Quantifying the kinetic limitations of atmospheric gas-to-particle conversion
Abstract
Atmospheric aerosol particles, from anthropogenic and biogenic sources, remain a major uncertainty in the Earth system: they impact the climate by directly scattering and absorbing solar radiation, as well as regulating the properties of clouds. On regional scales, aerosols are among the main pollutants deteriorating air quality, their impacts on both poorly quantified. Reducing these uncertainties requires accurate knowledge on the composition, concentrations and size distributions of these particles as they reside in the atmosphere. Unfortunately, there are currently huge uncertainties in many fundamental parameters that are required to predict their environmental impacts. This is largely down to the fact that a significant fraction of atmospheric aerosol particles are comprised of organic material (20-90% of particle mass), containing potentially thousands of compounds with largely uncertain properties It is becoming increasingly evident that aerosols exist as metastable amorphous states, rather than simple liquid/solid mixtures. Empirical evidence suggests that particles can form glass like substances. As the glass transition temperature is approached, an increase in viscosity leads to a reduced rate of molecular diffusion and an arrested non-equilibrium structure. Partitioning between the gas and condensed phase is kinetically limited in such amorphous states. Traditional organic aerosol models do not account for this, they assume that 1) the aerosol phase is a well-mixed non-viscous liquid; 2) the aerosol phase instantaneously equilibrates with the gas phase constituents. This adds significant uncertainty to predictions of gas/particle mass transfer as mixing timescales are ultimately governed by the diffusion coefficients of the aerosol constituents in the aerosol, which, on the other hand, are connected to the viscosity of the particulate matter. For typical aerosol sizes, the characteristic time for mixing could increase from a few milliseconds to hours or even days. In this study, we present direct laboratory determination of viscosity/diffusing of atmospherically relevant species along with an evaluation of composition dependent predictive techniques. Output from highly detailed chemical mechanisms are used to probe potential sensitivities of these kinetic limitations and sensitivities to our predictive capability.
- Publication:
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AGU Fall Meeting Abstracts
- Pub Date:
- December 2013
- Bibcode:
- 2013AGUFM.A31D0112B
- Keywords:
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- 0305 ATMOSPHERIC COMPOSITION AND STRUCTURE Aerosols and particles