Molecular characteristics and diurnal variations of organic aerosols at a rural site in the North China Plain with implications for the influence of regional biomass burning

Abstract. Field burning of crop residue in early summer releases into the atmosphere a large amount of pollutants with significant impacts on the air quality and aerosol properties in the North China Plain (NCP). In order to investigate the influence of this regional anthropogenic activity on organic molecular characteristics of aerosol, we collected PM 2.5 filter samples every 3 hours at a rural site of NCP during June 10 th to 25 th , 2013, and analyzed them for more than 100 organic tracer compounds, including both primary ( n -alkanes, fatty acids/alcohols, sugar compounds, polycyclic aromatic hydrocarbons, hopanes, and phthalate esters) and secondary (phthalic acids, isoprene-, α -/ β -pinene, β -caryophellen-, and toluene-derived products) organic aerosol tracers, as well as for organic carbon (OC), elemental carbon (EC), and water-soluble organic carbon (WSOC). Total concentrations of the measured organics ranged from 177 to 6248 ng m −3 (mean 1806 ± 1308 ng m −3 ) during the study period, most of which were contributed by sugar compounds, followed by fatty acids and fatty alcohols. Levoglucosan (240 ± 288 ng m −3 ) was the most abundant single compound and strongly correlated with OC and WSOC, suggesting that biomass burning (BB) is an important source of summertime organic aerosols in this rural region. Based on analysis of fire spots and backward trajectories of air masses, two representative periods were classified, which are (1) Period 1 (P1), Jun 13 th 21:00–16 th 15:00, when air masses were uniformly from the southeast part of NCP, where intensified open-field burning of biomass fuels occurred and (2) Period 2 (P2), Jun 22 nd 12:00–24 th 06:00, which were representative of local emission. Nearly all the measured PM components showed much higher concentrations in P1 than in P2. Although n -alkanes, fatty acids, and fatty alcohols presented similar temporal/diurnal variations as those of levoglucosan throughout the entire period, their molecular distributions were more dominated by high molecular weight (HMW) compounds in P1, demonstrating an enhanced contribution from BB emissions. In contrast, intensified BB emission in P1 seems to have limited influences on the concentrations of polycyclic aromatic hydrocarbons (PAHs), hopenes and phthalate esters. Both 3-hydroxyglutaric acid and β -caryophyllinic acid showed strong linearly correlations with levoglucosan (R 2  = 0.72 and 0.80, respectively), indicating that biomass burning is also an important source for terpene-derived SOA formation. A tracer-based method was used to access the distribution of biomass-burning OC, fungal-spore OC and secondary organic carbon (SOC) derived from isoprene, α -/ β -pinene, β -caryophyllene, and toluene in the different periods. The results showed that the contribution of biomass- burning OC to total OC in P1 (27.6 %) was 1.7 times of that in P2 (17.1 %). However, the contribution of SOC from oxidation of the four kinds of VOCs increased slightly from 16.3 % in P1 to 21.1 % in P2.