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Huff Hartz et al. 2007
Huff Hartz, K.E., Weitkamp, E.A., Sage, A.M., Donahue, N.M. and Robinson, A.L. (2007). Laboratory measurements of the oxidation kinetics of organic aerosol mixtures using a relative rate constants approach. Journal of Geophysical Research 112: doi: 10.1029/2006JD007526. issn: 0148-0227.

Organic aerosols in the atmosphere are exposed to oxidants, but the oxidation kinetics are largely unknown. We investigate the decay of organic species in laboratory-generated organic aerosols exposed to atmospherically relevant ozone concentrations in a smog chamber. The experiments were conducted using five different organic aerosols, varying in complexity from three to twelve components. These mixtures include alkenoic acids, alkanoic acids, alkanedioic acids, n-alkanes, and sterols and are designed to simulate meat cooking emissions. A relative rate constants approach was used to compare reaction rates of individual organic species and to compare the reaction rates of the aerosol species to gas phase tracers. Significant decay was observed for all species (except for the n-alkanes) in at least one of the experimental systems. By relating the decomposition of condensed phase alkenoic acids to gas phase alkenes, we show that the reaction rate constants of oleic acid and palmitoleic acid evolve as the aerosol is processed, decreasing by a factor of ~10 over the course of a 4-hour experiment. The decay rate constants of cholesterol, oleic acid, and palmitic acid all depend strongly on aerosol composition, with more than an order of magnitude change in the effective rate constants depending on mixture composition. Effects of aerosol composition are likely to be even more significant in atmospheric aerosol, where particle compositions are highly variable. The data presented here indicate these mixture effects are complicated, making it difficult to extrapolate from simple laboratory systems to atmospherically relevant conditions.

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Abstract

Keywords
Atmospheric Composition and Structure, Aerosols and particles (0345, 4801, 4906), Atmospheric Composition and Structure, Chemical kinetic and photochemical properties, Atmospheric Composition and Structure, Instruments and techniques, Atmospheric Processes, Clouds and aerosols
Journal
Journal of Geophysical Research
http://www.agu.org/journals/jb/
Publisher
American Geophysical Union
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