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Environmental persistent free radicals (EPFRs) are new environmental health risk substances in the atmosphere, and their oxidative toxicity (OT) has not been strongly confirmed. In this study, the fugitive characteristics of EPFRs in road dust in a metropolitan city located in northwest China, and their potential oxidative toxicity were investigated. The results showed that the road dust contains Carbon-centered EPFRs with the mean mass concentration of (6.6 ± 5.0) × 10 17 spins/g. EPFRs in road dust are degradable and have a half-life of 4.5 years. The water insoluble (WIS) components contribute 71% to the oxidative toxicity of road dust and show a rapid toxicity generation process, while the oxidative toxicity generation rate of water-soluble dust is more stable. Based on the positive matrix factorization (PMF) model, the contribution of EPFRs-dominated factors to Total-OT and WIS-OT is 17.3% and 33.3%, respectively. The PMF model results indicated that different types of EPFRs contributed differently to the oxidative toxicity of road dust and Carbon-centered EPFRs are more likely to participate in reactive oxygen species generation. Our results highlight that the EPFRs are an important contributor to the oxidative toxicity of atmospheric particulate matter, and their oxidative toxicity is dependent on the types of free radicals. It also provides an important insight into the influence of other potentially toxic substances on the oxidative toxicity of atmospheric PM., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 Elsevier B.V. All rights reserved.)