Probing Into Ozone Production Through Photochemistry of Organic Peroxyl Radicals: Implications for Source Control

Abstract Ozone (O 3 ) pollution is a focus of the international community due to its health and environmental impacts. Organic peroxyl (RO 2 ) radicals play a significant role in O 3 initiation processes, which has implications for O 3 mitigation. RO 2 generated from volatile organic compounds (VOCs) sources contribute substantially to O 3 formation. However, quantifying the RO 2 from diverse sources is a great challenge. For the first time, we proposed a new hybrid Receptor‐Kinetic model to quantify sources contributions to RO 2 from the perspective of molecular level and functional groups of VOCs. We revealed that 3‐Hydroxy‐2‐butylperoxy (BUT2OLO 2 ), 4‐Hydroxy‐3‐methyl‐1‐butene‐3‐ylperoxy (ISOPBO 2 ) and 1‐Hydroxypropane‐2‐ylperoxy (HYPROPO 2 ) radicals were the dominant RO 2 , which were driven by reactions of cis/trans‐2‐butene (from Biogenic Emissions and Solvent Usage), isoprene (from Biogenic Emissions), and propylene (from Liquid Petroleum Gas Evaporation), respectively. The three dominant RO 2 radicals contributed significantly to O 3 production (28%, 10% and 14%), comparing with other 16 RO 2 . Sensitivity studies indicated that O 3 production can be decreased effectively by reducing the dominant RO 2 species for each source. Quantitative evidence suggested that targeting dominant RO 2 sources can be a novel direction for O 3 control.