<?xml version="1.0" encoding="UTF-8"?>
<!DOCTYPE article PUBLIC "-//NLM//DTD Journal Publishing DTD v3.0 20080202//EN" "http://dtd.nlm.nih.gov/publishing/3.0/journalpublishing3.dtd">
<article xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink" article-type="research-article" dtd-version="3.0" xml:lang="en">
<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>Göttingen, Germany</publisher-loc>
</publisher>
</journal-meta>
<article-meta>
<article-id pub-id-type="doi">10.5194/acpd-7-11973-2007</article-id>
<title-group>
<article-title>Reversible and irreversible processing of biogenic olefins on acidic aerosols</article-title>
</title-group>
<contrib-group><contrib contrib-type="author" xlink:type="simple"><name name-style="western"><surname>Liggio</surname>
<given-names>J.</given-names>
</name>
<xref ref-type="aff" rid="aff1">
<sup>1</sup>
</xref>
</contrib>
<contrib contrib-type="author" xlink:type="simple"><name name-style="western"><surname>Li</surname>
<given-names>S.-M.</given-names>
</name>
<xref ref-type="aff" rid="aff1">
<sup>1</sup>
</xref>
</contrib>
</contrib-group><aff id="aff1">
<label>1</label>
<addr-line>Air Quality Research Division, Atmospheric Science and Technology Directorate, Science and Technology Branch, Environment Canada, 4905 Dufferin Street, Toronto, Ontario, M3H 5T4, Canada</addr-line>
</aff>
<pub-date pub-type="epub">
<day>14</day>
<month>08</month>
<year>2007</year>
</pub-date>
<volume>7</volume>
<issue>4</issue>
<fpage>11973</fpage>
<lpage>12009</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>
<self-uri xlink:href="http://www.atmos-chem-phys-discuss.net/7/11973/2007/acpd-7-11973-2007.html">This article is available from http://www.atmos-chem-phys-discuss.net/7/11973/2007/acpd-7-11973-2007.html</self-uri>
<self-uri xlink:href="http://www.atmos-chem-phys-discuss.net/7/11973/2007/acpd-7-11973-2007.pdf">The full text article is available as a PDF file from http://www.atmos-chem-phys-discuss.net/7/11973/2007/acpd-7-11973-2007.pdf</self-uri>
<abstract>
<p>Recent evidence has suggested that heterogeneous chemistry of oxygenated
hydrocarbons, primarily carbonyls, plays a role in the formation of
secondary organic aerosol (SOA); however, evidence is emerging that direct
uptake of alkenes on acidic aerosols does occur and can contribute to SOA
formation. In the present study, significant uptake of monoterpenes,
oxygenated monoterpenes and sesquiterpenes to acidic sulfate aerosols is
found under various conditions in a reaction chamber. Proton transfer mass
spectrometry is used to quantify the organic gases, while an aerosol mass
spectrometer is used to quantify the organic mass uptake and obtain
structural information for heterogeneous products. Aerosol mass spectra are
consistent with several mechanisms including acid catalyzed olefin
hydration, cationic polymerization and organic ester formation, while
measurable decreases in the sulfate mass on a per particle basis suggest
that the formation of organosulfate compounds is also likely. A portion of
the heterogeneous reactions appears to be reversible, consistent with
reversible olefin hydration reactions. A slow increase in the organic mass
after a fast initial uptake is attributed to irreversible reactions,
consistent with polymerization and organosulfate formation. Uptake
coefficients (&amp;gamma;) were estimated for a fast initial uptake governed
by the mass accommodation coefficient (&amp;alpha;) and ranged from 1&amp;times;10&lt;sup&gt;-6&lt;/sup&gt;&amp;ndash;2.5&amp;times;10&lt;sup&gt;&amp;minus;2&lt;/sup&gt;.
Uptake coefficients for a subsequent slower reactive uptake ranged from 1&amp;times;10&lt;sup&gt;-7&lt;/sup&gt;&amp;ndash;1&amp;times;10&lt;sup&gt;-4&lt;/sup&gt;.
