Atmospheric oxalic acid and SOA production from glyoxal: Results of aqueous photooxidation experiments

Aqueous-phase photooxidation of glyoxal, a ubiquitous water-soluble gas-phase oxidation product of many compounds, is a potentially important global and regional source of oxalic acid and secondary organic aerosol (SOA). Reaction kinetics and product analysis are needed to validate and refine current aqueous-phase mechanisms to facilitate prediction of in-cloud oxalic acid and SOA formation from glyoxal. In this work, aqueous-phase photochemical reactions of glyoxal and hydrogen peroxide were conducted at pH values typical of clouds and fogs (i.e., pH = 4-5). Experimental time series concentrations were compared to values obtained using a published kinetic model and reaction rate constants from the literature. Experimental results demonstrate the formation of oxalic acid, as predicted by the published aqueous phase mechanism. However, the published mechanism did not reproduce the glyoxylic and oxalic acid concentration dynamics. Formic acid and larger multifunctional compounds, which were not previously predicted, were also formed. An expanded aqueous-phase oxidation mechanism for glyoxal is proposed that reasonably explains the concentration dynamics of formic and oxalic acids and includes larger multifunctional compounds. The coefficient of determination for oxalic acid prediction was improved from 0.001 to > 0.8 using the expanded mechanism. The model predicts that less than 1% of oxalic acid is formed through the glyoxylic acid pathway. This work supports the hypothesis that SOA forms through cloud processing of glyoxal and other water-soluble products of alkenes and aromatics of anthropogenic, biogenic and marine origin and provides reaction kinetics needed for oxalic acid prediction. (C) 2007 Elsevier Ltd. All rights reserved.