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<front>
<journal-meta>
<journal-id journal-id-type="publisher">ACP</journal-id>
<journal-title-group>
<journal-title>Atmospheric Chemistry and Physics</journal-title>
<abbrev-journal-title abbrev-type="publisher">ACP</abbrev-journal-title>
</journal-title-group>
<issn pub-type="epub">1680-7324</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/acp-7-609-2007</article-id>
<title-group>
<article-title>Technical Note: Performance of Chemical Ionization Reaction Time-of-Flight Mass Spectrometry (CIR-TOF-MS) for the measurement of atmospherically significant oxygenated volatile organic compounds</article-title>
</title-group>
<contrib-group><contrib contrib-type="author" xlink:type="simple"><name name-style="western"><surname>Wyche</surname>
<given-names>K. P.</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>Blake</surname>
<given-names>R. S.</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>Ellis</surname>
<given-names>A. M.</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>Monks</surname>
<given-names>P. S.</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>Brauers</surname>
<given-names>T.</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>Koppmann</surname>
<given-names>R.</given-names>
</name>
<xref ref-type="aff" rid="aff2">
<sup>2</sup>
</xref>
<xref ref-type="aff" rid="aff4">
<sup>4</sup>
</xref>
</contrib>
<contrib contrib-type="author" xlink:type="simple"><name name-style="western"><surname>Apel</surname>
<given-names>E. C.</given-names>
</name>
<xref ref-type="aff" rid="aff3">
<sup>3</sup>
</xref>
</contrib>
</contrib-group><aff id="aff1">
<label>1</label>
<addr-line>Department of Chemistry, University of Leicester, Leicester, UK</addr-line>
</aff>
<aff id="aff2">
<label>2</label>
<addr-line>Institut für Chemie und Dynamik der Geosphäre II, Forschungszentrum Jülich, Jülich, Germany</addr-line>
</aff>
<aff id="aff3">
<label>3</label>
<addr-line>National Centre for Atmospheric Research, Boulder, Colorado, USA</addr-line>
</aff>
<aff id="aff4">
<label>4</label>
<addr-line>now at: Bergische Universität Wuppertal, Fachbereich C, Atmosphärenphysik, Wuppertal, Germany</addr-line>
</aff>
<pub-date pub-type="epub">
<day>08</day>
<month>02</month>
<year>2007</year>
</pub-date>
<volume>7</volume>
<issue>3</issue>
<fpage>609</fpage>
<lpage>620</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.net/7/609/2007/acp-7-609-2007.html">This article is available from http://www.atmos-chem-phys.net/7/609/2007/acp-7-609-2007.html</self-uri>
<self-uri xlink:href="http://www.atmos-chem-phys.net/7/609/2007/acp-7-609-2007.pdf">The full text article is available as a PDF file from http://www.atmos-chem-phys.net/7/609/2007/acp-7-609-2007.pdf</self-uri>
<abstract>
<p>The performance of a new chemical ionization reaction time-of-flight
mass spectrometer (CIR-TOF-MS) utilising the environment chamber
SAPHIR (Simulation of Atmospheric Photochemistry In a large Reaction
Chamber- Forschungzentrum Jülich, Germany) is described. The
work took place as part of the ACCENT (Atmospheric Composition and
Change the European NeTwork for excellence) supported oxygenated
volatile organic compound (OVOC) measurement intercomparison during
January 2005. The experiment entailed the measurement of 14
different atmospherically significant OVOCs at various mixing ratios
in the approximate range 10.0&amp;ndash;0.6 ppbV. The CIR-TOF-MS operated
