Atmospheric Chemistry and Physics Discussions
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2008
10.5194/acpd-8-20661-2008
http://www.atmos-chem-phys-discuss.net/8/20661/2008/
http://www.atmos-chem-phys-discuss.net/8/20661/2008/acpd-8-20661-2008.html
http://www.atmos-chem-phys-discuss.net/8/20661/2008/acpd-8-20661-2008.pdf
20661
20685
2008-12-10
Analysis of atmospheric neutral and charged molecular clusters in boreal forest using pulse-height CPC
K. Lehtipalo
katrianne.lehtipalo@helsinki.fi
M. Sipilä
I. Riipinen
T. Nieminen
M. Kulmala
Department of Physical Sciences, University of Helsinki, Finland
also at: Helsinki Institute of Physics, Helsinki, Finland
We measured the size distribution of atmospheric neutral and charged
clusters and particles down to mobility diameter around 1.5 nm by
applying pulse-height CPC technique at SMEAR II station in Hyytiälä,
southern Finland during spring 2007 and May 2008. The concentration of
molecular clusters smaller than 3 nm seems to be highly variable in
boreal forest environment. The concentration varied typically between
500–50 000 cm<sup>−3</sup>, the medians being
8060 cm<sup>−3</sup> in year 2007 and 3380 cm<sup>−3</sup> in 2008. By
comparing to concentrations measured with ion spectrometers, we
conclude that ion clusters and neutral clusters produced by ion-ion
recombination are usually not sufficient to explain all of the
observed clusters; the median fraction of recombination products from
all neutral clusters was 4.9%. Before and during most new particle
formation events the cluster formation rate rose only slightly, or
remained close to stable. Nocturnal formation of clusters was also
frequently observed.
Aalto,~P., Hämeri,~K., Becker,~E., Weber,~R., Salm,~J., Mäkelä, ~J M., Hoell,~C., O'Dowd,~C D., Karlsson,~H., Hansson,~H.-C., Väkevä,~M., Koponen,~I K., Buzorius,~G., and Kulmala,~M.: Physical characterization of aerosol particles in boreal forests, Tellus 53B, 344–358, 2001.
Asmi, E., Sipilä, M., Manninen, H. E., Vanhanen, J., Lehtipalo, K., Gagné, S., Neitola, K., Mirme, A., Mirme, S., Tamm, E., Uin, J., Komsaare, K., Attoui, M., and Kulmala, M.: Results of the first air ion spectrometer calibration and intercomparison workshop, Atmos. Chem. Phys. Discuss., 8, 17257–17295, 2008.
Bonn,~B., Kulmala,~M., Riipinen,~I., Sihto,~S.-L., and Ruuskanen,~T.: How biogenic terpenes govern the correlation between sulphuric acid concentrations and new particle formation, J Geophys. Res., 113, D12209, doi:10.1029/2007JD009327, 2008.
Brunekreef,~B. and Holgate,~S.: Air pollution and health, Lancet, 360, 1233–1242, 2002.
Dal Maso,~M., Kulmala,~M., Riipinen,~I., Wagner,~R., Hussein,~T., Aalto, ~P P., and Lehtinen, K E J.: Formation and growth of fresh atmospheric aerosols: eight years of aerosol size distribution data from SMEAR II, Hyytiälä, Finland, Boreal Environ. Res., 10, 323–336, 2005.
Dick,~W D., McMurry,~P H., Weber,~R J., and Quant,~R.: White-light detection for nanoparticle sizing with the TSI ultrafine condensation particle counter, J. Nanopart. Res., 2, 85–90, 2000.
Gagné,~S., Laakso,~L., Petäjä,~T., Kerminen,~V.-M., and Kulmala, ~M.: Analysis on one year of Ion-DMPS data from the SMEAR II station, Hyytiälä, Tellus, 60B, 318–329, 2008.
Hanson,~D R., Eisele,~F L., Ball,~S M., and McMurry,~P M.: Sizing small sulfuric acid particles with an ultrafine particle condensation nucleus counter, Aerosol Sci. Tech., 36, 554–559, 2002.
Hanson,~D R., and Eisele,~F L.: Measurement of prenucleation molecular clusters in the \chemNH_3, \chemH_2SO_4, \chemH_2O system, J. Geophys. Res., 107(D12), 4158, doi:10.1029/2001JD001100, 2002.
