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<front>
<journal-meta>
<journal-id journal-id-type="publisher">ACPD</journal-id>
<journal-title-group>
<journal-title>Atmospheric Chemistry and Physics Discussions</journal-title>
<abbrev-journal-title abbrev-type="publisher">ACPD</abbrev-journal-title>
</journal-title-group>
<issn pub-type="epub">1680-7375</issn>
<publisher><publisher-name>Copernicus GmbH</publisher-name>
<publisher-loc>GÃ¶ttingen, Germany</publisher-loc>
</publisher>
</journal-meta>
<article-meta>
<article-id pub-id-type="doi">10.5194/acpd-10-25959-2010</article-id>
<title-group>
<article-title>Homogenous nucleation of sulfuric acid and water at atmospherically relevant conditions</article-title>
</title-group>
<contrib-group><contrib contrib-type="author" xlink:type="simple"><name name-style="western"><surname>Brus</surname>
<given-names>D.</given-names>
</name>
<xref ref-type="aff" rid="aff1">
<sup>1</sup>
</xref>
<xref ref-type="aff" rid="aff2">
<sup>2</sup>
</xref>
</contrib>
<contrib contrib-type="author" xlink:type="simple"><name name-style="western"><surname>Neitola</surname>
<given-names>K.</given-names>
</name>
<xref ref-type="aff" rid="aff2">
<sup>2</sup>
</xref>
</contrib>
<contrib contrib-type="author" xlink:type="simple"><name name-style="western"><surname>PetÃ¤jÃ¤</surname>
<given-names>T.</given-names>
</name>
<xref ref-type="aff" rid="aff3">
<sup>3</sup>
</xref>
</contrib>
<contrib contrib-type="author" xlink:type="simple"><name name-style="western"><surname>Vanhanen</surname>
<given-names>J.</given-names>
</name>
<xref ref-type="aff" rid="aff3">
<sup>3</sup>
</xref>
</contrib>
<contrib contrib-type="author" xlink:type="simple"><name name-style="western"><surname>HyvÃ¤rinen</surname>
<given-names>A.-P.</given-names>
</name>
<xref ref-type="aff" rid="aff2">
<sup>2</sup>
</xref>
</contrib>
<contrib contrib-type="author" xlink:type="simple"><name name-style="western"><surname>SipilÃ¤</surname>
<given-names>M.</given-names>
</name>
<xref ref-type="aff" rid="aff3">
<sup>3</sup>
</xref>
</contrib>
<contrib contrib-type="author" xlink:type="simple"><name name-style="western"><surname>Paasonen</surname>
<given-names>P.</given-names>
</name>
<xref ref-type="aff" rid="aff3">
<sup>3</sup>
</xref>
</contrib>
<contrib contrib-type="author" xlink:type="simple"><name name-style="western"><surname>Lihavainen</surname>
<given-names>H.</given-names>
</name>
<xref ref-type="aff" rid="aff2">
<sup>2</sup>
</xref>
</contrib>
<contrib contrib-type="author" xlink:type="simple"><name name-style="western"><surname>Kulmala</surname>
<given-names>M.</given-names>
</name>
<xref ref-type="aff" rid="aff3">
<sup>3</sup>
</xref>
</contrib>
</contrib-group><aff id="aff1">
<label>1</label>
<addr-line>Laboratory of Aerosol Chemistry and Physics, Institute of Chemical Process Fundamentals Academy of Sciences of the Czech Republic, RozvojovÃ¡ 135, 165 02 Prague 6, Czech Republic</addr-line>
</aff>
<aff id="aff2">
<label>2</label>
<addr-line>Finnish Meteorological Institute, Erik PalmÃ©nin aukio 1, P.O. Box 503, 00100 Helsinki, Finland</addr-line>
