<?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>GÃ¶ttingen, Germany</publisher-loc>
</publisher>
</journal-meta>
<article-meta>
<article-id pub-id-type="doi">10.5194/acpd-11-5589-2011</article-id>
<title-group>
<article-title>H&lt;sub&gt;2&lt;/sub&gt; vertical profiles in the continental boundary layer: measurements at the Cabauw tall tower in the Netherlands</article-title>
</title-group>
<contrib-group><contrib contrib-type="author" xlink:type="simple"><name name-style="western"><surname>Popa</surname>
<given-names>M. E.</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>Vermeulen</surname>
<given-names>A. T.</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>van den Bulk</surname>
<given-names>W. C. 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>Jongejan</surname>
<given-names>P. A. C.</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>Batenburg</surname>
<given-names>A. M.</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>Zahorowski</surname>
<given-names>W.</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>RÃ¶ckmann</surname>
<given-names>T.</given-names>
</name>
<xref ref-type="aff" rid="aff2">
<sup>2</sup>
</xref>
</contrib>
</contrib-group><aff id="aff1">
<label>1</label>
<addr-line>Energy research Centre of the Netherlands, Petten, The Netherlands</addr-line>
</aff>
<aff id="aff2">
<label>2</label>
<addr-line>Institute for Marine and Atmospheric Research Utrecht, Utrecht University, Utrecht, The Netherlands</addr-line>
</aff>
<aff id="aff3">
<label>3</label>
<addr-line>Australian Nuclear Science and Technology Organisation, Menai, New South Wales, Australia</addr-line>
</aff>
<pub-date pub-type="epub">
<day>15</day>
<month>02</month>
<year>2011</year>
</pub-date>
<volume>11</volume>
<issue>2</issue>
<fpage>5589</fpage>
<lpage>5639</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/11/5589/2011/acpd-11-5589-2011.html">This article is available from http://www.atmos-chem-phys-discuss.net/11/5589/2011/acpd-11-5589-2011.html</self-uri>
<self-uri xlink:href="http://www.atmos-chem-phys-discuss.net/11/5589/2011/acpd-11-5589-2011.pdf">The full text article is available as a PDF file from http://www.atmos-chem-phys-discuss.net/11/5589/2011/acpd-11-5589-2011.pdf</self-uri>
<abstract>
<p>In-situ, quasi-continuous measurements of atmospheric hydrogen (H&lt;sub&gt;2&lt;/sub&gt;)
have been performed since 2007 at the Cabauw tall tower station in the
Netherlands. Mole fractions of H&lt;sub&gt;2&lt;/sub&gt;, CO and several greenhouse gases are
determined simultaneously in air sampled successively at four heights,
between 20 and 200 m above ground level. &lt;sup&gt;222&lt;/sup&gt;Rn measurements are
performed in air sampled at 20 and 200 m.

&lt;br&gt;&lt;br&gt;
This H&lt;sub&gt;2&lt;/sub&gt; dataset represents the first in-situ, quasi-continuous
measurement series of vertical profiles of H&lt;sub&gt;2&lt;/sub&gt; in the lower continental
boundary layer. From the three-year long time series, we characterize the
main features and variability patterns of H&lt;sub&gt;2&lt;/sub&gt; and CO on various time
scales; the time series is too short to justify an attempt to determine
multi-annual trends. Seasonal cycles are present in both H&lt;sub&gt;2&lt;/sub&gt; and CO, and
their amplitude varies with the sampling height. The seasonality is evident
in both the &quot;baseline&quot; values and in the short term (diurnal to synoptic
time scales) variability, the latter being significantly larger during
winter.
&lt;br&gt;&lt;br&gt;
The observed H&lt;sub&gt;2&lt;/sub&gt; short term signals and vertical gradients are in many
cases well correlated to other species, especially to CO. On the other hand,
H&lt;sub&gt;2&lt;/sub&gt; has at times a behaviour which differentiates it from all the other
species measured, due to its particular distribution of sources and sinks,
that is, with the main source in our area (anthropogenic emissions) and the
main sink (soil uptake) both near ground level.
&lt;br&gt;&lt;br&gt;
The local to regional soil sink of H&lt;sub&gt;2&lt;/sub&gt; is observable as H&lt;sub&gt;2&lt;/sub&gt;
depletion at the lower sampling levels in some of the stable nights,
although the signals at Cabauw are smaller than observed at other stations.
Positive vertical gradients are another consequence of the soil uptake. Our
estimation for the regional H&lt;sub&gt;2&lt;/sub&gt; soil uptake flux, using the radon tracer
method, is (&amp;minus;1.89 &amp;plusmn; 0.26) &amp;times; 10&lt;sup&gt;&amp;minus;5&lt;/sup&gt; g/(m&lt;sup&gt;2&lt;/sup&gt;h), significantly
smaller than other recent results from Europe. Local soil and weather
characteristics might be responsible for the very low soil uptake of
H&lt;sub&gt;2&lt;/sub&gt;. Our result could also be biased by the absence of radon flux
estimates that could reliably approximate the fluxes during the relevant
time intervals in our study domain.
