1Environmental Chemical Processes Laboratory, Department of Chemistry, University of Crete, 71003, P.O. Box 2208, Heraklion, Greece
2Institute of Chemical Engineering and High Temperature Chemical Processes (ICE-HT), Foundation for Research and Technology Hellas (FORTH), Patras, 26504, Greece
3Center for Climate Systems Research, Columbia University, New York, NY 10025, USA
4NASA Goddard Institute for Space Studies, New York, NY 10025, USA
5Laboratoire des Sciences du Climat et de l'Environnement (LSCE), CNRS/CEA, 91190 Gif sur Yvette, France
6School of Earth and Atmospheric Sciences, Georgia Institute of Technology, 311 Ferst Drive, Atlanta, GA 30332-0100, USA
7School of Chemical and Biomolecular Engineering, Georgia Institute of Technology, 311 Ferst Drive, Atlanta, GA 30332-0100, USA
8Institute of Low Temperature Science, Hokkaido University, Sapporo, Japan
9TNO Built Environment and Geosciences, Department of Air Quality and Climate, P.O. Box 80015, 3508 TA Utrecht, The Netherlands
Received: 17 Dec 2010 – Published in Atmos. Chem. Phys. Discuss.: 07 Jan 2011
Abstract. Organic acids attract increasing attention as contributors to atmospheric acidity, secondary organic aerosol mass and aerosol hygroscopicity. Oxalic acid is globally the most abundant dicarboxylic acid, formed via chemical oxidation of gas-phase precursors in the aqueous phase of aerosols and droplets. Its lifecycle and atmospheric global distribution remain highly uncertain and are the focus of this study. The first global spatial and temporal distribution of oxalate, simulated using a state-of-the-art aqueous-phase chemical scheme embedded within the global 3-dimensional chemistry/transport model TM4-ECPL, is here presented. The model accounts for comprehensive gas-phase chemistry and its coupling with major aerosol constituents (including secondary organic aerosol). Model results are consistent with ambient observations of oxalate at rural and remote locations (slope = 1.16 ± 0.14, r2 = 0.36, N = 114) and suggest that aqueous-phase chemistry contributes significantly to the global atmospheric burden of secondary organic aerosol. In TM4-ECPL most oxalate is formed in-cloud and less than 5 % is produced in aerosol water. About 62 % of the oxalate is removed via wet deposition, 30 % by in-cloud reaction with hydroxyl radical, 4 % by in-cloud reaction with nitrate radical and 4 % by dry deposition. The in-cloud global oxalate net chemical production is calculated to be about 21–37 Tg yr−1 with almost 79 % originating from biogenic hydrocarbons, mainly isoprene. This condensed phase net source of oxalate in conjunction with a global mean turnover time against deposition of about 5 days, maintain oxalate's global tropospheric burden of 0.2–0.3 Tg, i.e. 0.05–0.1 Tg-C that is about 5–9 % of model-calculated water soluble organic carbon burden.
Revised: 03 Jun 2011 – Accepted: 10 Jun 2011 – Published: 22 Jun 2011
Citation: Myriokefalitakis, S., Tsigaridis, K., Mihalopoulos, N., Sciare, J., Nenes, A., Kawamura, K., Segers, A., and Kanakidou, M.: In-cloud oxalate formation in the global troposphere: a 3-D modeling study, Atmos. Chem. Phys., 11, 5761-5782, doi:10.5194/acp-11-5761-2011, 2011.