</aff>
<aff id="aff3">
<label>3</label>
<addr-line>Department of Physics, University of Helsinki, P.O. Box 64, 00014 Helsinki, Finland</addr-line>
</aff>
<pub-date pub-type="epub">
<day>03</day>
<month>11</month>
<year>2010</year>
</pub-date>
<volume>10</volume>
<issue>11</issue>
<fpage>25959</fpage>
<lpage>25989</lpage>
<permissions>
<license xlink:type="simple">
<license-p>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.</license-p>
</license>
</permissions>
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<self-uri xlink:href="http://www.atmos-chem-phys-discuss.net/10/25959/2010/acpd-10-25959-2010.pdf">The full text article is available as a PDF file from http://www.atmos-chem-phys-discuss.net/10/25959/2010/acpd-10-25959-2010.pdf</self-uri>
<abstract>
<p>In this study the homogeneous nucleation rates of sulfuric acid and water
were measured by using a flow tube technique. The goal was to directly
compare particle formation rates obtained from atmospheric measurements with
nucleation rates of freshly nucleated particles measured with particle size
magnifier (PSM) which has detection efficiency of unity for particles having
mobility diameter of 1.5 nm. The gas phase sulfuric acid concentration in
this study was measured with the chemical ionization mass spectrometer
(CIMS), commonly used in field measurements. The wall losses of sulfuric
acid were estimated from measured concentration profiles along the flow
tube. The initial concentrations of sulfuric acid estimated from loss
measurements ranged from 10&lt;sup&gt;8&lt;/sup&gt; to 3Ã—10&lt;sup&gt;9&lt;/sup&gt; molecules cm&lt;sup&gt;âˆ’3&lt;/sup&gt;.
The nucleation rates obtained in this study cover about three orders of
magnitude from 10&lt;sup&gt;âˆ’1&lt;/sup&gt; to 10&lt;sup&gt;2&lt;/sup&gt; cm&lt;sup&gt;3&lt;/sup&gt; s&lt;sup&gt;âˆ’1&lt;/sup&gt; for commercial
ultrafine condensation particle counter (UCPC) TSI model 3025A and from
10&lt;sup&gt;1&lt;/sup&gt; to 10&lt;sup&gt;4&lt;/sup&gt; cm&lt;sup&gt;3&lt;/sup&gt; s&lt;sup&gt;âˆ’1&lt;/sup&gt; for PSM. The nucleation rates and
the slopes (&lt;i&gt;d&lt;/i&gt;ln&lt;i&gt;J&lt;/i&gt;/&lt;i&gt;d&lt;/i&gt;ln[H&lt;sub&gt;2&lt;/sub&gt;SO&lt;sub&gt;4&lt;/sub&gt;]) show satisfactory agreement when
compared to empirical kinetic and activation models and the latest
atmospheric nucleation data.</p>
</abstract>
<counts><page-count count="31"/></counts>
</article-meta>
</front>
<body/>
<back>
<ref-list>
<title>References</title>
<ref id="ref1">
<label>1</label><mixed-citation publication-type="other" xlink:type="simple"> Ball S. M., Hanson D. R., and Eisele F. L., and McMurry P. H.: Laboratory studies of particle nucleation: Initial results for H&lt;sub&gt;2&lt;/sub&gt;SO&lt;sub&gt;4&lt;/sub&gt;, H&lt;sub&gt;2&lt;/sub&gt;O, and NH&lt;sub&gt;3&lt;/sub&gt; vapors., J. Geophys. Res., 104(D19), 23709â€“23718, 1999. </mixed-citation>
</ref>
<ref id="ref2">