&lt;br&gt;&lt;br&gt;
H&lt;sub&gt;2&lt;/sub&gt;/CO ratios of the traffic emissions computed from our data, with an
average of 0.54 &amp;plusmn; 0.07 mol:mol, are larger and more scattered than
estimated in some of the previous studies in Europe. This difference can be
explained by a different driving regime, due to the frequent traffic jams in
the influence area of Cabauw. In contrast, the H&lt;sub&gt;2&lt;/sub&gt;/CO ratios of the
large scale pollution events, with an average of 0.36 &amp;plusmn; 0.05 mol:mol,
are very similar to results of previous studies; these ratios were observed
to slightly increase with sampling height, possibly due to a stronger
influence of soil uptake at the lower sampling heights.</p>
</abstract>
<counts><page-count count="51"/></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"> Aalto, T., Lallo, M., Hatakka, J., and Laurila, T.: Atmospheric hydrogen variations and traffic emissions at an urban site in Finland, Atmos. Chem. Phys., 9, 7387â€“7396, http://dx.doi.org/10.5194/acp-9-7387-2009doi:10.5194/acp-9-7387-2009, 2009. </mixed-citation>
</ref>
<ref id="ref2">
<label>2</label><mixed-citation publication-type="other" xlink:type="simple"> Bakwin, P. S. and Tans, P. P.: Measurements of carbon dioxide on a very tall tower, Tellus, 47B, 535â€“549, 1995. </mixed-citation>
</ref>
<ref id="ref3">
<label>3</label><mixed-citation publication-type="other" xlink:type="simple"> Barnes, D. H., Wofsy, S. C., Fehlau, B. P., Gottlieb, E. W., Elkins, J. W., Dutton, G. S., and Novelli, P. C.: Hydrogen in the atmosphere: Observations above a forest canopy in a polluted environment, J. Geophys. Res. Atmos., 108, 4197, http://dx.doi.org/10.1029/2001JD001199doi:10.1029/2001JD001199, 2003. </mixed-citation>
</ref>
<ref id="ref4">
<label>4</label><mixed-citation publication-type="other" xlink:type="simple"> Biraud, S., Ciais, P., Ramonet, M., Simmonds, P., Kazan, V., Monfray, P., O&apos;Doherty, S., Spain, T. G., and Jennings, S. G.: European greenhouse gas emissions estimated from continuous atmospheric measurements and radon 222 at Mace Head, Ireland, J. Geophys. Res., 105, 1351â€“1366, 2000. </mixed-citation>
</ref>
<ref id="ref5">
<label>5</label><mixed-citation publication-type="other" xlink:type="simple"> Bonasoni, P., Calzolari, F., Colombo, T., Corazza, E., Santaguida, R., and Tesi, G.: CO and H&lt;sub&gt;2&lt;/sub&gt; continuous measurements at Mt.Cimone (Italy): Preliminary results, Atmos. Environ., 31, 959â€“967, http://dx.doi.org/10.1016/S1352-2310(96)00259-2doi:10.1016/S1352-2310(96)00259-2, 1997. </mixed-citation>
</ref>
<ref id="ref6">
<label>6</label><mixed-citation publication-type="other" xlink:type="simple"> Bond, S. W., Alvarez, R., Vollmer, M. K., Steinbacher, M., Weilenmann, M., and Reimann, S.: Molecular hydrogen (H&lt;sub&gt;2&lt;/sub&gt;) emissions from gasoline and diesel vehicles, Sci. Total Environ., 408, 3596â€“3606, http://dx.doi.org/10.1016/j.scitotenv.2010.04.055doi:10.1016/j.scitotenv.2010.04.055, 2010. </mixed-citation>
</ref>
<ref id="ref7">
<label>7</label><mixed-citation publication-type="other" xlink:type="simple"> Bond, S. W., Vollmer, M. K., Steinbacher, M., Henne, S., and Reimann, S.: Atmospheric molecular hydrogen (H&lt;sub&gt;2&lt;/sub&gt;): Observations at the high altitude site Jungfraujoch, Switzerland, Tellus B, 64â€“76, http://dx.doi.org/10.1111/j.1600-0889.2010.00509.xdoi:10.1111/j.1600-0889.2010.00509.x, 2010. </mixed-citation>
</ref>
<ref id="ref8">
<label>8</label><mixed-citation publication-type="other" xlink:type="simple"> Bousquet, P., Yver, C., Pison, I., Li, Y. S., Fortems, A., Hauglustaine, D., Szopa, S., Rayner, P. J., Novelli, P., Langenfelds, R., Steele, P., Ramonet, M., Schmidt, M., Foster, P., Morfopoulos, C., and Ciais, P.: A three-dimensional synthesis inversion of the molecular hydrogen cycle: Sources and sinks budget and implications for the soil uptake, J. Geophys. Res., 116, D01302, http://dx.doi.org/10.1029/2010JD014599doi:10.1029/2010JD014599, 2011. </mixed-citation>
