Amy M. Sage

Rethinking Organic Aerosols: Semivolatile Emissions and Photochemical Aging

Most primary organic-particulate emissions are semivolatile; thus, they partially evaporate with atmospheric dilution, creating substantial amounts of low-volatility gas-phase material. Laboratory experiments show that photo-oxidation of diesel emissions rapidly generates organic aerosol, greatly exceeding the contribution from known secondary organic-aerosol precursors. We attribute this unexplained secondary organic-aerosol production to the oxidation of low-volatility gas-phase species. Accounting for partitioning and photochemical processing of primary emissions creates a more regionally distributed aerosol and brings model predictions into better agreement with observations. Controlling organic particulate-matter concentrations will require substantial changes in the approaches that are currently used to measure and regulate emissions.

Laboratory measurements of the oxidation kinetics of organic aerosol mixtures using a relative rate constants approach

[1] 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.