Studies of the environmental fate through the interactions of particle-associated polycyclic aromatic hydrocarbons (PAHs) with environmentally persistent free radicals (EPFRs) are presented. The formation of PAHs and EPFRs typically occurs side by side during combustion-processes. The laboratory simulation studies of the model PAH molecule 1-Methylnaphthalene (1-MN) interaction with model EPFRs indicate a transformational synergy between these two pollutants due to mutual and matrix interactions. EPFRs, thorough its redox cycle result in the oxidation of PAHs into oxy-/hydroxy-PAHs. EPFRs have been shown before to produce OH radical during its redox cycle in aqueous media and this study has shown that produced OH radical can transform other PM constituents resulting in alteration of PM chemistry. In model PM, EPFRs driven oxidation process of 1-MN produced 1,4-naphthoquinone, 1-naphthaldehyde, 4-hydroxy-4-methylnaphthalen-1-one, and various isomers of (hydroxymethyl) naphthalene. Differences were observed in oxidation product yields, depending on whether EPFRs and PAHs were cohabiting the same PM or present on separate PM. This effect is attributed to the OH radical concentration gradient as a factor in the oxidation process, further strengthening the hypothesis of EPFRs' role in the PAH oxidation process. This finding is revealing new environmental role of EPFRs in a natural degradation process of PAHs. Additionally, it points to implications of such PM surface chemistry in the changing mobility of PAHs into an aqueous medium, thus increasing their bioavailability.
Keywords: 1-Methylnaphthalene; EPR; OH radical; Oxy-/hydroxy-PAHs; PM(2.5); Spin trapping.
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