Influence of photochemical loss of volatile organic compounds on understanding ozone formation mechanism

Abstract

Abstract. Volatile organic compounds (VOCs) tend to be consumed by atmospheric oxidants, resulting in substantial photochemical loss during transport. An observation-based model was used to evaluate the influence of photochemical loss of VOCs on the sensitivity regime and mechanisms of ozone formation. Our results showed that a VOC-limited regime based on observed VOC concentrations shifted to a transition regime with a photochemical initial concentration of VOCs (PIC-VOCs) in the morning. The net ozone formation rate was underestimated by 3 ppb h−1 (∼36 ppb d−1) based on the measured VOCs when compared with the PIC-VOCs. The relative contribution of the RO2 path to ozone production based on the PIC-VOCs accordingly increased by 13.4 %; in particular, the contribution of alkene-derived RO2 increased by approximately 10.2 %. In addition, the OH–HO2 radical cycle was obviously accelerated by highly reactive alkenes after accounting for photochemical loss of VOCs. The contribution of local photochemistry might be underestimated for both local and regional ozone pollution if consumed VOCs are not accounted for, and policymaking on ozone pollution prevention should focus on VOCs with a high reactivity.