Effect of ions on sulfuric acid-water binary particle formation II: Experimental data and comparison with QC-normalized classical nucleation theory

Jonathan Duplissy (1, 2) , J. Merikanto (3) , A. Franchin (2) , G. Tsagkogeorgas (4) , J. Kangasluoma (2) , D. Wimmer (5, 2) , H. Vuollekoski (2) , S. Schobesberger (6, 2) , K. Lehtipalo (2) , R.C. Flagan (7) , D. Brus (3) , N.M. Donahue (8) , H. Vehkämäki (2) , J. Almeida (9, 5) , A. Amorim (10) , P. Barmet (11, 12) , F. Bianchi (13, 11) , M. Breitenlechner (14) , E.M. Dunne (15, 3) , R. Guida (9) , H. Henschel (3) , H. Junninen (2) , J. Kirkby (5, 9) , A. Kürten (5) , A. Kupc (16) , Anni Määttänen (17) , V. Makhmutov (18) , S. Mathot (9) , T. Nieminen (1) , A. Onnela (9) , A.P. Praplan (2) , F. Riccobono (11) , L. Rondo (5) , G. Steiner (14, 16, 2) , A. Tome (10) , H. Walther (11) , U. Baltensperger (11) , K.S. Carslaw (15) , J. Dommen (11) , A. Hansel (14) , T. Petäjä (2) , M. Sipilä (2) , F. Stratmann (4) , A. Vrtala (16) , P.E. Wagner (16) , D.R. Worsnop (2) , J. Curtius (8) , M. Kulmala (2)

1 HIP - Helsinki Institute of Physics
2 Department of Physics [Helsinki]
3 FMI - Finnish Meteorological Institute
4 TROPOS - Leibniz Institute for Tropospheric Research
5 IAU - Institute for Atmospheric and Environmental Sciences [Frankfurt/Main]
6 Department of Atmospheric Sciences [Seattle]
7 Departments of Environmental Science and Engineering and Chemical Engineering
8 CAPS - Center for Atmospheric Particle Studies [Pittsburgh]
9 CERN Theoretical Physics Department
10 CENTRA-SIM
11 LAC - Laboratory of Atmospheric Chemistry [Paul Scherrer Institute]
12 Department Construction, Traffic and Environment
13 IAC - Institute for Atmospheric and Climate Science [Zürich]
14 Institut für Ionenphysik und Angewandte Physik - Institute for Ion Physics and Applied Physics [Innsbruck]
15 SEE - School of Earth and Environment [Leeds]
16 Aerosol Physics and Environmental Physics [Vienna]
17 PLANETO - LATMOS
18 Solar and Cosmic Ray Research Laboratory [Moscow]

We report comprehensive, demonstrably contaminant-free measurements of binary particle formation rates by sulfuric acid and water for neutral and ion-induced pathways conducted in the European Organization for Nuclear Research Cosmics Leaving Outdoor Droplets chamber. The recently developed Atmospheric Pressure interface-time of flight-mass spectrometer was used to detect contaminants in charged clusters and to identify runs free of any contaminants. Four parameters were varied to cover ambient conditions: sulfuric acid concentration (105 to 109 mol cm−3), relative humidity (11% to 58%), temperature (207 K to 299 K), and total ion concentration (0 to 6800 ions cm−3). Formation rates were directly measured with novel instruments at sizes close to the critical cluster size (mobility size of 1.3 nm to 3.2 nm). We compare our results with predictions from Classical Nucleation Theory normalized by Quantum Chemical calculation (QC-normalized CNT), which is described in a companion paper. The formation rates predicted by the QC-normalized CNT were extended from critical cluster sizes to measured sizes using the UHMA2 sectional particle microphysics model. Our results show, for the first time, good agreement between predicted and measured particle formation rates for the binary (neutral and ion-induced) sulfuric acid-water system. Formation rates increase with RH, sulfuric acid, and ion concentrations and decrease with temperature at fixed RH and sulfuric acid concentration. Under atmospheric conditions, neutral particle formation dominates at low temperatures, while ion-induced particle formation dominates at higher temperatures. The good agreement between the theory and our comprehensive data set gives confidence in using the QC-normalized CNT as a powerful tool to study neutral and ion-induced binary particle formation in atmospheric modeling.

Mots clés: binary particle formation; ion-induced nucleation; sulfuric acid; classical nucleation theory

Domaines: Physique Atmosphérique et Océanique [physics.ao-ph]; Planétologie et astrophysique de la terre [astro-ph.EP]

Jonathan Duplissy, J. Merikanto, A. Franchin, G. Tsagkogeorgas, J. Kangasluoma, et al.. Effect of ions on sulfuric acid-water binary particle formation II: Experimental data and comparison with QC-normalized classical nucleation theory. Journal of Geophysical Research: Atmospheres, 2016, 121 (4), pp.1752-1775. ⟨10.1002/2015JD023539⟩. ⟨insu-01240195⟩