Organic radicals driving polycyclic aromatic hydrocarbon polymerization with peracetic acid activation in soil

The use of peracetic acid (PAA) in advanced oxidation processes has gained significant attention recently, but the knowledge of activating PAA to degrade polycyclic aromatic hydrocarbons (PAHs) is limited due to the variety and selectivity of reactive substances in PAA oxidation system. This paper presented the first systemically study on the degradation of PAHs by PAA activation in soil. It was found that heat-activated peracetic acid (heat/PAA) was capable of degrading phenanthrene (PHE) efficiently with degradation efficiency > 90 % within 30 min. Experimental results demonstrated that a series of reactive oxygen species (ROS) including organic radicals (RO^•), hydroxyl radicals (HO^•) and singlet oxygen (¹O₂) were generated, while acetylperoxyl (CH₃C(O)OO^•) and acetyloxyl (CH₃C(O)O^•) radicals were primarily responsible for PHE degradation in soil. Further analysis shows that polymerization products such as diphenic acid, 2'-formyl-2-biphenylcarboxylic acid and other macromolecules were dominant products of PHE degradation, suggesting polymerization driving PHE degradation instead of the conventional mineralization process. Toxicity analysis shows that most of the polymerization products had less toxicity than that of PHE. These results indicate that PAA activation was a highly effective remediation method for PAHs contaminated soil, which also provided a novel mechanism for pollutant degradation with the PAA activation process for environmental remediation.