1Leibniz Institute for Tropospheric Research, Leipzig, Germany
2Department of Atmospheric Science, Colorado State University, Fort Collins, CO, USA
*now at: Department of Marine Earth and Atmospheric Science, North Carolina State University, Raleigh, NC, USA
**now at: National Environmental Research Institute, Aarhus University, Roskilde, Denmark
Received: 23 Jul 2009 – Published in Atmos. Chem. Phys. Discuss.: 07 Aug 2009
Abstract. The influence of varying levels of water mixing ratio, r, during the formation of secondary organic aerosol (SOA) from the ozonolysis of α-pinene on the SOA hygroscopicity and volatility was investigated. The reaction proceeded and aerosols were generated in a mixing chamber and the hygroscopic characteristics of the SOA were determined with the Leipzig Aerosol Cloud Interaction Simulator (LACIS) and a Cloud Condensation Nuclei counter (CCNc). In parallel, a High-Resolution Time-of-Flight Aerodyne Aerosol Mass Spectrometer (HR-ToF-AMS) located downstream of a thermodenuder (TD) sampling from the mixing chamber, to collect mass spectra of particles from the volatile and less-volatile fractions of the SOA. Results showed that both hygroscopic growth and the volatile fraction of the SOA increased with increases in r inside the mixing chamber during SOA generation. An effective density of 1.40 g cm−3 was observed for the generated SOA when the reaction proceeded with r>1 g kg−1. Changes in the concentrations of the fragment CO2+ and the sum of CxHyOz+ (short name CHO) and CxHy+ (short name CH) fragments as measured by the HR-ToF-AMS were used to estimate changes in the oxidation level of the SOA with reaction conditions, using the ratios CO2+ to CH and CHO to CH. Under humid conditions, both ratios increased, corresponding to the presence of more oxygenated functional groups (i.e., multifunctional carboxylic acids). This result is consistent with the α-pinene ozonolysis mechanisms which suggest that water interacts with the stabilized Criegee intermediate. The volatility and the hygroscopicity results show that SOA generation via ozonolysis of α-pinene in the presence of water vapour (r<16.9 g kg−1) leads to the formation of more highly oxygenated compounds that are more hygroscopic and more volatile than compounds formed under dry conditions.
Revised: 09 Apr 2010 – Accepted: 19 Apr 2010 – Published: 23 Apr 2010
Poulain, L., Wu, Z., Petters, M. D., Wex, H., Hallbauer, E., Wehner, B., Massling, A., Kreidenweis, S. M., and Stratmann, F.: Towards closing the gap between hygroscopic growth and CCN activation for secondary organic aerosols – Part 3: Influence of the chemical composition on the hygroscopic properties and volatile fractions of aerosols, Atmos. Chem. Phys., 10, 3775-3785, doi:10.5194/acp-10-3775-2010, 2010.