Strong relations of peroxyacetyl nitrate (PAN) formation to alkene and nitrous acid during various episodes

Peroxyacetyl nitrate (PAN) is one of the critical secondary pollutants in photochemical smog. This study investigated the relationship between PAN and PAN precursors with the Regional Atmospheric Chemical Mechanism version 2 model in six episodes recorded in Zhengzhou. In all episodes, peroxyacetyl radical (PA) was primarily produced by acetaldehyde oxidation, with more than 70% contributions. In photochemical episodes and photochemical-haze co-occurring episodes (combined episodes), methylglyoxal secondarily contributes 8.1%-10.6% to PA while in haze pollution, the propagation of other radicals to PA is the second most important source (12.0%-19.1%). Among anthropogenic non-methane hydrocarbons, alkene restricted PAN formation as first-generation precursors, with the relative incremental reactivity of PAN (RIR_PAN) more than 0.6 during three-type episodes. Nitrous acid (HONO) also played important role in PAN formation. Especially during photochemical episodes, RIR_PAN(HONO) reached 0.79, which was comparable to the RIR_PAN value of alkene. Through sensitivity analysis of the relative formation of PAN to O₃ (the amount of PAN generated when 100 ppb O₃ formed), HONO was identified as the key precursor of PAN in haze pollution by promoting the oxidation of NMHC, while alkene predominated the relative formation of PAN to O₃ in photochemical and combined pollution through producing acetaldehyde. The sensitivity of PAN to HONO is obviously enhanced with higher NOx/VOC ratios during photochemical and combined pollution.