</ref>
<ref id="ref9">
<label>9</label><mixed-citation publication-type="other" xlink:type="simple"> Cofer III, W. R.,, Harriss, R. C., Levine, J. S., and Edahl, Jr., R. A.: Vertical distributions of molecular hydrogen off the eastern and Gulf coasts of the United States, J. Geophys. Res., 91, 14561â€“14567, 1986. </mixed-citation>
</ref>
<ref id="ref10">
<label>10</label><mixed-citation publication-type="other" xlink:type="simple"> Conrad, R.: Soil Microbial Processes and the Cycling of Atmospheric Trace Gases, Royal Society of London Philosophical Transactions Series A, 351, 219â€“230, 1995. </mixed-citation>
</ref>
<ref id="ref11">
<label>11</label><mixed-citation publication-type="other" xlink:type="simple"> Conrad, R.: Soil microorganisms as controllers of atmospheric trace gases (H&lt;sub&gt;2&lt;/sub&gt;, CO, CH&lt;sub&gt;4&lt;/sub&gt;, OCS, N&lt;sub&gt;2&lt;/sub&gt;O, and NO), Microbiol. Mol. Biol. R., 60, 609, 609â€“640, 1996. </mixed-citation>
</ref>
<ref id="ref12">
<label>12</label><mixed-citation publication-type="other" xlink:type="simple"> Conrad, R. and Seiler, W.: Decomposition of atmospheric hydrogen by soil microorganisms and soil enzymes, Soil Biol. Biochem., 13, 43â€“49, 1981. </mixed-citation>
</ref>
<ref id="ref13">
<label>13</label><mixed-citation publication-type="other" xlink:type="simple"> Conrad, R.: Contribution of hydrogen to methane production and control of hydrogen concentrations in methanogenic soils and sediments, FEMS Microbiology Ecology, 28, 193â€“202, 1999. </mixed-citation>
</ref>
<ref id="ref14">
<label>14</label><mixed-citation publication-type="other" xlink:type="simple"> Conrad, R. and Seiler, W.: Influence of Temperature, Moisture, and Organic Carbon on the Flux of H&lt;sub&gt;2&lt;/sub&gt; and CO Between Soil and Atmosphere: Field Studies in Subtropical Regions, J. Geophys. Res., 90, 5699â€“5709, 1985. </mixed-citation>
</ref>
<ref id="ref15">
<label>15</label><mixed-citation publication-type="other" xlink:type="simple"> Constant, P., Poissant, L., and Villemur, R.: Annual hydrogen, carbon monoxide and carbon dioxide concentrations and surface to air exchanges in a rural area (QuÃ©bec, Canada), Atmos. Environ., 42, 5090â€“5100, 2008. </mixed-citation>
</ref>
<ref id="ref16">
<label>16</label><mixed-citation publication-type="other" xlink:type="simple"> Constant, P., Poissant, L., and Villemur, R.: Tropospheric H&lt;sub&gt;2&lt;/sub&gt; budget and the response of its soil uptake under the changing environment, Sci. Total Environ., 407, 1809â€“1823, 2009. </mixed-citation>
</ref>
<ref id="ref17">
<label>17</label><mixed-citation publication-type="other" xlink:type="simple"> Derwent, R., Simmonds, P., O&apos;Doherty, S., Manning, A., Collins, W., and Stevenson, D.: Global environmental impacts of the hydrogen economy, International Journal of Nuclear Hydrogen Production and Applications, 1, 57â€“67, 2006. </mixed-citation>
</ref>
<ref id="ref18">
<label>18</label><mixed-citation publication-type="other" xlink:type="simple"> Ehhalt, D. H. and Rohrer, F.: The tropospheric cycle of H&lt;sub&gt;2&lt;/sub&gt;: a critical review, Tellus B, 61, 500â€“535, 2009. </mixed-citation>
</ref>
<ref id="ref19">
<label>19</label><mixed-citation publication-type="other" xlink:type="simple"> Ehhalt, D. H., Israel, G., Roether, W., and Stich, W.: Tritium and deuterium content of atmospheric hydrogen, J. Geophys. Res., 68, 3747â€“3751, 1963. </mixed-citation>
</ref>
<ref id="ref20">
