Fast generation of peroxides via atmospheric particulate photosensitization.

Liang, Zhancong; Zhou, Liyuan; Chan, Chak K · Sci Adv · 2025

basic_science · Level V

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Abstract

Peroxide species, including hydrogen peroxide (H<sub>2</sub>O<sub>2</sub>) and organic peroxides, are key oxidants in shaping the atmospheric oxidative capacity. However, their formation pathways remain elusive under high-NO<sub>x</sub> conditions, where gas-phase mechanisms are suppressed. Herein, we report an "in-particle" peroxide formation pathway driven by photosensitization reactions in biomass burning organic aerosol. This mechanism remains highly efficient even in polluted, high-NO<sub>x</sub> environments, leading to orders-of-magnitude increase in particulate H<sub>2</sub>O<sub>2</sub> concentrations in the presence of sunlight than that expected from gas-phase partitioning. These findings suggest that intensifying wildfires in our warming world, beyond their primary emissions, may substantially alter the atmospheric oxidation chemistry and exacerbate air quality degradation.