Activating peroxides to produce active substances is the key to advanced oxidation processes (AOPs), but this usually requires energy or is accompanied by additional contaminants. In this study, diclofenac (DCF) was effectively removed by peracetic acid (PAA) in phosphate buffer (PBS). According to the results of radical scavenging experiments and electron paramagnetic resonance (EPR), hydroxyl radical (•OH) and organic radicals (i.e., CHC(=O)OO• and CHC(=O)O•) generated from PBS-activated PAA might be the dominant reactive species responsible for DCF degradation. At neutral pH, PBS/PAA system exhibited the best degradation efficiency on DCF. Presence of NO, SO and Cl had little effect on the removal of DCF, while HCO and natural organic matter (NOM) significantly inhibited DCF degradation in PBS/PAA system, resulting in the lower degradation efficiency of DCF in natural waters than that in ultrapure water. Finally, four possible degradation pathways, including hydroxylation, formylation, dehydrogenation and dechlorination, were proposed based on the detected reaction products. This study suggests that PBS used to control solution pH should be applied cautiously in PAA-based AOPs.
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