1Department of Chemistry and Biochemistry, University of Delaware, Newark, Delaware 19716, USA
2Atmospheric Chemistry Division, National Center for Atmospheric Research, 1850 Table Mesa Dr., Boulder, Colorado 80305, USA
3Department of Applied Physics, University of Eastern Finland, 70211 Kuopio , Finland
4Department of Physical Sciences, University of Helsinki, 00014 Helsinki , Finland
*now at: Department of Chemical Engineering, University of Texas at Austin, Austin, Texas 78712, USA
Received: 05 Mar 2013 – Published in Atmos. Chem. Phys. Discuss.: 30 May 2013
Abstract. Atmospheric new particle formation (NPF) is a key source of ambient ultrafine particles that may contribute substantially to the global production of cloud condensation nuclei (CCN). While NPF is driven by atmospheric nucleation, its impact on CCN concentration depends strongly on atmospheric growth mechanisms since the growth rate must exceed the loss rate due to scavenging in order for the particles to reach the CCN size range. In this work, chemical composition measurements of 20 nm diameter particles during NPF in Hyytiälä, Finland, in March–April 2011 permit identification and quantitative assessment of important growth channels. In this work we show the following: (A) sulfuric acid, a key species associated with atmospheric nucleation, accounts for less than half of particle mass growth during this time period; (B) the sulfate content of a growing particle during NPF is quantitatively explained by condensation of gas-phase sulfuric acid molecules (i.e., sulfuric acid uptake is collision-limited); (C) sulfuric acid condensation substantially impacts the chemical composition of preexisting nanoparticles before new particles have grown to a size sufficient to be measured; (D) ammonium and sulfate concentrations are highly correlated, indicating that ammonia uptake is driven by sulfuric acid uptake; (E) sulfate neutralization by ammonium does not reach the predicted thermodynamic end point, suggesting that a barrier exists for ammonia uptake; (F) carbonaceous matter accounts for more than half of the particle mass growth, and its oxygen-to-carbon ratio (~ 0.5) is characteristic of freshly formed secondary organic aerosol; and (G) differences in the overall growth rate from one formation event to another are caused by variations in the growth rates of all major chemical species, not just one individual species.
Revised: 11 Sep 2013 – Accepted: 12 Sep 2013 – Published: 17 Oct 2013
Pennington, M. R., Bzdek, B. R., DePalma, J. W., Smith, J. N., Kortelainen, A.-M., Hildebrandt Ruiz, L., Petäjä, T., Kulmala, M., Worsnop, D. R., and Johnston, M. V.: Identification and quantification of particle growth channels during new particle formation, Atmos. Chem. Phys., 13, 10215-10225, doi:10.5194/acp-13-10215-2013, 2013.