Investigation on the budget of peroxyacetyl nitrate (PAN) in the Yangtze River Delta: Unravelling local photochemistry and regional impact.

Peroxyacetyl nitrate (PAN) is a significant indicator of atmospheric photochemical pollution, which can influence the regional distribution of ozone (O) and hydroxyl radical (OH) through long-range transport. However, investigations of PAN incorporating comprehensive measurement and explicit modeling analysis are limited, hindering complete understandings of its temporal behavior, sources, and impacts on photochemistry. Here we conducted a 1-year continuous observation of PAN and relative atmospheric species in Nanjing located in Yangtze River Delta (YRD). The annual mean concentration of PAN was 0.62 ± 0.49 ppbv and showed a bimodal monthly variation, peaking in April-June and November-January, respectively. This pattern is different from the typical pattern of photochemistry, suggesting important contributions of other non-photochemical processes. We further analyzed the PAN budget using an observation-based model, by which, PAN from local photochemical production and regional source could be decoupled. Our results revealed that local photochemical production of PAN is the sole contributor to PAN in summer, whereas about half of the total PAN concentration is attributed to regional source in winter. Although the formation of PAN can suppress the atmospheric oxidation capacity by consuming the peroxyacetyl radical and nitrogen dioxide (NO), our analyses suggested this effect is minor at our station (-3.2 ± 1.1 % in summer and - 7.2 ± 2.8 % in winter for O formation). However, it has the potential to enhance O and OH formation by 14.16 % and 5.93 %, if transported to cleaner environments with air pollutants halved. Overall, our study highlights the importance of both local photochemistry and regional process in PAN budget and provides a useful evaluation on the impact of PAN on atmospheric oxidation capacity.