ACP Atmospheric Chemistry and Physics ACP 1680-7324 Copernicus GmbH Göttingen, Germany 10.5194/acp-10-2919-2010 The role of sulphates and organic vapours in growth of newly formed particles in a eucalypt forest Ristovski Z. D. 1 Suni T. 2 Kulmala M. 2 Boy M. 2 Meyer N. K. 1 5 Duplissy J. 3 6 Turnipseed A. 4 Morawska L. 1 Baltensperger U. 3 ILAQH, Queensland University of Technology, P.O. Box 4233, Brisbane QLD, 4001, Australia Div. of Atmospheric Sciences and Geophysics, Department of Physics, University of Helsinki, P.O. Box 64, 00014, Finland Laboratory of Atmospheric Chemistry, Paul Scherrer Institut, 5232 Villigen, Switzerland ANCAR/ACD, BAI Group, 3450 Mitchell Lane, Boulder, CO 80301, USA now at: Laboratory for Energy Systems Analysis, Paul Scherrer Institut, 5232 Villigen, Switzerland now at: Physic Department, CERN, 1211, Switzerland 29 03 2010 10 6 2919 2926 This is an open-access article ditributed under the terms of the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original author and source are credited. This article is available from http://www.atmos-chem-phys.net/10/2919/2010/acp-10-2919-2010.html The full text article is available as a PDF file from http://www.atmos-chem-phys.net/10/2919/2010/acp-10-2919-2010.pdf

The influence of biogenic particle formation on climate is a well recognised phenomenon. To understand the mechanisms underlying the biogenic particle formation, determining the chemical composition of the new particles and therefore the species that drive the particle production is of utmost importance. Due to the very small amount of mass involved, indirect approaches are frequently used to infer the composition. We present here the results of such an indirect approach by simultaneously measuring volatile and hygroscopic properties of newly formed particles in a forest environment. It is shown that the particles are composed of both sulphates and organics, with the amount of sulphate component strongly depending on the available gas-phase sulphuric acid, and the organic components having the same volatility and hygroscopicity as photo-oxidation products of a monoterpene such as α-pinene. Our findings agree with a two-step process through nucleation and cluster formation followed by simultaneous growth by condensation of sulphates and organics that take the particles to climatically relevant sizes.

 References Anttila, T. and Kerminen, V.-M.: Condensational growth of atmospheric nuclei by organic vapours, J. Aerosol Science, 34, 41–61, 2003. Berndt, T., Boge, O., Stratmann, F., Heintzenberg, J., and Kulmala, M.: Rapid formation of sulfuric acid particles at near-atmospheric conditions, Science, 307, 698–700, 2005. Boy, M., Kulmala, M., Ruuskanen, T. M., Pihlatie, M., Reissell, A., Aalto, P. P., Keronen, P., Dal Maso, M., Hellen, H., Hakola, H., Jansson, R., Hanke, M., and Arnold, F.: Sulphuric acid closure and contribution to nucleation mode particle growth, Atmos. Chem. Phys., 5, 863–878, 2005. Boy, M., Hellmuth, O., Korhonen, H., Nilsson, E. D., ReVelle, D., Turnipseed, A., Arnold, F., and Kulmala, M.: MALTE – model to predict new aerosol formation in the lower troposphere, Atmos. Chem. Phys., 6, 4499–4517, 2006. Cavalli, F., Facchini, M. C., Decesari, S., Emblico, L., Mircea, M., Jensen, N. R., and Fuzzi, S.: Size-segregated aerosol chemical composition at a boreal site in southern Finland, during the QUEST project, Atmos. Chem. Phys., 6, 993–1002, 2006. Duplissy, J., Gysel, M., Alfarra, M. R., Dommen, J., Metzger, A., Prevot, A. S. H., Weingartner, E., Laaksonen, A., Raatikainen, T., Good, N., Turner, S. F., McFiggans, G., and Baltensperger, U.: Cloud forming potential of secondary organic aerosol under near atmospheric conditions, Geophys. Res. Lett., 35, L03818, doi:10.1029/2007GL031075, 2008. Ehn, M., Petäjä, T., Aufmhoff, H., Aalto, P., Hämeri, K., Arnold, F., Laaksonen, A., and Kulmala, M.: Hygroscopic properties of ultrafine aerosol