On the formation of sulphuric acid – amine clusters in varying atmospheric conditions and its influence on atmospheric new particle formation

P Paasonen,T Olenius,A Laaksonen,H Vehkamäki,L G Huey,O Kupiainen,C Plass-Duelmer,M Hu,W Birmili,T Petäjä,A Wiedensohler,M Kulmala,I K Ortega,T Kurtén,V Loukonen,J N Smith,V.-M Kerminen,A Hamed,M J Mcgrath

doi:10.5194/acp-12-9113-2012

Abstract

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 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).

Highlights

The formation of new aerosol particles and their growth has been observed to take place in a wide variety of environments (Kulmala et al, 2004; Kulmala and Kerminen, 2008; Mirme et al, 2010; Zhang et al, 2012)
We examine in detail JA2B2, the formation rate of clusters including two or more sulphuric acid molecules and two or more amine molecules
We modelled the formation rate of clusters consisting of two sulphuric acid and two amine molecules with a kinetic cluster model (DACM)

Summary

Introduction

The formation of new aerosol particles and their growth has been observed to take place in a wide variety of environments (Kulmala et al, 2004; Kulmala and Kerminen, 2008; Mirme et al, 2010; Zhang et al, 2012). The most important vapour for atmospheric new particle formation is thought to be sulphuric acid, yet significant uncertainties related to the actual formation mechanism and role of other vapours in this process remain (Kerminen et al, 2010; Sipilaet al., 2010; Kirkby et al, 2011; Zhang et al, 2012). Field measurements indicate that the formation rate of new aerosol particles tend to be proportional to the ambient sulphuric acid concentration ([H2SO4]) to the power of 1–2 (Weber et al, 1996; Sihto et al, 2006; Riipinen et al, 2007; Kuang et al, 2008; Paasonen et al, 2010), but larger power values have been presented The corresponding semi-empirical expressions for the particle formation rate, J , may be written as:

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