Large contributions of biogenic and anthropogenic sources to fine organic aerosols in Tianjin, North China

Abstract. In order to better understand the molecular composition and sources of organic aerosols in Tianjin, a coastal megacity in North China, ambient fine aerosol (PM2.5) samples were collected on a day/night basis during November–December 2016 and May–June 2017. Organic molecular compositions in PM2.5, including aliphatic lipids (n-alkanes, fatty acids and fatty alcohols), sugar compounds and photooxidation products from isoprene, monoterpene, β-caryophyllene, naphthalene and toluene, were analysed using gas chromatography-mass spectrometry. Fatty acids, fatty alcohols and saccharides were identified as the most abundant organic compound classes among all the tracers during both seasons. High concentrations of most organics at night in winter may be attributed to intensive residential activities such as house heating and the low boundary layer height. Based on the tracer methods, the contributions of the sum of primary and secondary organic carbon (POC and SOC) to aerosol organic carbon (OC) were 24.8 % (daytime) versus 27.6 % (nighttime) in winter and 38.9 % (daytime) versus 32.5 % (nighttime) in summer. In detail, POC derived from fungal spores, plant debris, and biomass burning accounted for 2.78–31.6 % (12.4 %) of OC in the daytime versus 4.72–45.9 % (16.3 %) at night in winter, and 1.28–9.89 % (5.24 %) versus 2.08–47.2 % (10.6 %) in summer. Biomass burning derived OC was the predominant source of POC in this study, especially at night (16.0 ± 6.88 % in winter and 9.62 ± 8.73 % in summer). Biogenic SOC from isoprene, α/β-pinene and β-caryophyllene exhibited obvious seasonal and diurnal variations, contributing 2.23 ± 1.27 % (2.30 ± 1.35 % in the daytime and 2.18 ± 1.19 % at night) and 8.60 ± 4.02 % (8.98 ± 3.67 % and 8.21 ± 4.39 %) to OC in winter and summer, respectively. Isoprene and α/β-pinene SOC were obviously elevated in summer, especially in the daytime, mainly due to strong photooxidation. Anthropogenic SOC from toluene and naphthalene oxidation contributed higher to OC in summer (21.0 ± 18.5 %) than in winter (9.58 ± 3.68 %). In summer, toluene SOC was the dominant contributor to aerosol OC, and biomass burning OC also accounted for a large portion to OC, especially in the nighttime, which indicate that land/sea breezes also play an important role in aerosol chemistry at the coastal city of Tianjin in North China.