Evolution of Particle Composition in CLOUD Nucleation Experiments
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EGU Journal Logos (RGB) Open Access Open Access Open Access Advances in Annales Nonlinear Processes Geosciences Geophysicae in Geophysics Open Access Open Access Natural Hazards Natural Hazards and Earth System and Earth System Sciences Sciences Discussions Open Access Open Access Atmos. Chem. Phys., 13, 5587–5600, 2013 Atmospheric Atmospheric www.atmos-chem-phys.net/13/5587/2013/ doi:10.5194/acp-13-5587-2013 Chemistry Chemistry © Author(s) 2013. CC Attribution 3.0 License. and Physics and Physics Discussions Open Access Open Access Atmospheric Atmospheric Measurement Measurement Techniques Techniques Discussions Open Access Evolution of particle composition in CLOUD nucleation Open Access experiments Biogeosciences Biogeosciences Discussions H. Keskinen1, A. Virtanen1, J. Joutsensaari1, G. Tsagkogeorgas2, J. Duplissy3, S. Schobesberger3, M. Gysel4, F. Riccobono4, J. G. Slowik4, F. Bianchi4, T. Yli-Juuti3, K. Lehtipalo3, L. Rondo5, M. Breitenlechner6, A. Kupc7, 5 8 9,10 11 5 3 3 12 Open Access J. Almeida , A. Amorim , E. M. Dunne , A. J. Downard , S. Ehrhart , A. Franchin , M.K. Kajos , J. Kirkby , Open Access A. Kurten¨ 6, T. Nieminen3, V. Makhmutov13, S. Mathot12, P. Miettinen1, A. Onnela12, T. Petaj¨ a¨3, A. Praplan4, Climate F. D. Santos8, S. Schallhart3, M. Sipila¨3,14, Y. Stozhkov13, A. Tome´15, P. Vaattovaara1, D. WimmerClimate5, A. Prevot 4, J. Dommen4, N. M. Donahue16, R.C. Flagan11, E. Weingartner4, Y.Viisanen17, I. Riipinenof18, A.the Hansel Past6,19, J. Curtius5, of the Past M. Kulmala3, D. R. Worsnop1,3,20, U. Baltensperger4, H. Wex2, F. Stratmann2, and A. Laaksonen1,17 Discussions 1Dept. of Applied Physics, University of Eastern Finland, Kuopio, Finland Open Access 2Dept. of Physics, Leibniz Institute for Tropospheric Research, Leibniz, Germany Open Access 3Dept. of Physics, University of Helsinki, Helsinki, Finland Earth System Earth System 4Laboratory of Atmospheric Chemistry, Paul Scherrer Institute, Villigen, Switzerland Dynamics 5Institute for Atmospheric and Environmental Sciences, Johann Wolfgang Goethe University Frankfurt,Dynamics Frankfurt, Germany Discussions 6Institute for Ion and Applied Physics, University of Innsbruck, Innsbruck, Austria 7Faculty of Physics, University of Vienna, Vienna, Austria Open Access 8University of Lisbon, Lisbon, Portugal Geoscientific Geoscientific Open Access 9 School of Earth and Environment, University of Leeds, Leeds, UK Instrumentation Instrumentation 10Finnish Meteorological Institute, Kuopio, Finland 11Division of Chemistry and Chemical Engineering, California Institute of Technology, California,Methods USA and Methods and 12Centre europeen´ pour la recherche nucleaire´ (CERN), Geneva, Switzerland Data Systems Data Systems 13 Solar and Cosmic Ray Research Laboratory, Lebedev Physical Institute, Moscow, Russia Discussions Open Access 14Institute of Physics, University of Helsinki, Helsinki, Finland Open Access 15 Geoscientific University of Beira Interior, Beira, Portugal Geoscientific 16Carnegie Mellon University, Center of Atmospheric Particle Studies, Pittsburgh, USA Model Development 17Finnish Meteorological Institute, Helsinki, Finland Model Development Discussions 18University of Stockholm, Stockholm, Sweden 19Ionicon Analytik GmbH, Innbruck, Austria Open Access 20 Open Access Aerodyne Research, Billerica, Massachusetts, USA Hydrology and Hydrology and Correspondence to: H. Keskinen (helmi.keskinen@uef.fi) Earth System Earth System Received: 22 November 2012 – Published in Atmos. Chem. Phys. Discuss.: 4 December 2012 Sciences Sciences Revised: 6 May 2013 – Accepted: 7 May 2013 – Published: 6 June 2013 Discussions Open Access Open Access Ocean Science Abstract. Sulphuric acid, ammonia, amines, and oxidised or- and ion composition. HygroscopicityOcean Science was studied by a hy- ganics play a crucial role in nanoparticle formation in the groscopic tandem differential mobility analyser and a cloud Discussions atmosphere. In this study, we investigate the composition condensation nuclei counter, ethanol affinity by an organic of nucleated nanoparticles formed from these compounds in differential mobility analyser and particle oxidation level Open Access the CLOUD (Cosmics Leaving Outdoor Droplets) chamber by a high-resolution time-of-flight aerosol massOpen Access spectrom- experiments at CERN (Centre europeen´ pour la recherche eter. The ion composition was studied by an atmospheric Solid Earth nucleaire).