Highly Elevated Levels and Particle-Size Distributions of Environmentally Persistent Free Radicals in Haze-Associated Atmosphere.

Abstract

Levels and particle-size distributions of environmentally persistent free radicals (EPFRs) in haze-associated atmospheric particulate matter (PM) have not been highlighted, even though they may enter the human body along with PM and adversely affect human health. This study quantified the levels of EPFRs in airborne PM with different aerodynamic diameters (dae) using electron paramagnetic resonance (EPR) spectroscopy. EPR spectra showed a single, unstructured signal from persistent semiquinone radicals. The average concentration of EPFRs in the airborne PM during haze events was 2.18 × 1220 spins/g (range: 3.06 × 1019-6.23 × 1020 spins/g), approximately 2 orders of magnitude higher than that reported previously in the US atmosphere. Particle-size distributions of EPFRs in four different PM fractions (dae > 10 μm, 10 μm < dae < 2.5 μm, 2.5 μm <dae < 1 μm, dae < 1 μm) indicated the highest levels of EPFRs in the PM fraction with dae < 1 μm, with average 1/e lifetime of 59.2 days. A significant occurrence of EPFRs in PM samples collected from coal-burning activities (1.52 × 1022 spins/g), automobile exhaust (3.0 × 1022 spins/g), and biomass burning activities (1.14 × 1022 spins/g) was detected, which may be potential primary sources of EPFRs in airborne PM. The results in this study may help to understand the sources and potential risks of EPFRs in airborne fine particles.