Buffering of atmospheric nanoparticle growth by temperature-dependent shifts in molecular composition, volatility and diffusivity

Abstract

Abstract. Aerosols have a profound influence on climate and human health, but new particle formation in the atmosphere has remained a scientific conundrum. In particular, the growth rates of atmospheric nanoparticles are often smaller and less dependent on condensable vapor concentration than expected. Here, we take a new integrative approach to analyze observational data from field measurements and chamber experiments, which were previously unexplained and appeared inconsistent with theory and model predictions. We show that the observed growth rates can be predicted when the temperature dependence and multiphase kinetics of gas-particle partitioning are resolved. Slow surface-to-bulk transport limits the rates of vapor uptake by semi-solid particles with low diffusivity, whereas shifts in the volatility distribution following the Clausius-Clapeyron equation enhance growth rates at low temperature and concentration levels. These antagonistic effects lead to an effective buffering of the organic vapor concentration dependence of nanoparticle growth in secondary organic aerosols. Our study reveals how counteracting temperature dependencies of organic vapor oxidation, volatility and diffusivity can explain the convergence of growth rates around a few nanometers per hour under widely varying atmospheric conditions.