<label>20</label><mixed-citation publication-type="other" xlink:type="simple"> Ehhalt, D. H., Schmidt, U., and Heidt, L. E.: Vertical Profiles of Molecular Hydrogen in the Troposphere and Stratosphere, J. Geophys. Res., 82, 5907â€“5911, 1977. </mixed-citation>
</ref>
<ref id="ref21">
<label>21</label><mixed-citation publication-type="other" xlink:type="simple"> Ehhalt, D. H., Davidson, J. A., Cantrell, C. A., Friedman, I., and Tyler, S.: The kinetic isotope effect in the reaction of H&lt;sub&gt;2&lt;/sub&gt; with OH, J. Geophys. Res., 94, 9831â€“9836, 1989. </mixed-citation>
</ref>
<ref id="ref22">
<label>22</label><mixed-citation publication-type="other" xlink:type="simple"> Fabian, P., Borchers, R., Weiler, K. H., Schmidt, U., Volz, A., Ehhalt, D. H., Seiler, W., and MÃ¼ller, F.: Simultaneously Measured Vertical Profiles of H&lt;sub&gt;2&lt;/sub&gt;, CH&lt;sub&gt;4&lt;/sub&gt;, CO, N&lt;sub&gt;2&lt;/sub&gt;O, CFCl3, and CF2Cl2 in the Mid-Latitude Stratosphere and Troposphere, J. Geophys. Res., 84, 3149â€“3154, http://dx.doi.org/10.1029/JC084iC06p03149doi:10.1029/JC084iC06p03149, 1979. </mixed-citation>
</ref>
<ref id="ref23">
<label>23</label><mixed-citation publication-type="other" xlink:type="simple"> Friedman, I. and Scholz, T. G.: Isotopic composition of atmospheric hydrogen, 1967â€“1969, J. Geophys. Res., 79, 785â€“788, 1974. </mixed-citation>
</ref>
<ref id="ref24">
<label>24</label><mixed-citation publication-type="other" xlink:type="simple"> Gaudry, A., Polian, G., Ardouin, B., and Lambert, G.: Radon-calibrated emissions of CO&lt;sub&gt;2&lt;/sub&gt; from South Africa, Tellus B, 42, 9â€“19, 1990. </mixed-citation>
</ref>
<ref id="ref25">
<label>25</label><mixed-citation publication-type="other" xlink:type="simple"> Gerst, S. and Quay, P.: The deuterium content of atmospheric molecular hydrogen: Method and initial measurements, J. Geophys. Res., 105, 26433â€“26445, 2000. </mixed-citation>
</ref>
<ref id="ref26">
<label>26</label><mixed-citation publication-type="other" xlink:type="simple"> Gerst, S. and Quay, P.: Deuterium component of the global molecular hydrogen cycle, J. Geophys. Res., 106, 5021â€“5031, 2001. </mixed-citation>
</ref>
<ref id="ref27">
<label>27</label><mixed-citation publication-type="other" xlink:type="simple"> Glueckauf, E. and Kitt, G. P.: The hydrogen content of atmospheric air at ground level, Q. J. Roy. Meteor. Soc., 83, 522â€“528, 1957. </mixed-citation>
</ref>
<ref id="ref28">
<label>28</label><mixed-citation publication-type="other" xlink:type="simple"> GÃ¶dde, M., Meuser, K., and Conrad, R.: Hydrogen consumption and carbon monoxide production in soils with different properties, Biol. Fert. Soils, 32, 129â€“134, 2000. </mixed-citation>
</ref>
<ref id="ref29">
<label>29</label><mixed-citation publication-type="other" xlink:type="simple"> Grant, A., Stanley, K. F., Henshaw, S. J., Shallcross, D. E., and O&apos;Doherty, S.: High-frequency urban measurements of molecular hydrogen and carbon monoxide in the United Kingdom, Atmos. Chem. Phys., 10, 4715â€“4724, http://dx.doi.org/10.5194/acp-10-4715-2010doi:10.5194/acp-10-4715-2010, 2010. </mixed-citation>
</ref>
<ref id="ref30">
<label>30</label><mixed-citation publication-type="other" xlink:type="simple"> Grant, A., Witham, C. S., Simmonds, P. G., Manning, A. J., and O&apos;Doherty, S.: A 15 year record of high-frequency, in situ measurements of hydrogen at Mace Head, Ireland, Atmos. Chem. Phys., 10, 1203â€“1214, http://dx.doi.org/10.5194/acp-10-1203-2010doi:10.5194/acp-10-1203-2010, 2010. </mixed-citation>
</ref>
<ref id="ref31">
<label>31</label><mixed-citation publication-type="other" xlink:type="simple"> Guo, R. and Conrad, R.: Extraction and characterization of soil hydrogenases oxidizing atmospheric hydrogen, Soil Biol. Biochem., 40, 1149â€“1154, 2008. </mixed-citation>
</ref>