<label>2</label><mixed-citation publication-type="other" xlink:type="simple"> Benson, D. R., Young, L. H., Kameel, F. R., and Lee, S.-H.: Laboratory-measured nucleation rates of sulfuric acid and water binary homogeneous nucleation from the SO&lt;sub&gt;2&lt;/sub&gt; + OH reaction, Geophys. Res. Lett., 35, L11801, doi:10.1029/2008GL033387, 2008. </mixed-citation>
</ref>
<ref id="ref3">
<label>3</label><mixed-citation publication-type="other" xlink:type="simple"> Berndt, T., BÃ¶ge, O., Stratmann, F., Heintzenberg, J., and Kulmala, M.: Rapid formation of sulfuric acid particles at near atmospheric conditions, Science, 307, 698â€“700, 2005. </mixed-citation>
</ref>
<ref id="ref4">
<label>4</label><mixed-citation publication-type="other" xlink:type="simple"> Berndt, T., Stratmann, F., SipilÃ¤, M., Vanhanen, J., PetÃ¤jÃ¤, T., MikkilÃ¤, J., GrÃ¼ner, A., Spindler, G., Lee Mauldin III, R., Curtius, J., Kulmala, M., and Heintzenberg, J.: Laboratory study on new particle formation from the reaction OH + SO&lt;sub&gt;2&lt;/sub&gt;: influence of experimental conditions, H&lt;sub&gt;2&lt;/sub&gt;O vapour, NH&lt;sub&gt;3&lt;/sub&gt; and the amine tert-butylamine on the overall process, Atmos. Chem. Phys., 10, 7101â€“7116, doi:10.5194/acp-10-7101-2010, 2010. </mixed-citation>
</ref>
<ref id="ref5">
<label>5</label><mixed-citation publication-type="other" xlink:type="simple"> Brus, D., HyvÃ¤rinen, A.-P., Viisanen, Y., Kulmala, M., and Lihavainen, H.: Homogeneous nucleation of sulfuric acid and water mixture: experimental setup and first results, Atmos. Chem. Phys., 10, 2631â€“2641, doi:10.5194/acp-10-2631-2010, 2010. </mixed-citation>
</ref>
<ref id="ref6">
<label>6</label><mixed-citation publication-type="other" xlink:type="simple"> Eisele, F. L. and Hanson, D. R: First measurements of prenucleation molecular clusters, J. Phys. Chem. A, 104, 830â€“836, 2000. </mixed-citation>
</ref>
<ref id="ref7">
<label>7</label><mixed-citation publication-type="other" xlink:type="simple"> Eisele, F. L. and Tanner, D.: Measurement of the gas phase concentration of H&lt;sub&gt;2&lt;/sub&gt;SO&lt;sub&gt;4&lt;/sub&gt; and methane sulfonic acid and estimates of H&lt;sub&gt;2&lt;/sub&gt;SO&lt;sub&gt;4&lt;/sub&gt; production and loss in the atmosphere, J. Geophys. Res., 98, 9001â€“9010, 1993. </mixed-citation>
</ref>
<ref id="ref8">
<label>8</label><mixed-citation publication-type="other" xlink:type="simple"> Hanson, D. R. and Eisele, F. L.: Diffusion of H&lt;sub&gt;2&lt;/sub&gt;SO&lt;sub&gt;4&lt;/sub&gt; in humidified nitrogen: Hydrated H&lt;sub&gt;2&lt;/sub&gt;SO&lt;sub&gt;4&lt;/sub&gt;, J. Phys. Chem. A, 104, 1715â€“1719, 2000. </mixed-citation>
</ref>
<ref id="ref9">
<label>9</label><mixed-citation publication-type="other" xlink:type="simple"> Hanson D. R. and Lovejoy E. R.: Measurements of the thermodynamics of the hydrated dimmer and trimer of sulfuric acid, J. Phys. Chem. A, 110(31), 9525â€“9527, 2006. </mixed-citation>
</ref>
<ref id="ref10">
<label>10</label><mixed-citation publication-type="other" xlink:type="simple"> Herrmann, E., Brus, D., HyvÃ¤rinen, A.-P., Stratmann, F., Wilck, M., Lihavainen, H. and Kulmala, M.: A computational fluid dynamics approach to nucleation in the water-sulfuric acid-system, J. Phys. Chem. A, 114(31), 8033â€“8042, 2010. </mixed-citation>