particles in the boreal forest: diurnal variation, solubility and the influence of sulfuric acid, Atmos. Chem. Phys., 7, 211–222, 2007. He, C., Murray, F., and Lyons, T.: Monoterpene and isoprene emissions from 15 Eucalyptus species in Australia, Atmos. Env., 34, 645–655, 2000. He, C., Murray, F., and Lyons, T.: Seasonal variations in monoterpene emissions from Eucalyptus species, Chemosphere Ð Global Change Science, 2, 65–76, 2000. Jimenez, J. L., Canagaratna, M. R., Donahue, N. M., et al.: Evolution of Organic Aerosols in the Atmosphere, Science, 326, 1525–1529, doi:10.1126/science.1180353, 2009. Johnson, G. R., Ristovski, Z., and Morawska, L.: Method for measuring the hygroscopic behaviour of lower volatility fractions in an internally mixed aerosol, J. Aerosol Sci., 35, 443–455, 2004. Johnson, G. R., Ristovski, Z. D., D'Anna, B., and Morawska, L.: Hygroscopic behavior of partially volatilized coastal marine aerosols using the volatilization and humidification tandem differential mobility analyzer technique, J. Geophys. Res.-Atmos., 110, D20203, doi:10.1029/2004JD005657, 2005. Johnson, G. R., Fletcher, C., Meyer, N.M., Modini, R., and Ristovski, Z. D.: A robust, portable H-TDMA for field use, J. Aerosol Sci., 39(10), 850–861, 2008. Kalberer, M., Paulsen, D., Sax, M., Steinbacher, M., Dommen, J., Prevot, A. S. H., Fisseha, R., Weingartner, E., Frankevich, V., Zenobi, R., and Baltensperger, U.: Identification of Polymers as Major Components of Atmospheric Organic Aerosols, Science, 303, 1659–1662, 2004. Kerminen, V.-M., Lihavainen, H., Komppula, M., Viisanen, Y., and Kulmala, M.: Direct observational evidence linking atmospheric aerosol formation and cloud droplet activation, Geophys. Res. Lett., 32, L14803, doi:10.1029/2005GL023130., 2005. Kulmala, M., Pirjola, L., and Makela, J. M.: Stable sulphate clusters as a source of new atmospheric particles, Nature, 404, 66–69, 2000. Kulmala, M., Vehkamaki, H., Petaja, T., Dal Maso, M., Lauri, A., Kerminen, V. M., Birmili, W., and McMurry, P. H.: Formation and growth rates of ultrafine particles: A review of observations, J. Aerosol Sci., 35, 143–176, 2004. Kulmala, M., Mordas, G., Petaja, T., Gronholm, T., Aalto, P. P., Vehkamaki, H., Hienola, A. I., Herrmann, E., Sipila, M., Riipinen, I., Manninen, H. E., Hameri, K., Stratmann, F., Bilde, M., Winkler, P. M., Birmili, W., and Wagner, P. E.: The condensation particle counter battery (CPCB): A new tool to investigate the activation properties of nanoparticles, J. Aerosol Sci., 38, 289–304, 2007a. Kulmala, M., Riipinen, I., Sipila, M., Manninen, H. E., Petaja, T., Junninen, H., Dal Maso, M., Mordas, G., Mirme, A., Vana, M., Hirsikko, A., Laakso, L., Harrison, R. M., Hanson, I., Leung, C., Lehtinen, K. E. J., and Kerminen, V. M.: Toward direct measurement of atmospheric nucleation, Science, 318, 82–92, 2007b. Laaksonen, A., Kulmala, M., O'Dowd, C. D., Joutsensaari, J., Vaattovaara, P., Mikkonen, S., Lehtinen, K. E. J., Sogacheva, L., Dal Maso, M., Aalto, P., Petäjä, T., Sogachev, A., Yoon, Y. J., Lihavainen, H., Nilsson, D., Facchini, M. C., Cavalli, F., Fuzzi, S., Hoffmann, T., Arnold, F., Hanke, M., Sellegri, K., Umann, B., Junkermann, W., Coe, H., Allan, J. D., Alfarra, M. R., Worsnop, D. R., Riekkola, M.-L., Hyötyläinen, T., and Viisanen, Y.: The role of VOC oxidation products in continental new particle formation, Atmos. Chem. Phys., 8, 2657–2665, 2008. Meskhidze, N. and Nenes, A.: Phytoplankton and cloudiness in the southern ocean, Science, 314, 1419–1423, 2006. Meyer, N. K., Duplissy, J., Gysel, M., Metzger, A., Dommen, J., Weingartner, E., Alfarra, M. R., Prevot, A. S. H., Fletcher, C., Good, N., McFiggans, G., Jonsson, Ã…. M., Hallquist, M., Baltensperger, U., and Ristovski, Z. D.: Analysis of the hygroscopic and volatile properties of ammonium sulphate seeded and unseeded SOA particles, Atmos. Chem. Phys., 9, 721–732, 2009. Modini, R. L., Ristovski, Z. D., Johnson, G. R., He, C., Surawski, N., Morawska, L., Suni, T., and