Springtime influences of Asian outflow and photochemistry on the distributions of diacids, oxoacids and α-dicarbonyls in the aerosols from the western North Pacific Rim

Abstract

Abstract Total suspended particle (TSP) samples were collected at Cape Hedo, Okinawa on a basis of 24, 12 and 3 h intervals in March to April 2007, when the Asian outflow is enhanced. The filter samples were analysed for dicarboxylic acids, oxoacids, benzoic acid and α-dicarbonyls to better understand the sources, chemical composition and photochemical ageing of organic aerosols during long-range transport. Their molecular distributions showed a predominance of oxalic acid (C2) followed by malonic (C3) and succinic (C4) acids. Day/night samples did not show clear diurnal variations, suggesting that local anthropogenic influence is not important. The highest concentrations of C2 and other diacid species were observed in April 10 when air masses were delivered from north China. Higher concentrations were observed when air masses arrived from East Asia and coastal China. The 3 h samples showed higher concentrations of oxalic acid at 16:30 or at 13:30 during April 14 and 16, whereas higher relative abundance of C2 in total diacids and higher concentration ratios (C2/C3, C2/C4, C3/C4, C2/Gly, and C2/ωC2) were observed at 7:30 during April 14–16. These results suggest that aerosols were accumulated in the atmosphere during night and photochemically modified early in the morning. Oxalic acid–C/OC did not show a prominent peak in 3-h samples. Temporal variations in the concentrations of diacids, oxoacids and α-dicarbonyls, relative abundances and diacid–C/OC ratios together with 5 day back trajectory analyses show that the aerosols from Cape Hedo are strongly influenced by long-range atmospheric transport from East Asia, especially in China. Strong correlations of C2 with nss-SO42− and NO3− in night-time suggest a secondary formation of water-soluble diacids via heterogeneous aqueous phase oxidation during long-range transport.