<ref id="ref32">
<label>32</label><mixed-citation publication-type="other" xlink:type="simple"> Hammer, S. and Levin, I.: Seasonal variation of the molecular hydrogen uptake by soils inferred from continuous atmospheric observations in Heidelberg, southwest Germany, Tellus B, 61, 556â€“565, 2009. </mixed-citation>
</ref>
<ref id="ref33">
<label>33</label><mixed-citation publication-type="other" xlink:type="simple"> Hammer, S., Vogel, F., Kaul, M., and Levin, I.: The H&lt;sub&gt;2&lt;/sub&gt;/CO ratio of emissions from combustion sources: comparison of top-down with bottom-up measurements in southwest Germany, Tellus B, 61, 547â€“555, 2009. </mixed-citation>
</ref>
<ref id="ref34">
<label>34</label><mixed-citation publication-type="other" xlink:type="simple"> Harris, S. H., Smith, R. L., and Suflita, J. M.: In situ hydrogen consumption kinetics as an indicator of subsurface microbial activity, FEMS Microbiol. Ecol., 60, 220â€“228, 2007. </mixed-citation>
</ref>
<ref id="ref35">
<label>35</label><mixed-citation publication-type="other" xlink:type="simple"> Hauglustaine, D. A., and Ehhalt, D. H.: A three-dimensional model of molecular hydrogen in the troposphere, J. Geophys. Res. Atmos., 107, 4330, http://dx.doi.org/10.1029/2001JD001156doi:10.1029/2001JD001156, 2002. </mixed-citation>
</ref>
<ref id="ref36">
<label>36</label><mixed-citation publication-type="other" xlink:type="simple"> Henne, S., Brunner, D., Folini, D., Solberg, S., Klausen, J., and Buchmann, B.: Assessment of parameters describing representativeness of air quality in-situ measurement sites, Atmos. Chem. Phys., 10, 3561â€“3581, http://dx.doi.org/10.5194/acp-10-3561-2010doi:10.5194/acp-10-3561-2010, 2010. </mixed-citation>
</ref>
<ref id="ref37">
<label>37</label><mixed-citation publication-type="other" xlink:type="simple"> Hirsch, A. I.: On using radon-222 and CO&lt;sub&gt;2&lt;/sub&gt; to calculate regional-scale CO&lt;sub&gt;2&lt;/sub&gt; fluxes, Atmos. Chem. Phys., 7, 3737â€“3747, http://dx.doi.org/10.5194/acp-7-3737-2007doi:10.5194/acp-7-3737-2007, 2007. </mixed-citation>
</ref>
<ref id="ref38">
<label>38</label><mixed-citation publication-type="other" xlink:type="simple"> Holladay, J. D., Hu, J., King, D. L., and Wang, Y.: An overview of hydrogen production technologies, Catalysis Today, 139, 244â€“260, 2009. </mixed-citation>
</ref>
<ref id="ref39">
<label>39</label><mixed-citation publication-type="other" xlink:type="simple"> Hurst, D. F., Bakwin, P. S., Myers, R. C., and Elkins, J. W.: Behavior of trace gas mixing ratios on a very tall tower in North Carolina, J. Geophys. Res., 102(D7), 8825â€“8835, 1997. </mixed-citation>
</ref>
<ref id="ref40">
<label>40</label><mixed-citation publication-type="other" xlink:type="simple"> Jordan, A. and Steinberg, B.: Calibration of atmospheric hydrogen measurements, Atmos. Meas. Tech. Discuss., 3, 4931â€“4966, http://dx.doi.org/10.5194/amtd-3-4931-2010doi:10.5194/amtd-3-4931-2010, 2010. </mixed-citation>
</ref>
<ref id="ref41">
<label>41</label><mixed-citation publication-type="other" xlink:type="simple"> Khalil, M. A. K. and Rasmussen, R. A.: Global increase of atmospheric molecular hydrogen, Nature, 347, 743â€“745, 1990. </mixed-citation>
</ref>
<ref id="ref42">
<label>42</label><mixed-citation publication-type="other" xlink:type="simple"> King, G. M.: Uptake of Carbon Monoxide and Hydrogen at Environmentally Relevant Concentrations by Mycobacteria$\dagger$, Appl. Environ. Microbiol., 69, 7266â€“7272, http://dx.doi.org/10.1128/aem.69.12.7266-7272.2003doi:10.1128/aem.69.12.7266-7272.2003, 2003. </mixed-citation>
</ref>
<ref id="ref43">
