PAN-precursor relationship and process analysis of PAN variations in the Pearl River Delta region

Peroxy acetyl nitrate (PAN) is an important photochemical product formed from the reactions between volatile organic compounds (VOCs) and nitrogen oxides (NO_x) under sunlight. In this study, a field measurement was conducted at a rural site (the backgarden site, or BGS) of the Pearl River Delta (PRD) region in 2006, with the 10 min maximum PAN mixing ratios of 3.9 ppbv observed. The factors influencing the abundance of PAN at the BGS site was evaluated by the process analysis through theWeather Research and Forecasting-Community Multiscale Air Quality (WRF-CMAQ) model. The results suggested that the increase of PAN abundance at the BGS site was mainly controlled by the gas-phase chemistry, followed by vertical transport, while its loss was modulated mainly by dry deposition and horizontal transport. As the dominant important role of gas-phase chemistry, to provide detailed information on the photochemical formation of PAN, a photochemical box model with near-explicit chemical mechanism (i.e., the master chemical mechanism, MCM) was used to explore the relationship of photochemical PAN formation with its precursors based on the measured data at the BGS site. It was found that PAN formation was VOC-limited at the BGS site, with the oxidation of acetaldehyde the most important pathway for photochemical PAN production, followed by the oxidation and photolysis of methylglyoxal (MGLY). Among all the primary VOC precursors, isoprene and xylenes were the main contributors to PAN formation. Overall, our study provides new insights into the PAN photochemical formation and its controlling factors, and highlighted the importance of gas chemistry on the PAN abundance in the PRD region.