Stable carbon isotopic compositions of low-molecular-weight dicarboxylic acids, glyoxylic acid and glyoxal in tropical aerosols: implications for photochemical processes of organic aerosols

Abstract

Tropical aerosols of PM2.5 and PM10 were collected at a rural site in Morogoro, Tanzania (East Africa), and analysed for stable carbon isotopic composition (δ13C) of dicarboxylic acids (C2–C9), glyoxylic acid (ωC2) and glyoxal (Gly) using gas chromatography/isotope ratio mass spectrometer. PM2.5 samples showed that δ13C of oxalic (C2) acid are largest (mean, −18.3±1.7‰) followed by malonic (C3, −19.6±1.0‰) and succinic (C4, −21.8±2.2‰) acids, whereas those in PM10 are a little smaller: −19.9±3.1‰ (C2), −20.2±2.7‰ (C3) and −23.3±3.2‰ (C4). The δ13C of C2–C4 diacids showed a decreasing trend with an increase in carbon numbers. The higher δ13C values of oxalic acid can be explained by isotopic enrichment of 13C in the remaining C2 due to the atmospheric decomposition of oxalic acid or its precursors. δ13C of ωC2 and Gly that are precursors of oxalic acid also showed larger values (mean, −22.5‰ and −20.2‰, respectively) in PM2.5 than those (−26.7‰ and −23.7‰) in PM10. The δ13C values of ωC2 and Gly are smaller than those of C2 in both PM2.5 and PM10. On the other hand, azelaic acid (C9; mean, −28.5‰) is more depleted in 13C, which is consistent with the previous knowledge; that is, C9 is produced by the oxidation of unsaturated fatty acids emitted from terrestrial higher plants. A significant enrichment of 13C in oxalic acid together with its negative correlations with relative abundance of C2 in total diacids and ratios of water-soluble organic carbon and organic carbon further support that a photochemical degradation of oxalic acid occurs during long-range transport from source regions.

Keywords

• PM2.5 and PM10
• stable carbon isotope ratios
• oxalic acid
• diacids
• glyoxylic acid
• glyoxal
• organic aerosols
• Tanzania
• East Africa