<label>43</label><mixed-citation publication-type="other" xlink:type="simple"> King, G. M.: Contributions of Atmospheric CO and Hydrogen Uptake to Microbial Dynamics on Recent Hawaiian Volcanic Deposits, Appl. Environ. Microbiol., 69, 4067â€“4075, http://dx.doi.org/10.1128/aem.69.7.4067-4075.2003doi:10.1128/aem.69.7.4067-4075.2003, 2003. </mixed-citation>
</ref>
<ref id="ref44">
<label>44</label><mixed-citation publication-type="other" xlink:type="simple"> Lallo, M., Aalto, T., Laurila, T., and Hatakka, J.: Seasonal variations in hydrogen deposition to boreal forest soil in southern Finland, Geophys. Res. Lett., 35, L04402, http://dx.doi.org/10.1029/2007GL032357doi:10.1029/2007GL032357, 2008. </mixed-citation>
</ref>
<ref id="ref45">
<label>45</label><mixed-citation publication-type="other" xlink:type="simple"> Lallo, M., Aalto, T., Hatakka, J., and Laurila, T.: Hydrogen soil deposition at an urban site in Finland, Atmos. Chem. Phys., 9, 8559â€“8571, http://dx.doi.org/10.5194/acp-9-8559-2009doi:10.5194/acp-9-8559-2009, 2009. </mixed-citation>
</ref>
<ref id="ref46">
<label>46</label><mixed-citation publication-type="other" xlink:type="simple"> Lallo, M., Aalto, T., Laurila, T., and Hatakka, J.: Hydrogen soil deposition in northern boreal zone, Boreal Environ. Res, 14, 784â€“793, 2009. </mixed-citation>
</ref>
<ref id="ref47">
<label>47</label><mixed-citation publication-type="other" xlink:type="simple"> Langenfelds, R., Francey, R., Pak, B. C., Steele, L. P., Lloyd, J., Trudinger, C. M., and Allison, C. E.: Interannual growth rate variations of atmospheric CO&lt;sub&gt;2&lt;/sub&gt; and its delta13C, H&lt;sub&gt;2&lt;/sub&gt;, CH&lt;sub&gt;4&lt;/sub&gt;, and CO between 1992 and 1999 linked to biomass burning, Global Biogeochem. Cy., 16, 1048, http://dx.doi.org/10.1029/2001GB001466doi:10.1029/2001GB001466, 2002. </mixed-citation>
</ref>
<ref id="ref48">
<label>48</label><mixed-citation publication-type="other" xlink:type="simple"> Levin, I.: Atmosphaerisches CO&lt;sub&gt;2&lt;/sub&gt;, Quellen und Senken auf dem Europaeischen Kontinent, PhD, University of Heidelberg, Heidelberg, Germany, 1984. </mixed-citation>
</ref>
<ref id="ref49">
<label>49</label><mixed-citation publication-type="other" xlink:type="simple"> Levin, I., Glatzel-Mattheier, H., Marik, T., Cuntz, M., Schmidt, M., and Worthy, D. E.: Verification of German methane emission inventories and their recent changes based on atmospheric observations, J. Geophys. Res., 104, 3447â€“3456, 1999. </mixed-citation>
</ref>
<ref id="ref50">
<label>50</label><mixed-citation publication-type="other" xlink:type="simple"> Liebl, K. H. and Seiler, W.: CO and H&lt;sub&gt;2&lt;/sub&gt; destruction at the soil surface, in: Microbial Production and Utilization of Gases, edited by: Schlegel, H G., Goltze, G. G. A. N. P., GÃ¶ttingen, 215â€“229, 1976. </mixed-citation>
</ref>
<ref id="ref51">
<label>51</label><mixed-citation publication-type="other" xlink:type="simple"> Messager, C., Schmidt, M., Ramonet, M., Bousquet, P., Simmonds, P., Manning, A., Kazan, V., Spain, G., Jennings, S. G., and Ciais, P.: Ten years of CO&lt;sub&gt;2&lt;/sub&gt;, CH&lt;sub&gt;4&lt;/sub&gt;, CO and N&lt;sub&gt;2&lt;/sub&gt;O fluxes over Western Europe inferred from atmospheric measurements at Mace Head, Ireland, Atmos. Chem. Phys. Discuss., 8, 1191â€“1237, http://dx.doi.org/10.5194/acpd-8-1191-2008doi:10.5194/acpd-8-1191-2008, 2008. </mixed-citation>
</ref>
<ref id="ref52">
<label>52</label><mixed-citation publication-type="other" xlink:type="simple"> Moxley, J. M. and Cape, J. N.: Depletion of carbon monoxide from the nocturnal boundary layer, Atmos. Environ., 31, 1147â€“1155, 1997. </mixed-citation>
</ref>
<ref id="ref53">
<label>53</label><mixed-citation publication-type="other" xlink:type="simple"> Neubert, R. E. M., Spijkervet, L. L., Schut, J. K., Been, H. A., Meijer, H. A. J., voor IsotopenOnderzoek, C., and Groningen, N.: A computer-controlled continuous air drying and flask sampling system, J. Atmos. Ocean. Tech., 21, 651â€“659, 2004. </mixed-citation>