Hari,~P. and Kulmala,~M.: Station for measuring ecosystem-atmosphere relations (SMEAR II), Boreal Environ. Res., 10, 315–322, 2005.
Hirsikko,~A., Laakso,~L., Hõrrak,~U., Aalto,~P P., Kerminen,~V.-M., and Kulmala,~M.: Annual and size dependent variation of growth rates and ion concentrations in boreal forest, Boreal Environ. Res, 10, 357–369, 2005.
Hõrrak,~U., Salm,~J., and Tammet,~H.: Bursts if intermediate ions in atmospheric air, J. Geophys. Res., 103, 13909–13915, 1998.
Iida,~K., Stolzenburg,~M., McMurry,~P., Dunn,~M J., Smith,~J N., Eisele,~F., and Keady,~P.: Contribution of ion-induced nucleation to new particle formation: Methodology and its application to atmospheric observations in Boulder, Colorado, J. Geophys. Res., 111, D23201, doi:1029/2006JD007167, 2006.
IPCC: Summary for Policymakers. In: Climate Change 2007: The Physical Science Basis. Contribution of Working Group I to the Fourth Assessment Report of the Intergovernmental Panel on Climate Change, edited by: Solomon, S., Qin,~D., Manning,~M., Chen,~Z., Marquis,~M., Averyt,~K B., Tignor,~M., and Miller,~H L., Cambridge University Press, Cambridge, UK and New York, NY, USA, 2007.
Junninen,~H., Hulkkonen,~M., Riipinen,~I., Nieminen,~T., Hirsikko, ~A., Suni,~T., Boy,~M., Lee~S.-H., Vana,~M., Tammet,~H., Kerminen,~V.-M., and Kulmala,~M.: Observations on nocturnal growth of atmospheric clusters, Tellus, 60B, 365–371, 2008.
Kerminen,~V.-M., Pirjola,~L., and Kulmala,~M.: How significantly does coagulational scavenging limit atmospheric particle production?, J. Geophys. Res., 106, 24119–24126, 2001.
Kilpatrick,~W D.: An experimental mass-mobility relation for ions in air at atmospheric pressure, Proc. Annu. Conf. Mass Spectosc., 19, 320–325, 1971.
Kulmala,~M., Pirjola,~L., and Mäkelä,~J M.: Stable sulphate clusters as a~source of new atmospheric particles, Nature, 404, 66–69, 2000.
Kulmala,~M.: How particles nucleate and grow?, Science, 302, 1000–1001, 2003.
Kulmala,~M., Vehkamäki,~H., Petäjä,~T., Dal Maso,~M., Lauri,~A., Kerminen,~V.-M., Birmili,~W., and McMurry,~P H.: Formation and growth rates of ultrafine atmospheric particles: a~review of observations, J. Aerosol Sci., 35, 143–176, 2004a.
Kulmala,~M., Kerminen,~V.-M., Anttila,~T., Laaksonen,~A., and O'Dowd,~C D.: Organic aerosol formation via sulphate cluster activation, J. Geophys. Res., 109, D04205, doi:10.1029/2003JD003961, 2004b.
Kulmala~M., Lehtinen~K E J., Laakso,~L., Mordas,~G., and Hämeri,~K.: On the existence of neutral atmospheric clusters, Boreal Environ. Res., 10, 79–87, 2005.
Kulmala, M., Lehtinen, K. E. J., and Laaksonen, A.: Cluster activation theory as an explanation of the linear dependence between formation rate of 3 nm particles and sulphuric acid concentration, Atmos. Chem. Phys., 6, 787–793, 2006.
Kulmala,~M., Riipinen,~I., Sipilä,~M., Manninen,~H., Petäjä,~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.: Towards direct measurement of atmospheric nucleation, Science, 318, 89–92, supporting online material: www.sciencemag.org/cgi/content/full/1144124/DC1, 2007a.
Kulmala,~M., Mordas,~G., Petäjä,~T., Grönholm,~T., Aalto,~P P., Vehkamäki,~H., Hienola,~A I., Herrmann,~E., Sipilä,~M., Riipinen,~I., Manninen,~H E., Hämeri,~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, 2007b.
Laakso, L., Anttila, T., Lehtinen, K. E. J., Aalto, P. P., Kulmala, M., Hõrrak, U., Paatero, J., Hanke, M., and Arnold, F.: Kinetic nucleation and ions in boreal forest particle formation events, Atmos. Chem. Phys., 4, 2353–2366, 2004.
