Clustering Analysis on Drivers of O-3 Diurnal Pattern and Interactions with Nighttime NO3 and HONO

The long-path differential optical absorption spectroscopy (LP-DOAS) technique was deployed in Shanghai to continuously monitor ozone (O-3), formaldehyde (HCHO), nitrogen dioxide (NO2), nitrous acid (HONO), and nitrate radical (NO3) mixing ratios from September 2019 to August 2020. Through a clustering method, four typical clusters of the O-3 diurnal pattern were identified: high during both the daytime and nighttime (cluster 1), high during the nighttime but low during the daytime (cluster 2), low during both the daytime and nighttime (cluster 3), and low during the nighttime but high during the daytime (cluster 4). The drivers of O-3 variation for the four clusters were investigated for the day- and nighttime. Ambient NO caused the O-3 gap after midnight between clusters 1 and 2 and clusters 3 and 4. During the daytime, vigorous O-3 generation (clusters 1 and 4) was found to accompany higher temperature, lower humidity, lower wind speed, and higher radiation. Moreover, O-3 concentration correlated with HCHO for all clusters except for the low O-3 cluster 3, while O-3 correlated with HCHO/NOx, but anti-correlated with NOx for all clusters. The lower boundary layer height before midnight hindered O-3 diffusion and accordingly determined the final O-3 accumulation over the daily cycle for clusters 1 and 4. The interactions between the O-3 diel profile and other atmospheric reactive components established that higher HONO before sunrise significantly promoted daytime O-3 generation, while higher daytime O-3 led to a higher nighttime NO3 level. This paper summarizes the interplays between day- and nighttime oxidants and oxidation products, particularly the cause and effect for daytime O-3 generation from the perspective of nighttime atmospheric components.