</ref>
<ref id="ref54">
<label>54</label><mixed-citation publication-type="other" xlink:type="simple"> Novelli, P. C., Lang, P. M., Masarie, K. A., Hurst, D. F., Myers, R., and Elkins, J. W.: Molecular hydrogen in the troposphere: Global distribution and budget, J. Geophys. Res., 104, 30427â€“30444, 1999. </mixed-citation>
</ref>
<ref id="ref55">
<label>55</label><mixed-citation publication-type="other" xlink:type="simple"> Pison, I., Bousquet, P., Chevallier, F., Szopa, S., and Hauglustaine, D.: Multi-species inversion of CH&lt;sub&gt;4&lt;/sub&gt;, CO and H&lt;sub&gt;2&lt;/sub&gt; emissions from surface measurements, Atmos. Chem. Phys., 9, 5281â€“5297, http://dx.doi.org/10.5194/acp-9-5281-2009doi:10.5194/acp-9-5281-2009, 2009. </mixed-citation>
</ref>
<ref id="ref56">
<label>56</label><mixed-citation publication-type="other" xlink:type="simple"> Prather, M. J.: Atmospheric science: An Environmental Experiment with H&lt;sub&gt;2&lt;/sub&gt;?, Science, 302, 581â€“582, http://dx.doi.org/10.1126/science.1091060doi:10.1126/science.1091060, 2003. </mixed-citation>
</ref>
<ref id="ref57">
<label>57</label><mixed-citation publication-type="other" xlink:type="simple"> Price, H., JaeglÃ©, L., Rice, A., Quay, P., Novelli, P. C., and Gammon, R.: Global budget of molecular hydrogen and its deuterium content: Constraints from ground station, cruise, and aircraft observations, J. Geophys. Res. Atmos., 112, D22108, http://dx.doi.org/10.1029/2006JD008152doi:10.1029/2006JD008152, 2007. </mixed-citation>
</ref>
<ref id="ref58">
<label>58</label><mixed-citation publication-type="other" xlink:type="simple"> Rahn, T., Kitchen, N., and Eiler, J. M.: D/H ratios of atmospheric H&lt;sub&gt;2&lt;/sub&gt; in urban air: Results using new methods for analysis of nano-molar H&lt;sub&gt;2&lt;/sub&gt; samples, Geochim. Cosmochim. Acta, 66, 2475â€“2481, 2002. </mixed-citation>
</ref>
<ref id="ref59">
<label>59</label><mixed-citation publication-type="other" xlink:type="simple"> Rahn, T., Eiler, J. M., Boering, K. A., Wennberg, P. O., McCarthy, M. C., Tyler, S., Schauffler, S., Donnelly, S., and Atlas, E.: Extreme deuterium enrichment in stratospheric hydrogen and the global atmospheric budget of H&lt;sub&gt;2&lt;/sub&gt;, Nature, 424, 918â€“921, 2003. </mixed-citation>
</ref>
<ref id="ref60">
<label>60</label><mixed-citation publication-type="other" xlink:type="simple"> Rhee, T. S., Brenninkmeijer, C. A. M., and RÃ¶ckmann, T.: The overwhelming role of soils in the global atmospheric hydrogen cycle, Atmos. Chem. Phys., 6, 1611â€“1625, http://dx.doi.org/10.5194/acp-6-1611-2006doi:10.5194/acp-6-1611-2006, 2006. </mixed-citation>
</ref>
<ref id="ref61">
<label>61</label><mixed-citation publication-type="other" xlink:type="simple"> RÃ¶ckmann, T., Rhee, T. S., and Engel, A.: Heavy hydrogen in the stratosphere, Atmos. Chem. Phys., 3, 2015â€“2023, http://dx.doi.org/10.5194/acp-3-2015-2003doi:10.5194/acp-3-2015-2003, 2003. </mixed-citation>
</ref>
<ref id="ref62">
<label>62</label><mixed-citation publication-type="other" xlink:type="simple"> Sanderson, M. G., Collins, W. J., Derwent, R. G., and Johnson, C. E.: Simulation of Global Hydrogen Levels Using a Lagrangian Three-Dimensional Model, J. Atmos. Chem., 46, 15â€“28, 2003. </mixed-citation>
</ref>
<ref id="ref63">
<label>63</label><mixed-citation publication-type="other" xlink:type="simple"> Schmidt, U.: Molecular hydrogen in the atmosphere, Tellus, 26, 78â€“90, 1974. </mixed-citation>
</ref>
<ref id="ref64">
<label>64</label><mixed-citation publication-type="other" xlink:type="simple"> Schmidt, U.: The latitudinal and vertical distribution of molecular hydrogen in the troposphere, J. Geophys. Res., 83, 941â€“946, 1978. </mixed-citation>