throughout the exercise with the hydronium ion (H&lt;sub&gt;3&lt;/sub&gt;O&lt;sup&gt;+&lt;/sup&gt;) as
the primary chemical ionization (CI) reagent in order to facilitate
proton transfer to the analyte OVOCs. The results presented show
that the CIR time-of-flight mass spectrometer is capable of
detecting a wide range of atmospheric OVOCs at mixing ratios of
around 10 ppbV in &quot;real-time&quot; (i.e. detection on the one-minute time
scale), with sub-ppbV measurement also achieved following an
increase in averaging time to tens of minutes.  It is shown that in
general OVOC measurement is made with high accuracy and precision,
with integration time, mixing ratio and compound dependent values as
good as 4&amp;ndash;13% and 3&amp;ndash;15% respectively.  It is demonstrated
that CIR-TOF-MS has rapid multi-channel response at the required
sensitivity, accuracy and precision for atmospheric OVOC
measurement.</p>
</abstract>
<counts><page-count count="12"/></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"> Apel, E. C., Calvert, J. G., Gilpin, T. M., Fehsenfeld, F., and Lonneman, W. A.: Nonmethane Hydrocarbon Intercomparison Experiment (NOMHICE): Task 4, ambient air, J. Geophys. Res.-Atmos., 108(D12), 4359, doi:10.1029/2002JD002936, 2003. </mixed-citation>
</ref>
<ref id="ref2">
<label>2</label><mixed-citation publication-type="other" xlink:type="simple"> Blake, R. S., Whyte, C., Hughes, C. O., Ellis, A. M., and Monks, P. S.: Demonstration of proton-transfer reaction time-of-flight mass spectrometry for real-time analysis of trace volatile organic compounds, Anal. Chem., 76(13), 3841&amp;ndash;3845, 2004. </mixed-citation>
</ref>
<ref id="ref3">
<label>3</label><mixed-citation publication-type="other" xlink:type="simple"> Blake, R. S., Wyche, K. P., Ellis, A. M., and Monks, P. S.: Chemical ionization reaction time-of-flight mass spectrometry: Multi-reagent analysis for determination of trace gas composition, Int. J. Mass Spectrom., 254(1&amp;ndash;2), 85&amp;ndash;93, 2006. </mixed-citation>
</ref>
<ref id="ref4">
<label>4</label><mixed-citation publication-type="other" xlink:type="simple"> de Gouw, J. A., Goldan, P. D., Warneke, C., Kuster, W. C., Roberts, J. M., Marchewka, M., Bertman, S. B., Pszenny, A. A. P., and Keene, W. C.: Validation of proton transfer reaction-mass spectrometry (PTR-MS) measurements of gas-phase organic compounds in the atmosphere during the New England Air Quality Study (NEAQS) in 2002, J. Geophys. Res.-Atmos., 108(D21), 4359, doi:10.1029/2003JD003863, 2003. </mixed-citation>
</ref>
<ref id="ref5">
<label>5</label><mixed-citation publication-type="other" xlink:type="simple"> Ennis, C. J., Reynolds, J. C., Keely, B. J., and Carpenter, L. J.: A hollow cathode proton transfer reaction time of flight mass spectrometer, Int. J. Mass Spectrom., 247(1&amp;ndash;3), 72&amp;ndash;80, 2005. </mixed-citation>
</ref>
<ref id="ref6">
<label>6</label><mixed-citation publication-type="other" xlink:type="simple"> Hansel, A., Jordan, A., Holzinger, R., Prazeller, P., Vogel, W., and Lindinger, W.: Proton-Transfer Reaction Mass-Spectrometry &amp;ndash; Online Trace Gas-Analysis At The Ppb Level, Int. J. Mass Spectrom., 150, 609&amp;ndash;619, 1995. </mixed-citation>
</ref>
<ref id="ref7">
<label>7</label><mixed-citation publication-type="other" xlink:type="simple"> Hansel, A., Singer, W., Wisthaler, A., Schwarzmann, M., and Lindinger, W.: Energy dependencies of the proton transfer reactions \chemH_3O^+ + \chemCH_2O $\Leftrightarrow$ \chemCH_2OH^+ + \chemH_2O, Int. J. Mass Spectrom., 167, 697&amp;ndash;703, 1997. </mixed-citation>
