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- ItemEvolution of particle composition in CLOUD nucleation experiments(München : European Geopyhsical Union, 2013) Keskinen, H.; Virtanen, A.; Joutsensaari, J.; Tsagkogeorgas, G.; Duplissy, J.; Schobesberger, S.; Gysel, M.; Riccobono, F.; Slowik, J.G.; Bianchi, F.; Yli-Juuti, T.; Lehtipalo, K.; Rondo, L.; Breitenlechner, M.; Kupc, A.; Almeida, J.; Amorim, A.; Dunne, E.M.; Downard, A.J.; Ehrhart, S.; Franchin, A.; Kajos, M.K.; Kirkby, J.; Kürten, A.; Nieminen, T.; Makhmutov, V.; Mathot, S.; Miettinen, P.; Onnela, A.; Petäjä, T.; Praplan, A.; Santos, F.D.; Schallhart, S.; Sipilä, M.; Stozhkov, Y.; Tomé, A.; Vaattovaara, P.; Wimmer, D.; Prevot, A.; Dommen, J.; Donahue, N.M.; Flagan, R.C.; Weingartner, E.; Viisanen, Y.; Riipinen, I.; Hansel, A.; Curtius, J.; Kulmala, M.; Worsnop, D.R.; Baltensperger, U.; Wex, H.; Stratmann, F.; Laaksonen, A.Sulphuric acid, ammonia, amines, and oxidised organics play a crucial role in nanoparticle formation in the atmosphere. In this study, we investigate the composition of nucleated nanoparticles formed from these compounds in the CLOUD (Cosmics Leaving Outdoor Droplets) chamber experiments at CERN (Centre européen pour la recherche nucléaire). The investigation was carried out via analysis of the particle hygroscopicity, ethanol affinity, oxidation state, and ion composition. Hygroscopicity was studied by a hygroscopic tandem differential mobility analyser and a cloud condensation nuclei counter, ethanol affinity by an organic differential mobility analyser and particle oxidation level by a high-resolution time-of-flight aerosol mass spectrometer. The ion composition was studied by an atmospheric pressure interface time-of-flight mass spectrometer. The volume fraction of the organics in the particles during their growth from sizes of a few nanometers to tens of nanometers was derived from measured hygroscopicity assuming the Zdanovskii–Stokes–Robinson relationship, and compared to values gained from the spectrometers. The ZSR-relationship was also applied to obtain the measured ethanol affinities during the particle growth, which were used to derive the volume fractions of sulphuric acid and the other inorganics (e.g. ammonium salts). In the presence of sulphuric acid and ammonia, particles with a mobility diameter of 150 nm were chemically neutralised to ammonium sulphate. In the presence of oxidation products of pinanediol, the organic volume fraction of freshly nucleated particles increased from 0.4 to ~0.9, with an increase in diameter from 2 to 63 nm. Conversely, the sulphuric acid volume fraction decreased from 0.6 to 0.1 when the particle diameter increased from 2 to 50 nm. The results provide information on the composition of nucleated aerosol particles during their growth in the presence of various combinations of sulphuric acid, ammonia, dimethylamine and organic oxidation products.
- ItemExperimental investigation of ion-ion recombination under atmospheric conditions(München : European Geopyhsical Union, 2015) Franchin, A.; Ehrhart, S.; Leppä, J.; Nieminen, T.; Gagné, S.; Schobesberger, S.; Wimmer, D.; Duplissy, J.; Riccobono, F.; Dunne, E.M.; Rondo, L.; Downard, A.; Bianchi, F.; Kupc, A.; Tsagkogeorgas, G.; Lehtipalo, K.; Manninen, H.E.; Almeida, J.; Amorim, A.; Wagner, P.E.; Hansel, A.; Kirkby, J.; Le Rille, O.; Kürten, A.; Donahue, N.M.; Makhmutov, V.; Mathot, S.; Metzger, A.; Petäjä, T.; Schnitzhofer, R.; Sipilä, M.; Stozhkov, Y.; Tomé, A.; Kerminen, V.-M.; Carslaw, K.; Curtius, J.; Baltensperger, U.; Kulmala, M.We present the results of laboratory measurements of the ion–ion recombination coefficient at different temperatures, relative humidities and concentrations of ozone and sulfur dioxide. The experiments were carried out using the Cosmics Leaving OUtdoor Droplets (CLOUD) chamber at CERN, the walls of which are made of conductive material, making it possible to measure small ions. We produced ions in the chamber using a 3.5 GeV c−1 beam of positively charged pions (π+) generated by the CERN Proton Synchrotron (PS). When the PS was switched off, galactic cosmic rays were the only ionization source in the chamber. The range of the ion production rate varied from 2 to 100 cm−3 s−1, covering the typical range of ionization throughout the troposphere. The temperature ranged from −55 to 20 °C, the relative humidity (RH) from 0 to 70 %, the SO2 concentration from 0 to 40 ppb, and the ozone concentration from 200 to 700 ppb. The best agreement of the retrieved ion–ion recombination coefficient with the commonly used literature value of 1.6 × 10−6 cm3 s−1 was found at a temperature of 5 °C and a RH of 40 % (1.5 ± 0.6) × 10−6 cm3 s−1. At 20 °C and 40 % RH, the retrieved ion–ion recombination coefficient was instead (2.3 ± 0.7) × 10−6 cm3 s−1. We observed no dependency of the ion–ion recombination coefficient on ozone concentration and a weak variation with sulfur dioxide concentration. However, we observed a more than fourfold increase in the ion–ion recombination coefficient with decreasing temperature. We compared our results with three different models and found an overall agreement for temperatures above 0 °C, but a disagreement at lower temperatures. We observed a strong increase in the recombination coefficient for decreasing relative humidities, which has not been reported previously.
