Under What Conditions Can Equilibrium Gas-Particle Partitioning Be Expected to Hold in the Atmosphere?

Environ Sci Technol. 2015 Oct 6;49(19):11485-91. doi: 10.1021/acs.est.5b02587. Epub 2015 Sep 17.

Abstract

The prevailing treatment of secondary organic aerosol formation in atmospheric models is based on the assumption of instantaneous gas-particle equilibrium for the condensing species, yet compelling experimental evidence indicates that organic aerosols can exhibit the properties of highly viscous, semisolid particles, for which gas-particle equilibrium may be achieved slowly. The approach to gas-particle equilibrium partitioning is controlled by gas-phase diffusion, interfacial transport, and particle-phase diffusion. Here we evaluate the controlling processes and the time scale to achieve gas-particle equilibrium as a function of the volatility of the condensing species, its surface accommodation coefficient, and its particle-phase diffusivity. For particles in the size range of typical atmospheric organic aerosols (∼50-500 nm), the time scale to establish gas-particle equilibrium is generally governed either by interfacial accommodation or particle-phase diffusion. The rate of approach to equilibrium varies, depending on whether the bulk vapor concentration is constant, typical of an open system, or decreasing as a result of condensation into the particles, typical of a closed system.

Publication types

  • Research Support, U.S. Gov't, Non-P.H.S.

MeSH terms

  • Aerosols / chemistry*
  • Atmosphere*
  • Diffusion
  • Gases
  • Models, Theoretical
  • Particle Size
  • Volatilization

Substances

  • Aerosols
  • Gases