ACP Atmospheric Chemistry and Physics ACP 1680-7324 Copernicus GmbH Göttingen, Germany 10.5194/acp-10-3803-2010 Characterization of oligomers from methylglyoxal under dark conditions: a pathway to produce secondary organic aerosol through cloud processing during nighttime Yasmeen F. 1 2 Sauret N. 1 Gal J.-F. 1 Maria P.-C. 1 Massi L. 3 Maenhaut W. 4 Claeys M. 2 Laboratoire de Radiochimie Sciences Analytique et Environnement, Institut de Chimie de Nice (CNRS, FR 3037), University of Nice Sophia-Antipolis, Faculty of Sciences, Parc Valrose, 06108 Nice Cedex 2, France Department of Pharmaceutical Sciences, University of Antwerp (Campus Drie Eiken), Universiteitsplein 1, 2610 Antwerp, Belgium Plate-forme Technologique-Spectrométrie de Masse, Institut de Chimie de Nice (CNRS, FR 3037), University of Nice Sophia-Antipolis, Faculty of Sciences Parc Valrose, 06108 Nice Cedex 2, France Department of Analytical Chemistry, Institute for Nuclear Sciences, Ghent University, Proeftuinstraat 86, 9000 Gent, Belgium 23 04 2010 10 8 3803 3812 This is an open-access article ditributed under the terms of the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original author and source are credited. This article is available from http://www.atmos-chem-phys.net/10/3803/2010/acp-10-3803-2010.html The full text article is available as a PDF file from http://www.atmos-chem-phys.net/10/3803/2010/acp-10-3803-2010.pdf

Aqueous-phase oligomer formation from methylglyoxal, a major atmospheric photooxidation product, has been investigated in a simulated cloud matrix under dark conditions. The aim of this study was to explore an additional pathway producing secondary organic aerosol (SOA) through cloud processes without participation of photochemistry during nighttime. Indeed, atmospheric models still underestimate SOA formation, as field measurements have revealed more SOA than predicted. Soluble oligomers (<i>n</i> = 1–8) formed in the course of acid-catalyzed aldol condensation and acid-catalyzed hydration followed by acetal formation have been detected and characterized by positive and negative ion electrospray ionization mass spectrometry. Aldol condensation proved to be a favorable mechanism under simulated cloud conditions, while hydration/acetal formation was found to strongly depend on the pH of the system and only occurred at a pH<3.5. No evidence was found for formation of organosulfates. The aldol oligomer series starts with a β-hydroxy ketone via aldol condensation, where oligomers are formed by multiple additions of C<sub>3</sub>H<sub>4</sub>O<sub>2</sub> units (72 Da) to the parent β-hydroxy ketone. Ion trap mass spectrometry experiments were performed to structurally characterize the major oligomer species. A mechanistic pathway for the growth of oligomers under cloud conditions and in the absence of UV-light and OH radicals, which could substantially enhance in-cloud SOA yields, is proposed here for the first time.

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