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 the Weather 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.Atmosphere 2018, 9, 372 2 of 16 nitrogen oxides (NO x ), PAN could also be formed in air far away from these sources. PAN is relatively stable at low temperatures; however, it can be decomposed when the atmospheric temperature is high [2]. As a NO 2 reservoir species, it reduces NO 2 concentrations near the emission sources but releases NO 2 in regions remote from fresh emission sources [3]. It is, hence, concerning that PAN can affect NO x abundance and, ultimately, influence tropospheric ozone formation on local and regional scales.PAN is formed from the reaction of NO 2 and peroxy acetyl (PA) radical which is produced through photolysis and oxidation of a small number of oxygenated volatile organic compounds (OVOCs) (e.g., acetaldehyde (CH 3 CHO), acetone, methacrolein (MACR), methyl vinyl ketone (MVK), methyl ethyl ketone, and methylglyoxal (MGLY)) initiated by OH, NO 3 , and O 3 . Therefore, the abundances of aforementioned OVOCs will directly impact PAN levels in the atmosphere. Since PAN was first discovered in photochemical smog in Los Angeles in the 1950s, numerous studies have investigated the distribution and source contributions of PAN through field measurements and model simulations [3][4][5][6]. The characterization includes the abundance of PAN, the relationship with its precursors, and the contributions of regional transport i...