These processes are estimated to potentially produce greater
than 2.5 μg m&lt;sup&gt;&amp;minus;3&lt;/sup&gt; of SOA from the various biogenic hydrocarbons
under atmospheric conditions, which can be highly significant given the
large array of atmospheric olefins.</p>
</abstract>
<counts><page-count count="37"/></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"> Allan, J. D., Delia, A. E., Coe, H., Bower, K. N., Alfarra, M. R., Jimenez, J. L., Middlebrook, A. M., Drewnick, F., Onasch, T. B., Canagaratna, M. R., Jayne, J. T., and Worsnop, D. R.: A generalized method for the extraction of chemically resolved mass spectra from Aerodyne aerosol mass spectrometer data, J. Aerosol Sci., 35, 909&amp;ndash;922, 2004. </mixed-citation>
</ref>
<ref id="ref2">
<label>2</label><mixed-citation publication-type="other" xlink:type="simple"> Böge, O., Miao, Y., Plewka, A., and Herrmann, H.: Formation of secondary organic particle phase compounds from isoprene gas-phase oxidation products: An aerosol chamber and field study, Atmos. Environ., 40, 2501&amp;ndash;2509, 2006. </mixed-citation>
</ref>
<ref id="ref3">
<label>3</label><mixed-citation publication-type="other" xlink:type="simple"> Chandramouli, B., Jang, M., and Kamens Richard, M.: Gas-particle partitioning of semivolatile organic compounds (SOCs) on mixtures of aerosols in a smog chamber, Environ. Sci. Technol., 37, 18, 4113&amp;ndash;4121, 2003. </mixed-citation>
</ref>
<ref id="ref4">
<label>4</label><mixed-citation publication-type="other" xlink:type="simple"> Chwang, W. K., Nowlan, V. J., and Tidwell, T. T.: Reactivity of Cyclic and Acyclic Olefinic Hydrocarbons in Acid-Catalyzed Hydration, J. Am. Chem. Soc., 99, 22, 7233&amp;ndash;7238, 1977. </mixed-citation>
</ref>
<ref id="ref5">
<label>5</label><mixed-citation publication-type="other" xlink:type="simple"> Clegg, S. L., Brimblecombe, P., and Wexler, A. S.: A thermodynamic model of the system H-NH4-Na-SO4-NO3-Cl-H2O at 298.15 K, J. Phys. Chem., 102A, 2155&amp;ndash;2171, 1998. </mixed-citation>
</ref>
<ref id="ref6">
<label>6</label><mixed-citation publication-type="other" xlink:type="simple"> Eldering, A., and Cass, G.R.:Source-oriented model for air pollutant effects on visibility, J. Geophys. Res., 101(D14), 19 343&amp;ndash;19 369, 1996. </mixed-citation>
</ref>
<ref id="ref7">
<label>7</label><mixed-citation publication-type="other" xlink:type="simple"> Ferek, R. J., Lazrus, A. L., Haagenson, P. L., and Winchester, J. W.: Strong and weak acidity of aerosols collected over the northeastern United States, Environ. Sci. Technol., 17, 315&amp;ndash;324, 1983. </mixed-citation>
</ref>
<ref id="ref8">
<label>8</label><mixed-citation publication-type="other" xlink:type="simple"> Goldberg, M. S., Burnett, R. T., Valois, M.-F., Flegel, K., Bailar Iii, J. C., Brook, J., Vincent, R., and Radon, K.: Associations between ambient air pollution and daily mortality among persons with congestive heart failure, Environ. Res., 91, 1, 8&amp;ndash;20, 2003. </mixed-citation>
</ref>
<ref id="ref9">
<label>9</label><mixed-citation publication-type="other" xlink:type="simple"> Hakola, H., Laurila, T., Rinne, J., and Puhto, K.: The ambient concentrations of biogenic hydrocarbons at a northern European, boreal site, Atmos. Environ., 34, 4971&amp;ndash;4982, 2000. </mixed-citation>
</ref>
<ref id="ref10">
<label>10</label><mixed-citation publication-type="other" xlink:type="simple"> Hannigan, M. P., Cass, G. R., Penmann, B. W., Crespi, C. L., Lafleur, A. L., Busby Jr., W. F., Thilly, W. G., and Simoneit, B. R. T.: Bioassay-directed chemical analysis of Los Angeles airborne particulate matter using a human cell mutagenicity assay, Environ. Sci. Technol., 32, 22, 3502&amp;ndash;3514, 1998. </mixed-citation>
</ref>
<ref id="ref11">
