Secondary formation of oxalic acid and related organic species from biogenic sources in a larch forest at the northern slope of Mt. Fuji

Publication date: October 2017
Source:Atmospheric Environment, Volume 166
Author(s): Tomoki Mochizuki, Kimitaka Kawamura, Yuzo Miyazaki, Ryuichi Wada, Yoshiyuki Takahashi, Nobuko Saigusa, Akira Tani
To better understand the formation of water-soluble organic aerosols in the forest atmosphere, we measured low molecular weight (LMW) dicarboxylic acids, oxocarboxylic acids, α-dicarbonyls, unsaturated fatty acids (UFAs), and water-soluble organic carbon (WSOC) in aerosols from a Larix kaempferi forest located at the northern slope of Mt. Fuji, Japan, in summer 2012. Concentrations of dicarboxylic acids, oxocarboxylic acids, α-dicarbonyls, and WSOC showed maxima in daytime. Relative abundance of oxalic acid in LMW dicarboxylic acids was on average 52% and its average concentration was 214 ng m⁻³. We found that diurnal and temporal variations of oxalic acid are different from those of isoprene and α-pinene, whereas biogenic secondary organic aerosols (BSOAs) derived from isoprene and α-pinene showed similar variations with oxalic acid. The mass concentration ratios of oxalic acid/BSOAs were relatively constant, although a large variation in the concentrations of toluene that is an anthropogenic volatile organic compound was observed. These results suggest that formation of oxalic acid is associated with the oxidation of isoprene and α-pinene with O3 and other oxidants in the forest atmosphere. In addition, concentrations of UFAs were observed, for the first time, to decrease dramatically during daytime in the forest. Mass concentration ratios of azelaic acid to UFAs showed a positive correlation with O3, suggesting that UFAs are oxidized to yield azelaic acid, which may be further decomposed to oxalic acid in the forest atmosphere. We found that contributions of oxalic acid to WSOC are significantly high ranging from 3.7 to 9.7% (average 6.0%). This study demonstrates that forest ecosystem is an important source of oxalic acid and other dicarboxylic acids in the atmosphere.



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