Kulmala, M.: New particle formation and growth at a remote, sub-tropical coastal location, Atmos. Chem. Phys., 9, 7607–7621, 2009. O'Dowd, C. D., Aalto, P., Hameri, K., Kulmala, M., and Hoffmann, T.: Atmospheric particles from organic vapours, Nature, 416, 497–498, 2002. Paulsen, D., Dommen, J., Kalberer, M., Prevot, A. S. H., Richter, R., Sax, M., Steinbacher, M., Weingartner, E., and Baltensperger, U.: Secondary organic aerosol formation by irradiation of 1,3,5 trimethylbenzene-NOx-H2O in a new reaction chamber for atmospheric chemistry and physics, Environ. Sci. Technol., 39, 2668–2678, 2005. Petters, M. D. and Kreidenweis, S. M.: A single parameter representation of hygroscopic growth and cloud condensation nucleus activity, Atmos. Chem. Phys., 7, 1961–1971, 2007. Riipinen, I., Sihto, S.-L., Kulmala, M., Arnold, F., Dal Maso, M., Birmili, W., Saarnio, K., Teinilä, K., Kerminen, V.-M., Laaksonen, A., and Lehtinen, K. E. J.: Connections between atmospheric sulphuric acid and new particle formation during QUEST III–IV campaigns in Heidelberg and Hyytiälä, Atmos. Chem. Phys., 7, 1899–1914, 2007. Riipinen, I., Manninen, H. E., Yli-Juuti, T., Boy, M., Sipilä, M., Ehn, M., Junninen, H., Petäjä, T., and Kulmala, M.: Applying the Condensation Particle Counter Battery (CPCB) to study the water-affinity of freshly-formed 2–9 nm particles in boreal forest, Atmos. Chem. Phys., 9, 3317–3330, 2009. Riipinen, I., Pierce, J. R., Donahue, N. M., and Pandis, S. N.: Equilibration time scales of organic aerosol inside thermodenuders: Evaporation kinetics versus thermodynamics, Atmos. Environ., 44, 597–607, 2010. Ristovski, Z. D., Modini, R., Fletcher, C., and Johnson, G.: New Insights into the Composition and Structure of the Marine Aerosol Nanoparticles, in: Proceedings of the 18th International conference on nucleation and atmospheric aerosols, Prague, Czech Republic, 10–14 August 2009, 71–80, 2009. Stokes, R. H. and Robinson, R. A.: Interactions in aqueous nonelectrolyte solutions: I. Solute-solvent equilibria, J. Phys. Chem., 70, 2126–2130, 1966. Suni, T., Kulmala, M., Hirsikko, A., Bergman, T., Laakso, L., Aalto, P. P., Leuning, R., Cleugh, H., Zegelin, S., Hughes, D., van Gorsel, E., Kitchen, M., Vana, M., Hõrrak, U., Mirme, S., Mirme, A., Sevanto, S., Twining, J., and Tadros, C.: Formation and characteristics of ions and charged aerosol particles in a native Australian Eucalypt forest, Atmos. Chem. Phys., 8, 129–139, 2008. Surawski, N. C., Miljevic, B., Roberts, B., Modini, R., Situ, R., Brown, R., Bottle, S., and Ristovski, Z.: Particle Emissions, Volatility, and Toxicity from an Ethanol Fumigated Compression Ignition Engine, Environ. Sci. Tech., 44(1), 229–235, 2010. Topping, D. O., McFiggans, G. B., and Coe, H.: A curved multi-component aerosol hygroscopicity model framework: Part 2 – Including organic compounds, Atmos. Chem. Phys., 5, 1223–1242, 2005. Tunved, P., Hanson, H. C., Kerminen, V. M., Strom, J., Dal Maso, M., Lihavainen, H., Viisanen, Y., Aalto, P., Komppula, M., and Kulmala, M.: High natural aerosol loading over boreal forests, Science, 312, 261–263, 2006. Varutbangkul, V., Brechtel, F. J., Bahreini, R., Ng, N. L., Keywood, M. D., Kroll, J. H., Flagan, R. C., Seinfeld, J. H., Lee, A., and Goldstein, A. H.: Hygroscopicity of secondary organic aerosols formed by oxidation of cycloalkenes, monoterpenes, sesquiterpenes, and related compounds, Atmos. Chem. Phys., 6, 2367–2388, 2006. Vehkamaki, H., Napari, I., Kulmala, M., and Noppel, M.: Stable ammonium bisulphate clusters in the atmosphere, Phys. Rev. Lett., 93, 148501, doi:10.1103/PhysRevLett.93.148501, 2004. Winters, A. J., Adams M. A., Bleby, T. M., Rennenberg, H., Steigner, D., Steinbrecher, R., and Kreuzwieser. J.: Emissions of isoprene, monoterpene and short-chained carbonyl compounds from Eucalyptus spp. in southern Australia, Atmos. Environ., 43, 3053–3043, 2009.