<label>11</label><mixed-citation publication-type="other" xlink:type="simple"> Harrison, D., Hunter, M. C., Lewis, A. C., Seakins, P. W., Bonsang, B., Gros, V., Kanakidou, M., Touaty, M., Kavouras, I., Mihalopoulos, N., Stephanou, E., Alves, C., Nunes, T., and Pio, C.: Ambient isoprene and monoterpene concentrations in a Greek (Abies Borisii-regis) forest. Reconciliation with emissions measurements and efects on measured OH concentrations, Atmos. Environ., 35, 4699&amp;ndash;4711, 2001. </mixed-citation>
</ref>
<ref id="ref12">
<label>12</label><mixed-citation publication-type="other" xlink:type="simple"> Hastings, W. P., Koehler, C. A., Bailey, E. L., and De Haan, D. O.: Secondary Organic Aerosol Formation by Glyoxal Hydration and Oligomer Formation: Humidity Effects and Equilibrium Shifts during Analysis, Environ. Sci. Technol., 39, 8728&amp;ndash;8735, 2005. </mixed-citation>
</ref>
<ref id="ref13">
<label>13</label><mixed-citation publication-type="other" xlink:type="simple"> Heald, C. L., Jacob, D. J., Park, R. J., Russell, L. M., Huebert, B. J., Seinfeld, J. H., Liao, H., and Weber, R. J.: A large organic aerosol source in the free troposphere missing from current models, Geophys. Res. Lett., 32, L18809, doi:10.1029/2005GL023831, 2005. </mixed-citation>
</ref>
<ref id="ref14">
<label>14</label><mixed-citation publication-type="other" xlink:type="simple"> Hindman, E. E., Borys, R. D., Lowenthal, D. H., and Phillip, N.: Long-term, wintertime aerosol, cloud and precipitation measurements in the northern Colorado Rocky Mountains, Atmos. Res., 82, 194&amp;ndash;202, 2006. </mixed-citation>
</ref>
<ref id="ref15">
<label>15</label><mixed-citation publication-type="other" xlink:type="simple"> Hoffmann, T.: Adsorptive preconcentration technique including oxidant scavenging for the measurement of reactive natural hydrocarbons in ambient air, Fres. J. Anal. Chem., 351, 41&amp;ndash;47, 1995. </mixed-citation>
</ref>
<ref id="ref16">
<label>16</label><mixed-citation publication-type="other" xlink:type="simple"> Hoffmann, T., Odum, J. R., Bowman, F., Collins, D., Klockow, D., Flagan, R. C., and Seinfeld, J. H.: Formation of organic aerosols from the oxidation of biogenic hydrocarbons, J. Atmos. Chem., 26, 189&amp;ndash;222, 1997. </mixed-citation>
</ref>
<ref id="ref17">
<label>17</label><mixed-citation publication-type="other" xlink:type="simple"> Iinuma, Y., Müller, C., Böge, O., Gnauk, T., and Herrmann, H.: The formation of organic sulfate esters in the limonene ozonolysis secondary organic aerosol (SOA) under acidic conditions, Atmos. Environ., 41, 27, 5571&amp;ndash;5583, September 2007. </mixed-citation>
</ref>
<ref id="ref18">
<label>18</label><mixed-citation publication-type="other" xlink:type="simple"> Iraci, L. T. and Tolbert, M. A.: Heterogeneous interaction of formaldehyde with cold sulfuric acid: implications for the upper troposphere and lower stratosphere, J. Geophys. Res., 102(D13), 16 099&amp;ndash;16 107, 1997. </mixed-citation>
</ref>
<ref id="ref19">
<label>19</label><mixed-citation publication-type="other" xlink:type="simple"> Jang, M., Carroll, B., Chandramouli, B., and Kamens Richard, M.: Particle growth by acid-catalyzed heterogeneous reactions of organic carbonyls on preexisting aerosols, Environ. Sci. Technol., 37, 17, 3828&amp;ndash;3837, 2003. </mixed-citation>
</ref>
<ref id="ref20">
<label>20</label><mixed-citation publication-type="other" xlink:type="simple"> Jang, M. and Kamens, R.: Atmospheric secondary aerosol formation by heterogeneous reactions of aldehydes in the presence of a sulfuric acid aerosol catalyst, Environ. Sci. Technol., 35, 24, 4758-4766, 2001. </mixed-citation>
</ref>
<ref id="ref21">
<label>21</label><mixed-citation publication-type="other" xlink:type="simple"> Jayne, J. T., Leard, D. C., Zhang, X., Davidovits, P., Smith, K. A., Kolb, C. E., and Worsnop, D. R.: Development of an aerosol mass spectrometer for size and composition analysis of submicron particles, Aerosol Sci. Technol., 33, 1&amp;ndash;2, 49&amp;ndash;70, 2000. </mixed-citation>
