Why do organic aerosols exist? Understanding aerosol lifetimes using the two-dimensional volatility basis set

Abstract

Environmental context Fine particles (aerosols) containing organic compounds are central players in two important environmental issues: aerosol-climate effects and human health effects (including mortality). Although organics constitute half or more of the total fine-particle mass, their chemistry is extremely complex; of critical importance is ongoing oxidation chemistry in both the gas phase and the particle phase. Here we present a method for representing that oxidation chemistry when the actual composition of the organics is not known and show that relatively slow oxidant uptake to particles plays a key role in the very existence of organic aerosols. Abstract Organic aerosols play a critical role in atmospheric chemistry, human health and climate. Their behaviour is complex. They consist of thousands of organic molecules in a rich, possibly highly viscous mixture that may or may not be in phase equilibrium with organic vapours. Because the aerosol is a mixture, compounds from all sources interact and thus influence each other. Finally, most ambient organic aerosols are highly oxidised, so the molecules are secondary products formed from primary emissions by oxidation chemistry and possibly non-oxidative association reactions in multiple phases, including gas-phase oxidation, aqueous oxidation, condensed (organic) phase reactions and heterogeneous interactions of all these phases. In spite of this complexity, we can make a strong existential statement about organic aerosol: They exist throughout the troposphere because heterogeneous oxidation by OH radicals is more than an order of magnitude slower than comparable gas-phase oxidation. © 2013 CSIRO.