Articles | Volume 15, issue 23
Atmos. Chem. Phys., 15, 13615–13625, 2015
Atmos. Chem. Phys., 15, 13615–13625, 2015

Research article 09 Dec 2015

Research article | 09 Dec 2015

Viscosity controls humidity dependence of N2O5 uptake to citric acid aerosol

G. Gržinić1,2, T. Bartels-Rausch1, T. Berkemeier3, A. Türler1,2, and M. Ammann2 G. Gržinić et al.
  • 1Laboratory of Radiochemistry and Environmental Chemistry, Paul Scherrer Institute, 5232 Villigen, Switzerland
  • 2Department of Chemistry and Biochemistry, University of Bern, 3012 Bern, Switzerland
  • 3Multiphase Chemistry Department, Max Planck Institute for Chemistry, 55128 Mainz, Germany

Abstract. The heterogeneous loss of dinitrogen pentoxide (N2O5) to aerosol particles has a significant impact on the night-time nitrogen oxide cycle and therefore the oxidative capacity in the troposphere. Using a 13N short-lived radioactive tracer method, we studied the uptake kinetics of N2O5 on citric acid aerosol particles as a function of relative humidity (RH). The results show that citric acid exhibits lower reactivity than similar dicarboxylic and polycarboxylic acids, with uptake coefficients between ∼ 3 × 10-4–∼ 3 × 10-3 depending on humidity (17–70 % RH). At RH above 50 %, the magnitude and the humidity dependence can be best explained by the viscosity of citric acid as compared to aqueous solutions of simpler organic and inorganic solutes and the variation of viscosity with RH and, hence, diffusivity in the organic matrix. Since the diffusion rates of N2O5 in highly concentrated citric acid solutions are not well established, we present four different parameterizations of N2O5 diffusivity based on the available literature data or estimates for viscosity and diffusivity of H2O. Above 50 % RH, uptake is consistent with the reacto-diffusive kinetic regime whereas below 50 % RH, the uptake coefficient is higher than expected from hydrolysis of N2O5 within the bulk of the particles, and the uptake kinetics is most likely limited by loss on the surface only. This study demonstrates the impact of viscosity in highly oxidized and highly functionalized secondary organic aerosol material on the heterogeneous chemistry of N2O5 and may explain some of the unexpectedly low loss rates to aerosol derived from field studies.

Short summary
The heterogeneous loss of dinitrogen pentoxide (N2O5) to citric acid aerosol, a proxy for highly oxygenated secondary organic aerosol, is shown to be substantially lower than to other aqueous organic aerosol proxies investigated previously. This is attributed to the widely changing viscosity within the atmospherically relevant humidity range. It may explain some of the unexpectedly low loss rates of N2O5 to aerosol particles derived from field studies.
Final-revised paper