Beyond Substituted p-Phenylenediamine Antioxidants: Prevalence of Their Quinone Derivatives in PM_2.5

Substituted para-phenylenediamine (PPD) antioxidants have been extensively used to retard oxidative degradation of tire rubber and were found to pervade multiple environmental compartments. However, there is a paucity of research on the environmental occurrences of their transformation products. In this study, we revealed the co-occurrence of six PPD-derived quinones (PPD-Qs) along with eight PPDs in fine particulate matter (PM_2.5) from two Chinese megacities, in which N,N′-bis(1,4-dimethylpentyl)-p-phenylenediamine quinone (77PD-Q) was identified and quantified for the first time. Prevalent occurrences of these emerging PPD-Qs were found in Taiyuan (5.59–8480 pg/m³) and Guangzhou (3.61–4490 pg/m³). Significantly higher levels of PPDs/PPD-Qs were observed at a roadside site, implying the possible contribution of vehicle emissions. Correlation analysis implied potential consistencies in the fate of these PPD-Qs and suggested that most of them were originated from the transformation of their parent PPDs. For different subpopulation groups under different exposure scenarios, the estimated daily intakes of PPD-Qs (0.16–1.25 ng kg_bw–1 day–1) were comparable to those of their parent PPDs (0.19–1.41 ng kg_bw–1 day–1), suggesting an important but overlooked exposure caused by novel PPD-Qs. Given the prolonged exposure of these antioxidants and their quinone derivatives to traffic-relevant occupations, further investigations on their toxicological and epidemiological effects are necessary.