional groups of HA (i.e., quinones) enhance the electron transfer efficiency as electron shuttles; c) a weakly-bonded association of I− and PFOS with HA increases the reaction probability; and d) absorption of UV photons by HA itself produces eaq–. The degradation and defluorination efficiency of PFOS by UV/Iodide/HA process is dependent on pH and HA concentration. As pH increases from 7.0 to 10.0, the enhancement effect of HA improves significantly. The optimal HA concentration for the degradation of 0.03 mM PFOS is 1.0 mg L−1.