</ref>
<ref id="ref8">
<label>8</label><mixed-citation publication-type="other" xlink:type="simple"> Hanson, D. R., Greenberg, J., Henry, B. E., and Kosciuch, E.: Proton transfer reaction mass spectrometry at high drift tube pressure, Int. J. Mass Spectrom., 223(1&amp;ndash;3), 507&amp;ndash;518, 2003. </mixed-citation>
</ref>
<ref id="ref9">
<label>9</label><mixed-citation publication-type="other" xlink:type="simple"> Inomata, S., Tanimoto, H., Aoki, N., Hirokawa, J., and Sadanaga, Y.: A novel discharge source of hydronium ions for proton transfer reaction ionization: design, characterization, and performance, Rapid Communications in Mass Spectrometry, 20, 1025&amp;ndash;1029, 2006. </mixed-citation>
</ref>
<ref id="ref10">
<label>10</label><mixed-citation publication-type="other" xlink:type="simple"> Kalberer, M., Paulsen, D., Sax, M., Steinbacher, M., Dommen, J., Prèvôt, 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(5664), 1659&amp;ndash;1662, 2004. </mixed-citation>
</ref>
<ref id="ref11">
<label>11</label><mixed-citation publication-type="other" xlink:type="simple"> Karl, M., Brauers, T., Dorn, H. P., Holland, F., Komenda, M., Poppe, D., Rohrer, F., Rupp, L., Schaub, A., and Wahner, A.: Kinetic Study of the OH-isoprene and \chemO_3-isoprene reaction in the atmosphere simulation chamber, SAPHIR, Geophys. Res. Lett., 31(5), L05117, doi:10.1029/2003GL019189, 2004. </mixed-citation>
</ref>
<ref id="ref12">
<label>12</label><mixed-citation publication-type="other" xlink:type="simple"> Lewis, A. C., Hopkins, J. R., Carpenter, L. J., Stanton, J., Read, K. A., and Pilling, M. J.: Sources and sinks of acetone, methanol, and acetaldehyde in North Atlantic marine air, Atmos. Chem. Phys., 5, 1963&amp;ndash;1974, 2005. </mixed-citation>
</ref>
<ref id="ref13">
<label>13</label><mixed-citation publication-type="other" xlink:type="simple"> Lindinger, W., Hirber, J., and Paretzke, H.: An Ion/Molecule-Reaction Mass-Spectrometer Used For Online Trace Gas-Analysis, Int. J. Mass Spectrom. Ion Processes, 129, 79&amp;ndash;88, 1993. </mixed-citation>
</ref>
<ref id="ref14">
<label>14</label><mixed-citation publication-type="other" xlink:type="simple"> Monks, P. S.: Gas-phase radical chemistry in the troposphere, Chem. Soc. Rev., 34(5), 376&amp;ndash;395, 2005. </mixed-citation>
</ref>
<ref id="ref15">
<label>15</label><mixed-citation publication-type="other" xlink:type="simple"> Northway, M. J., de Gouw, J. A., Fahey, D. W., Gao, R. S., Warneke, C., Roberts, J. M., and Flocke, F.: Evaluation of the role of heterogeneous oxidation of alkenes in the detection of atmospheric acetaldehyde, Atmos. Environ., 38(35), 6017&amp;ndash;6028, 2004. </mixed-citation>
</ref>
<ref id="ref16">
<label>16</label><mixed-citation publication-type="other" xlink:type="simple"> Plass-Dülmer, C., Schmidbauer, N., Slemr, J., Slemr, F., and D&apos;Souza, H.: European hydrocarbon intercomparison experiment AMOHA part 4: Canister sampling of ambient air, J. Geophys. Res.-Atmos., 111(D4), D04306, doi:10.1029/2005JD006351, 2006. </mixed-citation>
</ref>
<ref id="ref17">
<label>17</label><mixed-citation publication-type="other" xlink:type="simple"> Singh, H. B., Kanakidou, M., Crutzen, P. J., and Jacob, D. J.: High-Concentrations And Photochemical Fate of Oxygenated Hydrocarbons In The Global Troposphere, Nature, 378(6552), 50&amp;ndash;54, 1995. </mixed-citation>
</ref>
<ref id="ref18">
