Anthropogenic Pollutants Induce Changes in Peroxyacetyl Nitrate Formation Intensity and Pathways in a Mountainous Background Atmosphere in Southern China.

Abstract

Mountainous background areas are typically considered to have a clean atmosphere where peroxyacetyl nitrate (PAN) can be decomposed. This study demonstrated that PAN was photochemically formed with a simulated production rate of 0.28 ± 0.06 ppbv h-1 in the Nanling mountains (1690 m a.s.l.) of South China and that net PAN formation was dependent on both volatile organic compounds (VOCs) and NOx precursors (transition regime). In contrast to dominated acetaldehyde oxidation in previous urban and rural research, PAN at Nanling was primarily formed by methylglyoxal (38%), acetaldehyde (28%), radicals (20%), and other oxygenated volatile organic compounds (OVOCs) (13%). Moreover, when polluted air masses invaded the Nanling mountains, the PAN production rate was altered, primarily because anthropogenic aromatics intensified PAN formation via the oxidized pathways of methylglyoxal, other OVOCs, and radicals. Finally, net PAN formation at Nanling reduced the hydroxyl radical level by consuming NOx, impaired local radical cycling, and thereby suppressed local O3 production. This suppressing effect was exacerbated on polluted days. The findings of this study deepen our understanding of PAN photochemistry and the impact of anthropogenic intrusions on the background atmosphere of mountainous regions.