1Department of Physics, University of Helsinki, Helsinki, Finland
2Department of Civil and Environmental Engineering, Portland State University, Portland, OR, USA
3Atmospheric Chemistry Division, National Center for Atmospheric Research, Boulder, CO, USA
4Finnish Meteorological Institute, Helsinki, Finland
5Department of Applied Environmental Science and Bert Bolin Centre for Climate Research, Stockholm University, Stockholm, Sweden
*now at: McKetta Department of Chemical Engineering, The University of Texas at Austin, Austin, TX, USA
Received: 11 Feb 2013 – Discussion started: 18 Mar 2013
Abstract. Climatic effects of newly-formed atmospheric secondary aerosol particles are to a large extent determined by their condensational growth rates. However, all the vapours condensing on atmospheric nanoparticles and growing them to climatically relevant sizes are not identified yet and the effects of particle phase processes on particle growth rates are poorly known. Besides sulfuric acid, organic compounds are known to contribute significantly to atmospheric nanoparticle growth. In this study a particle growth model MABNAG (Model for Acid-Base chemistry in NAnoparticle Growth) was developed to study the effect of salt formation on nanoparticle growth, which has been proposed as a potential mechanism lowering the equilibrium vapour pressures of organic compounds through dissociation in the particle phase and thus preventing their evaporation. MABNAG is a model for monodisperse aqueous particles and it couples dynamics of condensation to particle phase chemistry. Non-zero equilibrium vapour pressures, with both size and composition dependence, are considered for condensation. The model was applied for atmospherically relevant systems with sulfuric acid, one organic acid, ammonia, one amine and water in the gas phase allowed to condense on 3–20 nm particles. The effect of dissociation of the organic acid was found to be small under ambient conditions typical for a boreal forest site, but considerable for base-rich environments (gas phase concentrations of about 1010 cm−3 for the sum of the bases). The contribution of the bases to particle mass decreased as particle size increased, except at very high gas phase concentrations of the bases. The relative importance of amine versus ammonia did not change significantly as a function of particle size. While our results give a reasonable first estimate on the maximum contribution of salt formation to nanoparticle growth, further studies on, e.g. the thermodynamic properties of the atmospheric organics, concentrations of low-volatility organics and amines, along with studies investigating the applicability of thermodynamics for the smallest nanoparticles are needed to truly understand the acid-base chemistry of atmospheric nanoparticles.
Revised: 22 Nov 2013 – Accepted: 25 Nov 2013 – Published: 20 Dec 2013
Yli-Juuti, T., Barsanti, K., Hildebrandt Ruiz, L., Kieloaho, A.-J., Makkonen, U., Petäjä, T., Ruuskanen, T., Kulmala, M., and Riipinen, I.: Model for acid-base chemistry in nanoparticle growth (MABNAG), Atmos. Chem. Phys., 13, 12507-12524, doi:10.5194/acp-13-12507-2013, 2013.