<label>18</label><mixed-citation publication-type="other" xlink:type="simple"> Sinreich, R., Frieß, U., Wagner, T., and Platt, U.: Multi axis differential optical absorption spectroscopy (MAX-DOAS) of gas and aerosol distributions, Faraday Discuss., 130, 153&amp;ndash;164, 2005. </mixed-citation>
</ref>
<ref id="ref19">
<label>19</label><mixed-citation publication-type="other" xlink:type="simple"> \vSpan\vel, P. and Smith, D.: Reactions of Hydrated Hydronium Ions And Hydrated Hydroxide Ions, With Some Hydrocarbons And Oxygen-Bearing Organic-Molecules, J. Phys. Chem., 99(42), 15 551&amp;ndash;15 556, 1995. </mixed-citation>
</ref>
<ref id="ref20">
<label>20</label><mixed-citation publication-type="other" xlink:type="simple"> \vSpan\vel, P. and Smith, D.: Influence of water vapour on selected ion flow tube mass spectrometric analyses of trace gases in humid air and breath, Rapid Communications in Mass Spectrometry, 14(20), 1898&amp;ndash;1906, 2000. </mixed-citation>
</ref>
<ref id="ref21">
<label>21</label><mixed-citation publication-type="other" xlink:type="simple"> Warneke, C., Holzinger, R., Hansel, A., Jordan, A., Lindinger, W., Pöschl, U., Williams, J., Hoor, P., Fischer, H., Crutzen, P. J., Scheeren, H. A., and Lelieveld, J.: Isoprene and its oxidation products methyl vinyl ketone, methacrolein, and isoprene related peroxides measured online over the tropical rain forest of Surinam in March 1998, J. Atmos. Chem., 38(2), 167&amp;ndash;185, 2001. </mixed-citation>
</ref>
<ref id="ref22">
<label>22</label><mixed-citation publication-type="other" xlink:type="simple"> Warneke, C., van der Veen, C., Luxembourg, S., de Gouw, J. A., and Kok, A.: Measurements of benzene and toluene in ambient air using proton-transfer-reaction mass spectrometry: calibration, humidity dependence, and field intercomparison, Int. J. Mass Spectrom., 207(3), 167&amp;ndash;182, 2001. </mixed-citation>
</ref>
<ref id="ref23">
<label>23</label><mixed-citation publication-type="other" xlink:type="simple"> Warneke, C., de Gouw, J. A., Kuster, W. C., Goldan, P. D., and Fall, R.: Validation of Atmospheric VOC Measurement by Proton-Transfer-Reaction Mass Spectrometry using a Gas-Chromatographic Preparation Method, Environ. Sci. Technol., 37, 2494&amp;ndash;2501, 2003. </mixed-citation>
</ref>
<ref id="ref24">
<label>24</label><mixed-citation publication-type="other" xlink:type="simple"> Warneke, C., Kato, S., De Gouw, J. A., Goldan, P. D., Kuster, W. C., Shao, M., Lovejoy, E. R., Fall, R., and Fehsenfeld, F. C.: Online volatile organic compound measurements using a newly developed proton-transfer ion-trap mass spectrometry instrument during New England Air Quality Study &amp;ndash; Intercontinental Transport and Chemical Transformation 2004: Performance, intercomparison, and compound identification, Environ. Sci. Technol., 39(14), 5390&amp;ndash;5397, 2005. </mixed-citation>
</ref>
<ref id="ref25">
<label>25</label><mixed-citation publication-type="other" xlink:type="simple"> Wayne, R. P.: Chemical Instrumentation, Oxford, Oxford University Press, 1995. </mixed-citation>
</ref>
<ref id="ref26">
<label>26</label><mixed-citation publication-type="other" xlink:type="simple"> Wyche, K. P., Blake, R. S., Willis, K. A., Monks, P. S., and Ellis, A. M.: Differentiation of isobaric compounds using chemical ionization reaction mass spectrometry, Rapid Communications in Mass Spectrometry, 19(22), 3356&amp;ndash;3362, 2005. </mixed-citation>
</ref>
</ref-list>
</back>
</article>