Articles | Volume 15, issue 14
Atmos. Chem. Phys., 15, 7999–8012, 2015
Atmos. Chem. Phys., 15, 7999–8012, 2015

Research article 20 Jul 2015

Research article | 20 Jul 2015

Laboratory photochemical processing of aqueous aerosols: formation and degradation of dicarboxylic acids, oxocarboxylic acids and α-dicarbonyls

C. M. Pavuluri1, K. Kawamura1, N. Mihalopoulos1,2,3, and T. Swaminathan4 C. M. Pavuluri et al.
  • 1Institute of Low Temperature Science, Hokkaido University, Sapporo 060-0819, Japan
  • 2Environmental Chemical Processes Laboratory, Department of Chemistry, University of Crete, P.O. Box 2208, 71003 Voutes, Heraklion, Greece
  • 3Institute for Environmental Research and Sustainable Development, National Observatory of Athens, 15236 Palea Penteli, Greece
  • 4Department of Chemical Engineering, Indian Institute of Technology Madras, Chennai 600036, India

Abstract. To better understand the photochemical processing of dicarboxylic acids and related polar compounds, we conducted batch UV irradiation experiments on two types of aerosol samples collected from India, which represent anthropogenic (AA) and biogenic (BA) aerosols, for time periods of 0.5 to 120 h. The irradiated samples were analyzed for molecular compositions of diacids, oxoacids and α-dicarbonyls. The results show that photochemical degradation of oxalic (C2), malonic (C3) and other C8–C12 diacids overwhelmed their production in aqueous aerosols, whereas succinic acid (C4) and C5–C7 diacids showed a significant increase (ca. 10 times) during the course of irradiation experiments. The photochemical formation of oxoacids and α-dicarbonyls overwhelmed their degradation during the early stages of experiment except for ω-oxooctanoic acid (ωC8), which showed a similar pattern to that of C4. We also found a gradual decrease in the relative abundance of C2 to total diacids and an increase in the relative abundance of C4 during prolonged experiment. Based on the changes in concentrations and mass ratios of selected species with the irradiation time, we hypothesize that iron-catalyzed photolysis of C2 and C3 diacids controls their concentrations in Fe-rich atmospheric waters, whereas photochemical formation of C4 diacid (via ωC8) is enhanced with photochemical processing of aqueous aerosols in the atmosphere. This study demonstrates that the ambient aerosols contain abundant precursors that produce diacids, oxoacids and α-dicarbonyls, although some species such as oxalic acid decompose extensively during an early stage of photochemical processing.

Final-revised paper