</ref>
<ref id="ref22">
<label>22</label><mixed-citation publication-type="other" xlink:type="simple"> Jimenez, J. L., Jayne, J. T., Shi, Q., Kolb, C. E., Worsnop, D. R., Yourshaw, I., Seinfeld, J. H., Flagan, R. C., Zhang, X., Smith, K. A., Morris, J. W., and Davidovits, P.: Ambient aerosol sampling using the Aerodyne Aerosol Mass Spectrometer, J. Geophys. Res., 108(D7), 8425, doi:10.1029/2001JD001213, 2003. </mixed-citation>
</ref>
<ref id="ref23">
<label>23</label><mixed-citation publication-type="other" xlink:type="simple"> Katoshevski, D., Nenes, A., and Seinfeld, J. H.: A study of processes that govern the maintenance of aerosols in the marine boundary layer, J. Aerosol Sci., 30, 4, 503&amp;ndash;532, 1999. </mixed-citation>
</ref>
<ref id="ref24">
<label>24</label><mixed-citation publication-type="other" xlink:type="simple"> Kavouras, I. G., Mihalopoulos, N., and Stephanou, E. G.: Secondary organic aerosol formation vs primary organic aerosol emission: In situ evidence for the chemical coupling between monoterpene acidic photooxidation products and new particle formation over forests, Environ. Sci. Technol., 33, 7, 1028&amp;ndash;1037, 1999. </mixed-citation>
</ref>
<ref id="ref25">
<label>25</label><mixed-citation publication-type="other" xlink:type="simple"> Kroll, J. H., Ng, N. L., Murphy, S. M., Flagan, R. C., and Seinfeld, J. H.: Secondary Organic Aerosol Formation from Isoprene Photooxidation, Environ. Sci. Technol., 40, 6, 1869&amp;ndash;1877, 2006. </mixed-citation>
</ref>
<ref id="ref26">
<label>26</label><mixed-citation publication-type="other" xlink:type="simple"> Kroll, J. H., Ng, N. L., Murphy, S. M., Varutbangkul, V., Flagan, R. C., and Seinfeld, J. H.: Chamber studies of secondary organic aerosol growth by reactive uptake of simple carbonyl compounds, J. Geophys. Res., 110, D23207, doi:10.1029/2005JD006004, 2005. </mixed-citation>
</ref>
<ref id="ref27">
<label>27</label><mixed-citation publication-type="other" xlink:type="simple"> Li, S.-M., Macdonald, A. M., Strapp, J. W., Lee, Y. N., and Zhou, X. L.: Chemical and physical characterizations of atmospheric aerosols over southern California, J. Geophys. Res., 102(D17), 21 341&amp;ndash;21 353, 1997. </mixed-citation>
</ref>
<ref id="ref28">
<label>28</label><mixed-citation publication-type="other" xlink:type="simple"> Li, Y.-C. and Yu, J. Z.: Simultaneous Determination of Mono- and Dicarboxylic Acids, ö-Oxo-carboxylic Acids, Midchain Ketocarboxylic Acids, and Aldehydes in Atmospheric Aerosol Samples, Environ. Sci. Technol., 39, 7616&amp;ndash;7624, 2005. </mixed-citation>
</ref>
<ref id="ref29">
<label>29</label><mixed-citation publication-type="other" xlink:type="simple"> Liggio, J. and Li, S.-M.: Organosulfate formation during the uptake of Pinonaldehyde on Acidic Sulfate Aerosols, Geophys. Res. Lett., 33, L13808, doi:10.1029/2006GL026079, 2006a. </mixed-citation>
</ref>
<ref id="ref30">
<label>30</label><mixed-citation publication-type="other" xlink:type="simple"> Liggio, J. and Li, S.-M.: Reactive Uptake of Pinonaldehyde on Acidic Aerosols, J. Geophys. Res., 111, D24303, doi:10.1029/2005JD006978, 2006b. </mixed-citation>
</ref>
<ref id="ref31">
<label>31</label><mixed-citation publication-type="other" xlink:type="simple"> Liggio, J., Li, S.-M., Brook, J. R., and Mihele, C.: Direct polymerization of isoprene and α-pinene on acidic aerosols, Geophys. Res. Lett., 34, L05814, doi:10.1029/2006GL028468, 2007. </mixed-citation>
</ref>
<ref id="ref32">
<label>32</label><mixed-citation publication-type="other" xlink:type="simple"> Liggio, J., Mclaren, R., and Li, S.-M.: Reactive uptake of glyoxal by particulate matter, J. Geophys. Res., 110, D10304, doi:10.1029/2004JD005113, 2005. </mixed-citation>
</ref>
<ref id="ref33">