- ItemEffect of dimethylamine on the gas phase sulfuric acid concentration measured by Chemical Ionization Mass Spectrometry(Hoboken, NJ : Wiley, 2016) Rondo, L.; Ehrhart, S.; Kürten, A.; Adamov, A.; Bianchi, F.; Breitenlechner, M.; Duplissy, J.; Franchin, A.; Dommen, J.; Donahue, Neil M.; Dunne, E.M.; Flagan, R.C.; Hakala, J.; Hansel, A.; Keskinen, H.; Kim, J.; Jokinen, T.; Lehtipalo, K.; Leiminger, M.; Praplan, A.; Riccobono, F.; Rissanen, M.P.; Sarnela, N.; Schobesberger, S.; Simon, M.; Sipilä, M.; Smith, J.N.; Tomé, A.; Tröstl, J.; Tsagkogeorgas, G.; Vaattovaara, P.; Winkler, P.M.; Williamson, C.; Wimmer, D.; Baltensperger, U.; Kirkby, J.; Kulmala, M.; Petäjä, T.; Worsnop, D.R.; Curtius, J.Sulfuric acid is widely recognized as a very important substance driving atmospheric aerosol nucleation. Based on quantum chemical calculations it has been suggested that the quantitative detection of gas phase sulfuric acid (H2SO4) by use of Chemical Ionization Mass Spectrometry (CIMS) could be biased in the presence of gas phase amines such as dimethylamine (DMA). An experiment (CLOUD7 campaign) was set up at the CLOUD (Cosmics Leaving OUtdoor Droplets) chamber to investigate the quantitative detection of H2SO4 in the presence of dimethylamine by CIMS at atmospherically relevant concentrations. For the first time in the CLOUD experiment, the monomer sulfuric acid concentration was measured by a CIMS and by two CI-APi-TOF (Chemical Ionization-Atmospheric Pressure interface-Time Of Flight) mass spectrometers. In addition, neutral sulfuric acid clusters were measured with the CI-APi-TOFs. The CLOUD7 measurements show that in the presence of dimethylamine (<5 to 70 pptv) the sulfuric acid monomer measured by the CIMS represents only a fraction of the total H2SO4, contained in the monomer and the clusters that is available for particle growth. Although it was found that the addition of dimethylamine dramatically changes the H2SO4 cluster distribution compared to binary (H2SO4-H2O) conditions, the CIMS detection efficiency does not seem to depend substantially on whether an individual H2SO4 monomer is clustered with a DMA molecule. The experimental observations are supported by numerical simulations based on A Self-contained Atmospheric chemistry coDe coupled with a molecular process model (Sulfuric Acid Water NUCleation) operated in the kinetic limit.
- ItemAqueous phase oxidation of sulphur dioxide by ozone in cloud droplets(München : European Geopyhsical Union, 2016) Hoyle, C.R.; Fuchs, C.; Järvinen, E.; Saathoff, H.; Dias, A.; El Haddad, I.; Gysel, M.; Coburn, S.C.; Tröstl, J.; Bernhammer, A.-K.; Bianchi, F.; Breitenlechner, M.; Corbin, J.C.; Craven, J.; Donahue, N.M.; Duplissy, J.; Ehrhart, S.; Frege, C.; Gordon, H.; Höppel, N.; Heinritzi, M.; Kristensen, T.B.; Molteni, U.; Nichman, L.; Pinterich, T.; Prévôt, A.S.H.; Simon, M.; Slowik, J.G.; Steiner, G.; Tomé, A.; Vogel, A.L.; Volkamer, R.; Wagner, A.C.; Wagner, R.; Wexler, A.S.; Williamson, C.; Winkler, P.M.; Amorim, A.; Dommen, J.; Curtius, J.; Gallagher, M.W.; Flagan, R.C.; Hansel, A.; Kirkby, J.; Kulmala, M.; Möhler, O.; Stratmann, F.; Worsnop, D.R.; Baltensperger, U.The growth of aerosol due to the aqueous phase oxidation of sulfur dioxide by ozone was measured in laboratory-generated clouds created in the Cosmics Leaving OUtdoor Droplets (CLOUD) chamber at the European Organization for Nuclear Research (CERN). Experiments were performed at 10 and −10 °C, on acidic (sulfuric acid) and on partially to fully neutralised (ammonium sulfate) seed aerosol. Clouds were generated by performing an adiabatic expansion – pressurising the chamber to 220 hPa above atmospheric pressure, and then rapidly releasing the excess pressure, resulting in a cooling, condensation of water on the aerosol and a cloud lifetime of approximately 6 min. A model was developed to compare the observed aerosol growth with that predicted using oxidation rate constants previously measured in bulk solutions. The model captured the measured aerosol growth very well for experiments performed at 10 and −10 °C, indicating that, in contrast to some previous studies, the oxidation rates of SO2 in a dispersed aqueous system can be well represented by using accepted rate constants, based on bulk measurements. To the best of our knowledge, these are the first laboratory-based measurements of aqueous phase oxidation in a dispersed, super-cooled population of droplets. The measurements are therefore important in confirming that the extrapolation of currently accepted reaction rate constants to temperatures below 0 °C is correct.