</ref>
<ref id="ref11">
<label>11</label><mixed-citation publication-type="other" xlink:type="simple"> Iida, K., Stolzenburg, M., and McMurry, P. H.: Effect of Working Fluid on Sub-2 nm Particle Detection with a Laminar Flow Ultrafine Condensation Particle Counter, Aerosol Sci. Technol., 43, 81â€“96, 2009. </mixed-citation>
</ref>
<ref id="ref12">
<label>12</label><mixed-citation publication-type="other" xlink:type="simple"> Jaecker-Voirol, A., Mirabel, P., and Reiss, H.: Hydrates in supersaturated binary sulphuric acid-water vapor: A reexamination, J. Chem. Phys., 87, 4849â€“4852, 1987. </mixed-citation>
</ref>
<ref id="ref13">
<label>13</label><mixed-citation publication-type="other" xlink:type="simple"> Jaecker-Voirol A. and Mirabel P.: Nucleation rate in a binary mixture of sulfuric acid and water vapor, J. Phys. Chem., 92(12), 3518â€“3521, 1988. </mixed-citation>
</ref>
<ref id="ref14">
<label>14</label><mixed-citation publication-type="other" xlink:type="simple"> Kashchiev, D: On the relation between nucleation work, nucleus size and nucleation rate, J. Chem. Phys., 76, 5098â€“5102, 1982. </mixed-citation>
</ref>
<ref id="ref15">
<label>15</label><mixed-citation publication-type="other" xlink:type="simple"> Kulmala, M., Lazaridis, M., Laaksonen, A., and Vesala, T.: Extended hydrates interaction model: Hydrate formation and the energetics of binary homogeneous nucleation, J. Chem. Phys., 94(11), 7411â€“7413, 1991. </mixed-citation>
</ref>
<ref id="ref16">
<label>16</label><mixed-citation publication-type="other" xlink:type="simple"> Kulmala, M.: How particles nucleate and grow, Science, 302, 1000â€“1001, 2003. </mixed-citation>
</ref>
<ref id="ref17">
<label>17</label><mixed-citation publication-type="other" xlink:type="simple"> Kulmala, M., Lehtinen, K. E. J., and Laaksonen, A.: Cluster activation theory as an explanation of the linear dependence between formation rate of 3nm particles and sulphuric acid concentration, Atmos. Chem. Phys., 6, 787â€“793, doi:10.5194/acp-6-787-2006, 2006. </mixed-citation>
</ref>
<ref id="ref18">
<label>18</label><mixed-citation publication-type="other" xlink:type="simple"> Mauldin III, R. L., Frost, G., Chen, G., Tanner, D., Prevot, A., Davis, D., and Eisele, F.: OH measurements during the First Aerosol Characterization Experiment (ACE 1): Observations and model comparisons, J. Geophys. Res., 103, 16713â€“16729, 1998. </mixed-citation>
</ref>
<ref id="ref19">
<label>19</label><mixed-citation publication-type="other" xlink:type="simple"> McMurry, P. H.: Photochemical Aerosol Formation from SO&lt;sub&gt;2&lt;/sub&gt;: A Theoretical Analysis of Smog Chamber Data, J. Colloid Interface Sci., 78, 513â€“527, 1980. </mixed-citation>
</ref>
<ref id="ref20">
<label>20</label><mixed-citation publication-type="other" xlink:type="simple"> Metzger, A., Verheggen, B., Dommen, J., Duplissy, J., Prevot, A. S., Weingartner, E., Riipinen, I., Kulmala, M., Spracklen, D. V., Carslaw, K. S., and Baltensperger, U.: Evidence for the role of organics in aerosol particle formation under atmospheric conditions, P. Natl. Acad. Sci., 107, 6646â€“6651, doi:10.1073/pnas.0911330107, 2010. </mixed-citation>