´ The investigation was carried out via analysis of pressure interface time-of-flightSolid mass Earth spectrometer. The vol- the particle hygroscopicity, ethanol affinity, oxidation state, ume fraction of the organics in the particles during their Discussions Open Access Open Access Published by Copernicus Publications on behalf of the European Geosciences Union. The Cryosphere The Cryosphere Discussions 5588 H. Keskinen et al.: Evolution of particle composition in CLOUD nucleation experiments growth from sizes of a few nanometers to tens of nanome- recherche nucleaire),´ simulate these aerosol formation pro- ters was derived from measured hygroscopicity assuming the cesses (Kirkby et al., 2011). There have been several recent Zdanovskii–Stokes–Robinson relationship, and compared to studies concentrating on hygroscopic properties of SOA par- values gained from the spectrometers. The ZSR-relationship ticles, both in the laboratory and the field, to clarify their was also applied to obtain the measured ethanol affinities climatic effects (e.g. VanReken, et al., 2005; Juranyi´ et al., during the particle growth, which were used to derive the 2009; King et al., 2009; Wex et al., 2009; Massoli et al., volume fractions of sulphuric acid and the other inorganics 2010; Meyer et al., 2009; Duplissy et al., 2011). Recently, (e.g. ammonium salts). In the presence of sulphuric acid and Jimenez et al. (2009) and Massoli et al. (2010) summarised ammonia, particles with a mobility diameter of 150 nm were the effect of the oxidation state of SOA particles on their hy- chemically neutralised to ammonium sulphate. In the pres- groscopic properties. They found that higher oxidation levels ence of oxidation products of pinanediol, the organic volume led to higher hygroscopicity of the particles. fraction of freshly nucleated particles increased from 0.4 to As the chemical composition of the particles affects their ∼0.9, with an increase in diameter from 2 to 63 nm. Con- hygroscopic properties (Pruppacher and Klett, 1997), it is versely, the sulphuric acid volume fraction decreased from possible to infer information on their composition from hy- 0.6 to 0.1 when the particle diameter increased from 2 to groscopic growth measurements if the hygroscopic growth 50 nm. The results provide information on the composition factors of specific compounds are known (Raatikainen et of nucleated aerosol particles during their growth in the pres- al., 2010; Duplissy et al., 2011; Smith et al., 2012; Petaj¨ a¨ ence of various combinations of sulphuric acid, ammonia, et al., 2005). The composition of freshly nucleated atmo- dimethylamine and organic oxidation products. spheric particles in a eucalyptus forest has been studied by combining particle hygroscopic growth and volatility prop- erties (Ristovski et al., 2010). Also, ethanol affinity (i.e. the particles’ ability to uptake ethanol) can give complemen- 1 Introduction tary information on the particle composition in atmospheric studies, especially when the particles contain different com- Aerosol hygroscopicity, i.e. the ability of aerosol particles pounds with equal hygroscopic growth (Joutsensaari et al., to take up water, is important when estimating the effect of 2001; Vaattovaara et al., 2005). It is possible to gain infor- atmospheric aerosol particles on our climate. The aerosol di- mation on the nucleated nanoparticles’ size-dependent com- rect effect on climate (scattering of sunlight back to space) position during their growth via the direct and indirect ex- depends on the size of the atmospheric particles, which in perimental methods presented above. This can provide in- turn depends on the particle hygroscopicity and the surround- formation on the topical question of the organic contribu- ing relative humidity. Freshly nucleated nanoparticles in the tion to particle growth during nucleation (Pierce et al., 2011; atmosphere can grow into the size range where they are large Donahue et al., 2011; Riipinen et al., 2012). In this study enough to act as cloud condensation nuclei (Merikanto et we concentrate on studying the hygroscopicity of inorganic al., 2009), and therefore can become important for cloud and mixed inorganic/organic particles formed in the CERN processes. It is therefore important to include information CLOUD chamber. We use a hygroscopic tandem differen- on nucleated aerosol composition and hygroscopicity in cli- tial mobility analyser (H-TDMA) and a cloud condensation mate models to improve estimates of aerosol radiative forc- nuclei counter (CCNC). In addition, we combine the data ing. Nanoparticle formation via nucleation in the presence from an atmospheric pressure interface time-of-flight mass of atmospheric vapours and their subsequent condensational spectrometer (APi-TOF), H-TDMA, organic tandem differ- growth have been reported to produce atmospheric aerosol in ential analyser (O-TDMA) and an aerosol mass spectrometer a variety of environments (e.g. Kulmala et al., 2004; Hamed (AMS) to provide further information on the particle compo- et al., 2007). Numerous modelling studies suggest that these sition in the size