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 (RIRPAN) more than 0.6 during threetype episodes. Nitrous acid (HONO) also played important role in PAN formation. Especially during photochemical episodes, RIRPAN(HONO) reached 0.79, which was comparable to the RIRPAN 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.

Automated summary

This study examined the relationship between PAN and PAN precursors using the RACM2 model in six episodes in Zhengzhou. Acetaldehyde oxidation was found to be the primary source of peroxyacetyl radical (PA), contributing over 70%. In photochemical and combined episodes, methylglyoxal and other radicals also played a role in PA formation. Alkene was identified as a first-generation precursor of PAN, while nitrous acid (HONO) promoted PAN formation in haze pollution. Sensitivity analysis revealed higher NOx/VOC ratios enhanced PAN sensitivity to HONO in photochemical and combined pollution.