Abstract

Sulphuric acid is a key component in atmospheric new particle formation. However, sulphuric acid alone does not form stable enough clusters to initiate particle formation in atmospheric conditions. Strong bases, such as amines, have been suggested to stabilize sulphuric acid clusters and thus par... Show moreSulphuric acid is a key component in atmospheric new particle formation. However, sulphuric acid alone does not form stable enough clusters to initiate particle formation in atmospheric conditions. Strong bases, such as amines, have been suggested to stabilize sulphuric acid clusters and thus participate in particle formation. We modelled the formation rate of clusters with two sulphuric acid and two amine molecules (JA₂B₂) at varying atmospherically relevant conditions with respect to concentrations of sulphuric acid ([H₂SO₄]), dimethylamine ([DMA]) and trimethylamine ([TMA]), temperature and relative humidity (RH). We also tested how the model results change if we assume that the clusters with two sulphuric acid and two amine molecules would act as seeds for heterogeneous nucleation of organic vapours (other than amines) with higher atmospheric concentrations than sulphuric acid. The modelled formation rates JA₂B₂ were functions of sulphuric acid concentration with close to quadratic dependence, which is in good agreement with atmospheric observations of the connection between the particle formation rate and sulphuric acid concentration. The coefficients KA₂B₂ connecting the cluster formation rate and sulphuric acid concentrations as JA₂B₂=KA₂B₂[H₂SO₄]² turned out to depend also on amine concentrations, temperature and relative humidity. We compared the modelled coefficients KA₂B₂ with the corresponding coefficients calculated from the atmospheric observations (Kobs) from environments with varying temperatures and levels of anthropogenic influence. By taking into account the modelled behaviour of JA₂B₂ as a function of [H₂SO₄], temperature and RH, the atmospheric particle formation rate was reproduced more closely than with the traditional semi-empirical formulae based on sulphuric acid concentration only. The formation rates of clusters with two sulphuric acid and two amine molecules with different amine compositions (DMA or TMA or one of both) had different responses to varying meteorological conditions and concentrations of vapours participating in particle formation. The observed inverse proportionality of the coefficient Kobs with RH and temperature agreed best with the modelled coefficient KA₂B₂ related to formation of a cluster with two H₂SO₄ and one or two TMA molecules, assuming that these clusters can grow in collisions with abundant organic vapour molecules. In case this assumption is valid, our results suggest that the formation rate of clusters with at least two of both sulphuric acid and amine molecules might be the rate-limiting step for atmospheric particle formation. More generally, our analysis elucidates the sensitivity of the atmospheric particle formation rate to meteorological variables and concentrations of vapours participating in particle formation (also other than H₂SO₄). Show less