Direct contribution of ammonia to CCN-size alpha-pinene secondary organic aerosol formation

Abstract. Ammonia (NH3), a gasous compound ubiquitiously present in the atmosphere, is involved in the formation of secondary organic aerosol (SOA), but the exact mechanisum is still not well known. This study presents the results of SOA experiments from the photooxidation of α-pinene in the presence of NH3 in the reaction chamber. SOA was formed in nucleation experiment and in seeded experiment with ammonium sulfate particles as seeds. The chemical composition and time-series of compounds in the gas- and particle- phase were characterized by an on-line high-resolution time-of-flight proton transfer reaction mass spectrometer (HR-ToF-PTRMS) and a high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS), respectively. Our results show that for the aerosol particles in cloud condensation nuclei (CCN) size, the mass concentration of ammonium (NH4+) was still rising even after the mass concentration of organic component started to decrease due to aerosol wall deposition and evaporation, implying the continuous new formation of particle phase ammonium in the process. Stoichiometric neutralization analysis of aerosol indicates that organic acids have a central role in the formation of particle phase ammonium. Our measurements show a good correlation between the gas phase organic mono- and di-carboxylic acids formed in the photooxidation of α-pinene and the ammonium in the particle phase, thus highlighting the contribution of gas-phase organic acids to the ammonium formation in the CCN-size SOA particles. The work shows that the gas-phase organic acids contribute to the SOA formation by forming ammonium salts through acid-base reaction. The changes in aerosol mass, particle size and chemical composition resulting from the NH3-SOA interaction can potentially alter the aerosol direct and indirect forcing and therefore alter its impact on climate change.