Atmos. Chem. Phys. Discuss., 13, 2913-2954, 2013
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This discussion paper has been under review for the journal Atmospheric Chemistry and Physics (ACP). Please refer to the corresponding final paper in ACP.
Radical mechanisms of methyl vinyl ketone oligomerization through aqueous phase OH-oxidation: on the paradoxical role of dissolved molecular oxygen
P. Renard1, F. Siekmann1, A. Gandolfo1, J. Socorro1, G. Salque3, S. Ravier1, E. Quivet1, J.-L. Clément2, M. Traikia5, A.-M. Delort5,6, D. Voisin3, R. Thissen4, and A. Monod1
1Aix-Marseille Université, CNRS, LCE FRE 3416, 13331 Marseille, France
2Aix-Marseille Université, CNRS, ICR UMR 7273, 13397 Marseille, France
3Université Joseph Fourier, Grenoble 1/CNRS-INSU, Laboratoire de Glaciologie et Géophysique de l'Environnement, 54 rue Molière, 38402 Saint-Martin-d'Hères, France
4Institut de Planétologie et d'Astrophysique de Grenoble (IPAG) UMR5274, UJF-Grenoble1/CNRS-INSU, Grenoble, 38041, France
5Clermont Université, Université Blaise Pascal, Institut de Chimie de Clermont-Ferrand, BP 10448, 63000 Clermont-Ferrand, France
6CNRS, UMR 6296, ICCF, BP 80026, 63171 Aubière, France

Abstract. It is now accepted that one of the important pathways of Secondary Organic Aerosol (SOA) formation occurs through aqueous phase chemistry in the atmosphere. However, the liquid phase chemical mechanisms leading to macromolecules are still not well understood. For α-dicarbonyl precursors, such as methylglyoxal and glyoxal, radical reactions through OH-oxidation produce oligomers, irreversibly and faster than accretion reactions. Methyl vinyl ketone (MVK) was chosen in the present study as it is an α, β-unsaturated carbonyl that can undergo such reaction pathways in the aqueous phase and forms even high molecular weight oligomers. We present here experiments on the aqueous phase OH-oxidation of MVK, performed under atmospheric relevant conditions. Using NMR and UV absorption spectroscopy, high and ultra-high resolution mass spectrometry, we show that the fast formation of oligomers up to 1800 Da is due to radical oligomerization of MVK, and 13 series of oligomers (out of a total of 26 series) are identified. The influence of atmospherically relevant parameters such as temperature, initial concentrations of MVK and dissolved oxygen are presented and discussed. In agreement with the experimental observations, we propose a chemical mechanism of OH-oxidation of MVK in the aqueous phase that proceeds via radical oligomerization of MVK on the olefin part of the molecule. This mechanism highlights the paradoxical role of dissolved O2: while it inhibits oligomerization reactions, it contributes to produce oligomerization initiator radicals, which rapidly consume O2, thus leading to the supremacy of oligomerization reactions after several minutes of reaction. These processes, together with the large ranges of initial concentrations investigated (60–656 μM of dissolved O2 and 0.2–20 mM of MVK) show the fundamental role that O2 likely plays in atmospheric organic aerosol.

Citation: Renard, P., Siekmann, F., Gandolfo, A., Socorro, J., Salque, G., Ravier, S., Quivet, E., Clément, J.-L., Traikia, M., Delort, A.-M., Voisin, D., Thissen, R., and Monod, A.: Radical mechanisms of methyl vinyl ketone oligomerization through aqueous phase OH-oxidation: on the paradoxical role of dissolved molecular oxygen, Atmos. Chem. Phys. Discuss., 13, 2913-2954, doi:10.5194/acpd-13-2913-2013, 2013.
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