ACP Atmospheric Chemistry and Physics ACP 1680-7324 Copernicus GmbH Göttingen, Germany 10.5194/acp-11-10553-2011 Fragmentation vs. functionalization: chemical aging and organic aerosol formation Chacon-Madrid H. J. 1 Donahue N. M. 1 Center for Atmospheric Particle Studies, Carnegie Mellon University, Pittsburgh, Pennsylvania 15213, USA 25 10 2011 11 20 10553 10563 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/11/10553/2011/acp-11-10553-2011.html The full text article is available as a PDF file from http://www.atmos-chem-phys.net/11/10553/2011/acp-11-10553-2011.pdf

The transformation process that a carbon backbone undergoes in the atmosphere is complex and dynamic. Understanding all these changes for all the species in detail is impractical; however, choosing different molecules that resemble progressively higher stages of oxidation or aging and studying them can give us an insight into general characteristics and mechanisms. Here we determine secondary organic aerosol (SOA) mass yields of two sequences of molecules reacting with the OH radical at high NO<sub>x</sub>. Each sequence consists of species with similar vapor pressures, but a succession of oxidation states. The first sequence consists of <i>n</i>-pentadecane, <i>n</i>-tridecanal, 2-, 7-tridecanone, and pinonaldehyde. The second sequence consists of <i>n</i>-nonadecane, <i>n</i>-heptadecanal and <i>cis</i>-pinonic acid. Oxidized molecules tend to have lower relative SOA mass yields; however, oxidation state alone was not enough to predict how efficiently a molecule forms SOA. Certain functionalities are able to fragment more easily than others, and even the position of these functionalities on a molecule can have an effect. <i>n</i>-Alkanes tend to have the highest yields, and <i>n</i>-aldehydes the lowest. <i>n</i>-Ketones have slightly higher yields when the ketone moiety is located on the side of the molecule and not in the center. In general, oxidation products remain efficient SOA sources, though fragmentation makes them less effective than comparable alkanes.

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