</ref>
<ref id="ref21">
<label>21</label><mixed-citation publication-type="other" xlink:type="simple"> Paasonen, P., Nieminen, T., Asmi, E., Manninen, H. E., PetÃ¤jÃ¤, T., Plass-DÃ¼lmer, C., Flentje, H., Birmili, W., Wiedensohler, A., HÃµrrak, U., Metzger, A., Hamed, A., Laaksonen, A., Facchini, M. C., Kerminen, V.-M., and Kulmala, M.: On the roles of sulphuric acid and low-volatility organic vapours in the initial steps of atmospheric new particle formation, Atmos. Chem. Phys. Discuss., 10, 11795â€“11850, doi:10.5194/acpd-10-11795-2010, 2010. </mixed-citation>
</ref>
<ref id="ref22">
<label>22</label><mixed-citation publication-type="other" xlink:type="simple"> PetÃ¤jÃ¤, T., Mauldin, III, R. L., Kosciuch, E., McGrath, J., Nieminen, T., Paasonen, P., Boy, M., Adamov, A., Kotiaho, T., and Kulmala, M.: Sulfuric acid and OH concentrations in a boreal forest site, Atmos. Chem. Phys., 9, 7435â€“7448, doi:10.5194/acp-9-7435-2009, 2009. </mixed-citation>
</ref>
<ref id="ref23">
<label>23</label><mixed-citation publication-type="other" xlink:type="simple"> Riipinen, I., Sihto, S.-L., Kulmala, M., Arnold, F., Dal Maso, M., Birmili, W., Saarnio, K., TeinilÃ¤, 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, 1899â€“1914, doi:10.5194/acp-7-1899-2007, 2007. </mixed-citation>
</ref>
<ref id="ref24">
<label>24</label><mixed-citation publication-type="other" xlink:type="simple"> Salcedo, D., Villalta, P. W., Varutbangkul, V. Wormhoundt, J. C. , Miake-Lye, R. C., Worsnop, D. R., Ballenthin, J. O., Thorn, W. F., Viggiano, A. A., Miller, T. M., Flagan, R. C., and Seinfeld, J. H., Int. J. Mass. Spectrom. 231, 17â€“30, 2004. </mixed-citation>
</ref>
<ref id="ref25">
<label>25</label><mixed-citation publication-type="other" xlink:type="simple"> Sihto, S.-L., Kulmala, M., Kerminen, V.-M., Dal Maso, M., PetÃ¤jÃ¤, T., Riipinen, I., Korhonen, H., Arnold, F., Janson, R., Boy, M., Laaksonen, A., and Lehtinen, K. E. J.: Atmospheric sulphuric acid and aerosol formation: implications from atmospheric measurements for nucleation and early growth mechanisms, Atmos. Chem. Phys., 6, 4079â€“4091, doi:10.5194/acp-6-4079-2006, 2006. </mixed-citation>
</ref>
<ref id="ref26">
<label>26</label><mixed-citation publication-type="other" xlink:type="simple"> SipilÃ¤, M. Berndt, T., PetÃ¤jÃ¤, T., Brus, D., Vanhanen, J., Stratmann, F., Patokoski, J., Mauldin III, R. L., HyvÃ¤rinen, A.-P., Lihavainen, H., and Kulmala, M.: The role of sulfuric acid in atmospheric nucleation, Science, 327, 5970, 1243â€“1246, doi:10.1126/science.1180315, 2010. </mixed-citation>
</ref>
<ref id="ref27">
<label>27</label><mixed-citation publication-type="other" xlink:type="simple"> Sgro, L. A. and de la Mora, J. F.: A simple turbulent mixing CNC for charged particle detection down to 1.2 nm, Aerosol Sci. Technol., 38, 1â€“11, 2004. </mixed-citation>
</ref>
<ref id="ref28">
