Formation of Environmentally Persistent Free Radicals from the Irradiation of Polycyclic Aromatic Hydrocarbons

Abstract

Polycyclic aromatic hydrocarbons (PAHs) provide a complex matrix for environmentally persistent free radicals (EPFRs) to stabilize in particulate matter, allowing them to be transported over long distances in the atmosphere while participating in light-driven reactions and causing various cardiopulmonary diseases. In this study, four PAHs ranging from three to five rings (anthracene, phenanthrene, pyrene, and benzo[e]pyrene) were investigated for EPFR formation upon photochemical and aqueous-phase aging. Through electron paramagnetic resonance (EPR) spectroscopy, it was found that approximately 10¹⁵ to 10¹⁶ spins g^–1 of EPFRs were formed from the PAH upon aging. EPR analysis also revealed that carbon-centered and monooxygen-centered radicals were predominantly formed by irradiation. However, oxidation and fused-ring matrices have added complexity to the chemical environment of these carbon-centered radicals, as observed by their g-values. This study showed that atmospheric aging results not only in the transformation of PAH-derived EPFR but also in an increase in EPFR concentrations of up to 10¹⁷ spins g^–1. Therefore, because of their stability and photosensitivity, PAH-derived EPFRs have a major impact on the environment.