Mirme,~A., Tamm,~E., Mordas,~G., Vana,~M., Uin,~J., Mirme,~S., Bernotas,~T., Laakso,~L., Hirsikko,~A., and Kulmala,~M.: A~wide-range multi-channel Air Ions Spectrometer, Boreal Environ. Res., 12, 247–264, 2007.
Mäkelä,~J M., Jokinen,~V., Mattila,~T., Ukkonen,~A., and Keskinen, J.: Mobility distribution of acetone cluster ions, J. Aerosol Sci., 27, 175–190, 1996.
O'Dowd,~C D., Aalto,~P., Hämeri,~K., Kulmala,~M., and Hoffmann, T.: Atmospheric particles from organic vapours, Nature, 416, 497–498, 2002.
O'Dowd,~C D., Aalto,~P P., Yoon,~Y J., Hämeri,~K.: The use of the pulse height analyzer ultrafine condensation particle counter (PHA-UCPC) technique applied to sizing of nucleation mode particles of different chemical composition, J. Aerosol Sci., 35, 2, 205–216, 2003.
Saros,~M., Weber,~R J., Marti,~J., and McMurry,~P H.: Ultra fine aerosol measurement using a~condensation nucleus counter with pulse height analysis, Aerosol Sci. Technol., 25, 200–213, 1996.
Sipilä, M., Lehtipalo, K., Kulmala, M., Petäjä, T., Junninen, H., Aalto, P. P., Manninen, H. E., Kyrö, E.-M., Asmi, E., Riipinen, I., Curtius, J., Kürten, A., Borrmann, S., and O'Dowd, C. D.: Applicability of condensation particle counters to measure atmospheric clusters, Atmos. Chem. Phys., 8, 4049–4060, 2008.
Sipilä,~M., Lehtipalo,~K., Attoui,~M., Neitola,~K., Petäjä,~T., Aalto,~P P., O'Dowd,~C D., and Kulmala,~M.: Laboratory verification of PH-CPC's ability to monitor atmospheric sub-3 \unitnm clusters, Aerosol Sci. Technol., 43, 2, 126–135, 2009.
Spracklen, D. V., Carslaw, K. S., Kulmala, M., Kerminen, V.-M., Mann, G. W., and Sihto, S.-L.: The contribution of boundary layer nucleation events to total particle concentrations on regional and global scales, Atmos. Chem. Phys., 6, 5631–5648, 2006.
Tammet,~H. and Kulmala,~M.: Simulation tool for atmospheric aerosol nucleation bursts, J Aerosol Sci., 36, 173–196, 2005.
Tammet,~H.: 2006 Continuous scanning of the mobility and size distribution of charged clusters and nanometer particles in atmospheric air and the balanced scanning mobility analyzer BSMA, Atmos. Res., 82, 523–535, 2006.
Torpo,~L., Kurtén,~T., Vehkamäki,~H., Laasonen,~K., Sundberg, M R., and Kulmala,~M.: Significance of ammonia in atmospheric nanoclusters, J. Phys. Chem. A, 111, 10671–10674, 2007.
Turco,~R P., Zhao,~J X., and Yu,~F.: A~new source of tropospheric aerosols: Ion-ion recombination, Geophys. Res. Lett., 25, 635–638, 1998.
Vehkamäki,~H., Napari,~I., Kulmala,~M., and Noppel,~M.: Stable ammonium bisulphate clusters in the atmosphere, Phys. Rev. Lett., 93, 148501–148504, 2004.
Weber,~R J., McMurry,~P H., Eisele,~F L., and Tanner,~D J.: Measurement of expected nucleation precursor species and 3-500-nm diameter particles at Mauna Loa observatory, Hawaii, J. Atmos. Sci., 52, 2242–2257, 1995.
Weber,~R J., Stolzenburg,~M R., Pandis,~S N., and McMurry,~P H.: Inversion of ultrafine condensation nucleus counter pulse height distributions to obtain nanoparticle ($\sim $3–10 \unitnm) size distributions, J. Aerosol Sci., 29, 601–615, 1998.
Winkler,~P M., Steiner,~G., Vrtala,~A., Vehkamäki,~H., Noppel,~M., Lehtinen,~K E J., \hboxReischl,~G P., Wagner,~P E., and Kulmala,~M.: Heterogeneous nucleation experiments bridging scale from molecular ion clusters to nanoparticles, Science, 319, 1374–1377, 2008.