<label>28</label><mixed-citation publication-type="other" xlink:type="simple"> Stoltzenburg, M. R. and McMurry, P. H.: An ultrafine aerosol condensation nucleus counter, Aerosol Sci. Technol., 14, 48â€“65, 1991. </mixed-citation>
</ref>
<ref id="ref29">
<label>29</label><mixed-citation publication-type="other" xlink:type="simple"> Vanhanen, J., MikkilÃ¤, J., SipilÃ¤, M., Manninen, H. E., Lehtipalo, K., Siivola, E., PetÃ¤jÃ¤, T., and Kulmala, M.: Particle size magnifier for nano-CN detection, Aerosol Sci. Technol., in press, 2010. </mixed-citation>
</ref>
<ref id="ref30">
<label>30</label><mixed-citation publication-type="other" xlink:type="simple"> VehkamÃ¤ki, H., Kulmala, M., Napari, I., Lehtinen, K. E. J., Timmreck, C., Noppel M., and Laaksonen, A.: An improved parameterization for sulfuric acid-water nucleation rates for tropospheric and stratospheric conditions, J. Geophys. Res., 107(D22), 4622, doi:10.1029/2002JD002184, 2002. </mixed-citation>
</ref>
<ref id="ref31">
<label>31</label><mixed-citation publication-type="other" xlink:type="simple"> Weber, R. J., Marti, J., McMurry, P. H., Eisele, F., Tanner, D. J., and Jefferson, A.: Measured atmospheric new particle formation rates: implications for nucleation mechanisms, Chem. Eng. Commun., 151, 53â€“64, 1996. </mixed-citation>
</ref>
<ref id="ref32">
<label>32</label><mixed-citation publication-type="other" xlink:type="simple"> Weber, R. J., Marti, J. J., McMurry, P. H., Eisele, F. L., Tanner, D. J., and Jefferson, A.: Measurements of new particle formation and ultrafine particle growth rates at a clean continental site, J. Geophys. Res., 102, 4373â€“4385, 1997. </mixed-citation>
</ref>
<ref id="ref33">
<label>33</label><mixed-citation publication-type="other" xlink:type="simple"> Young, L. H., Benson, D. R., Kameel, F. R., Pierce, J. R., Junninen, H., Kulmala, M., and Lee, S.-H.: Laboratory studies of H&lt;sub&gt;2&lt;/sub&gt;SO&lt;sub&gt;4&lt;/sub&gt;/H&lt;sub&gt;2&lt;/sub&gt;O binary homogeneous nucleation from the SO&lt;sub&gt;2&lt;/sub&gt;+OH reaction: evaluation of the experimental setup and preliminary results, Atmos. Chem. Phys., 8, 4997â€“5016, doi:10.5194/acp-8-4997-2008, 2008. </mixed-citation>
</ref>
<ref id="ref34">
<label>34</label><mixed-citation publication-type="other" xlink:type="simple"> Zhang, R., Suh, I., Zhao, J., Zhang, D., Fortner, E. C., Tie, X., Molina, L. T., and Molina, M. J.: Atmospheric new particle formation enhanced by organic acids, Science, 304 (5676), 1487â€“1490, doi:10.1126/science.1095139, 2004. </mixed-citation>
</ref>
<ref id="ref35">
<label>35</label><mixed-citation publication-type="other" xlink:type="simple"> Zhang, R.: Getting to the Critical Nucleus of Aerosol Formation, Science, 328(5984), 1366â€“1367, doi:10.1126/science.1189732, 2010. </mixed-citation>
</ref>
<ref id="ref36">
<label>36</label><mixed-citation publication-type="other" xlink:type="simple"> Zhao, J., Eisele, F. L., Titcombe, M., Kuang, C., and McMurry, P. H.: Chemical ionization mass spectrometric measurements of atmospheric neutral clusters using the cluster-CIMS, J. Geophys. Res., 115, D08205, doi:10.1029/2009JD012606, 2010. </mixed-citation>
</ref>
</ref-list>
</back>
</article>