Vertical changes in volatile organic compounds (VOCs) and impacts on photochemical ozone formation

Abstract. Volatile organic compounds (VOCs) play crucial roles in regulating the formation of tropospheric ozone. However, limited knowledge on the interactions between vertical VOC variations and photochemical ozone formation in the planetary boundary layer (PBL) has hindered effective ozone control strategies, especially in large cities. In this study, we investigated the vertical changes in concentrations, compositions, and key driving factors of a large suite of VOCs using online gradient measurements taken from a 325 m tall tower in urban Beijing. The impacts of these vertical VOC variations on photochemical ozone formation were also analyzed using box model simulations. Our results indicate that VOCs exhibited distinct vertical variation patterns due to their differences in sources and chemical reactivities, along with the diurnal evolution of the PBL. During daytime, reactive VOCs (e.g., hydrocarbons) are rapidly oxidized as they mix upward, accompanied by the formation and accumulation of oxygenated VOCs (OVOCs) in the middle and upper layers. In addition, the photochemical formation of ozone responds positively to changes in both NOx and VOCs. As a result, the production rate of ozone declines with height due to the simultaneous decreases in concentrations of reactive VOCs and NOx but remains high in the middle and upper layers. The strong production of ozone aloft is primarily driven by the presence of high OVOC concentrations. Therefore, careful consideration should be given to the vertical variations in both photochemical ozone production rates and formation regimes in the whole PBL when developing regional ozone control strategies.