<label>33</label><mixed-citation publication-type="other" xlink:type="simple"> Limbeck, A., Kulmala, M., and Puxbaum, H.: secondary organic aerosol formation in the atmosphere via heterogeneous reaction of gaseous isoprene on acidic particles, Geophys. Res. Lett., 30(19), 1996, doi:10.1029/2003GL017738, 2003. </mixed-citation>
</ref>
<ref id="ref34">
<label>34</label><mixed-citation publication-type="other" xlink:type="simple"> Noziere, B. and Riemer, D. D.: The chemical processing of gas-phase carbonyl compounds by sulfuric acid aerosols: 2,4-pentandione, Atmos. Environ., 37, 841&amp;ndash;851, 2003. </mixed-citation>
</ref>
<ref id="ref35">
<label>35</label><mixed-citation publication-type="other" xlink:type="simple"> Pankow, J. F.: An absorption model of the gas/aerosol partitioning involved in the formation of secondary organic aerosol, Atmos. Environ., 28, 2, 189&amp;ndash;193, 1994. </mixed-citation>
</ref>
<ref id="ref36">
<label>36</label><mixed-citation publication-type="other" xlink:type="simple"> Peltier, R. E., Sullivan, A. P., Weber, R. J., Wollny, A. G., Holloway, J. S., Brock, C. A., Gouw, J. A. D., and Atlas, E. L.: No evidence for acid-catalyzed secondary organic aerosol formation in power plant plumes over metropolitan Atlanta, Georgia, Geophys. Res. Lett., 112, D10S18, doi:10.1029/2006JD007515, 2007. </mixed-citation>
</ref>
<ref id="ref37">
<label>37</label><mixed-citation publication-type="other" xlink:type="simple"> Pilinis, C., Pandis, S. N., and Seinfeld, J. H.: Sensitivity of direct climate forcing by atmospheric aerosols to aerosol size and composition, J. Geophys. Res., 100(D9), 18, 739&amp;ndash;754, 1995. </mixed-citation>
</ref>
<ref id="ref38">
<label>38</label><mixed-citation publication-type="other" xlink:type="simple"> Pszenny, A. A. P., Moldanova&apos;, J., Keene, W. C., Sander, R., Maben, J. R., Martinez, M., Crutzen, P. J., Perner, D., and Prinn, R. G.: Halogen cycling and aerosol pH in the Hawaiian marine boundary layer, Atmos. Chem. Phys., 4, 147&amp;ndash;168, 2004. </mixed-citation>
</ref>
<ref id="ref39">
<label>39</label><mixed-citation publication-type="other" xlink:type="simple"> Shi, Q., Davidovits, P., Jayne, J. T., Worsnop, D. R., and Kolb, C. E.: Uptake of gas-phase ammonia. 1. Uptake by aqueous surfaces as a function of pH, J. Phys. Chem., 103, 8812&amp;ndash;8823, 1999. </mixed-citation>
</ref>
<ref id="ref40">
<label>40</label><mixed-citation publication-type="other" xlink:type="simple"> Slebocka-Tilk, H. and Brown, R. S.: Acid-Catalyzed Hydration of anti-sesquinorbornene, J. Org. Chem., 61, 8079&amp;ndash;8082, 1996. </mixed-citation>
</ref>
<ref id="ref41">
<label>41</label><mixed-citation publication-type="other" xlink:type="simple"> Steinbacher, M., Dommen, J., Ammann, C., Spirig, C., Neftel, A., and Prevot, A. S. H.: Performance characteristics of a proton-transfer-reaction mass spectrometer (PTR-MS) derived from laboratory and field measurement, Int. J. Mass Spectrom., 239, 117&amp;ndash;128, 2004. </mixed-citation>
</ref>
<ref id="ref42">
<label>42</label><mixed-citation publication-type="other" xlink:type="simple"> Surratt, J. D., Kroll, J. H., Kleindienst, T. E., Edney, E. O., Claeys, M., Sorooshian, A., Ng, N. L., Offenberg, J. H., Lewandowski, M., Jaoui, M., Flagan, R. C., and Seinfeld, J. H.: Evidence for Organosulfates in Secondary Organic Aerosol, Environ. Sci. Technol., 41, 2, 517&amp;ndash;527, 2007. </mixed-citation>
</ref>
<ref id="ref43">
<label>43</label><mixed-citation publication-type="other" xlink:type="simple"> Tolbert, M. A., Pfaff, J., Jayaweera, I., and Prather, M. J.: Uptake of formaldehyde by sulfuric acid solutions: Impact on stratospheric ozone, J. Geophys. Res., 98(D2), 2957&amp;ndash;2962, 1993. </mixed-citation>
</ref>
<ref id="ref44">
<label>44</label><mixed-citation publication-type="other" xlink:type="simple"> Wade, L. G.: Organic chemistry, Prentice Hall, Upper Saddle River, Englewood Cliffs, N. J., 2003. </mixed-citation>
</ref>
</ref-list>
</back>
</article>