The role of H2SO4-NH3 anion clusters in ion-induced aerosol nucleation mechanisms in the boreal forest

Abstract

New particle formation (NPF) provides a large source of atmospheric aerosols, which affect the climate and human health. In recent chamber studies, ion-induced nucleation (IIN) has been discovered as an important pathway of forming particles; however, atmospheric investigation remains incomplete. For this study, we investigated the air anion compositions in the boreal forest in southern Finland for three consecutive springs, with a special focus on H2SO4-NH3 anion clusters. We found that the ratio between the concentrations of highly oxygenated organic molecules (HOMs) and H2SO4 controlled the appearance of H2SO4-NH3 clusters (3 < no. S < 13): all such clusters were observed when [HOM]∕[H2SO4] was smaller than 30. The number of H2SO4 molecules in the largest observable cluster correlated with the probability of ion-induced nucleation (IIN) occurrence, which reached almost 100% when the largest observable cluster contained six or more H2SO4 molecules. During selected cases when the time evolution of H2SO4-NH3 clusters could be tracked, the calculated ion growth rates exhibited good agreement across measurement methods and cluster (particle) sizes. In these cases, H2SO4-NH3 clusters alone could explain ion growth up to 3nm (mobility diameter). IIN events also occurred in the absence of H2SO4-NH3, implying that other NPF mechanisms also prevail at this site, most likely involving HOMs. It seems that H2SO4 and HOMs both affect the occurrence of an IIN event, but their ratio ([HOMs]∕[H2SO4]) defines the primary mechanism of the event. Since that ratio is strongly influenced by solar radiation and temperature, the IIN mechanism ought to vary depending on conditions and seasons.