Open AccessLaboratory measurements of the oxidation kinetics of organic aerosol mixtures using a relative rate constants approach
Author(s) -
Huff Hartz Kara E.,
Weitkamp Emily A.,
Sage Amy M.,
Donahue Neil M.,
Robinson Allen L.
Publication year - 2007
Publication title -
journal of geophysical research: atmospheres
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.67
H-Index - 298
eISSN - 2156-2202
pISSN - 0148-0227
DOI - 10.1029/2006jd007526
Subject(s) - aerosol , reaction rate constant , oleic acid , chemistry , ozone , environmental chemistry , kinetics , atmosphere (unit) , reaction rate , decomposition , particle (ecology) , analytical chemistry (journal) , organic chemistry , thermodynamics , catalysis , physics , quantum mechanics , biochemistry , oceanography , geology
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.