</ref>
<ref id="ref65">
<label>65</label><mixed-citation publication-type="other" xlink:type="simple"> Schmidt, M., Glatzel-Mattheier, H., Sartorius, H., Worthy, D. E., and Levin, I.: Western European N&lt;sub&gt;2&lt;/sub&gt;O emissions â€“ A top-down approach based on atmospheric observations, J. Geophys. Res., 106, 5507â€“5516, 2001. </mixed-citation>
</ref>
<ref id="ref66">
<label>66</label><mixed-citation publication-type="other" xlink:type="simple"> Schmidt, M., Graul, R., Sartorius, H., and Levin, I.: The Schauinsland CO&lt;sub&gt;2&lt;/sub&gt; record: 30 years of continental observations and their implications for the variability of the European CO2 budget, J. Geophys. Res, 108, 4619, http://dx.doi.org/10.1029/2002JD003085doi:10.1029/2002JD003085, 2003. </mixed-citation>
</ref>
<ref id="ref67">
<label>67</label><mixed-citation publication-type="other" xlink:type="simple"> Schmitt, S., Hanselmann, A., WollschlÃ¤ger, U., Hammer, S., and Levin, I.: Investigation of parameters controlling the soil sink of atmospheric molecular hydrogen, Tellus B, 61, 416â€“423, 2009. </mixed-citation>
</ref>
<ref id="ref68">
<label>68</label><mixed-citation publication-type="other" xlink:type="simple"> Schuler, S. and Conrad, R.: Hydrogen oxidation activities in soil as influenced by pH, temperature, moisture, and season, Biol. Fertil. Soils, 12, 127â€“130, 1991. </mixed-citation>
</ref>
<ref id="ref69">
<label>69</label><mixed-citation publication-type="other" xlink:type="simple"> Schultz, M. G., Diehl, T., Brasseur, G. P., and Zittel, W.: Air Pollution and Climate-Forcing Impacts of a Global Hydrogen Economy, Science, 302, 624â€“627, http://dx.doi.org/10.1126/science.1089527doi:10.1126/science.1089527, 2003. </mixed-citation>
</ref>
<ref id="ref70">
<label>70</label><mixed-citation publication-type="other" xlink:type="simple"> Scranton, M. I., Barger, W. R., and Herr, F. L.: Molecular hydrogen in the urban troposphere- Measurement of seasonal variability, J. Geophys. Res., 85, 5575â€“5580, 1980. </mixed-citation>
</ref>
<ref id="ref71">
<label>71</label><mixed-citation publication-type="other" xlink:type="simple"> Seiler, W., MÃ¼ller, F., and Oeser, H.: Vertical distribution of chlorofluoromethanes in the upper troposphere and lower stratosphere, Pure Appl. Geophys., 116, 554â€“566, 1978. </mixed-citation>
</ref>
<ref id="ref72">
<label>72</label><mixed-citation publication-type="other" xlink:type="simple"> Simmonds, P. G., Derwent, R. G., O&apos;Doherty, S., Ryall, D. B., Steele, L. P., Langenfelds, R. L., Salameh, P., Wang, H. J., Dimmer, C. H., and Hudson, L. E.: Continuous high-frequency observations of hydrogen at the Mace Head baseline atmospheric monitoring station over the 1994â€“1998 period, J. Geophys. Res., 105, 12105â€“12122, 2000. </mixed-citation>
</ref>
<ref id="ref73">
<label>73</label><mixed-citation publication-type="other" xlink:type="simple"> Smith-Downey, N. V., Randerson, J. T., and Eiler, J. M.: Temperature and moisture dependence of soil H&lt;sub&gt;2&lt;/sub&gt; uptake measured in the laboratory, Geophys. Res. Lett., 33, L14813, http://dx.doi.org/10.1029/2006GL026749doi:10.1029/2006GL026749, 2006. </mixed-citation>
</ref>
<ref id="ref74">
<label>74</label><mixed-citation publication-type="other" xlink:type="simple"> Smith-Downey, N. V., Randerson, J. T., and Eiler, J. M.: Molecular hydrogen uptake by soils in forest, desert, and marsh ecosystems in California, J. Geophys. Res. Biogeosci., 113, G03037, http://dx.doi.org/10.1029/2008JG000701doi:10.1029/2008JG000701, 2008. </mixed-citation>
</ref>
<ref id="ref75">
<label>75</label><mixed-citation publication-type="other" xlink:type="simple"> Steinbacher, M., Fischer, A., Vollmer, M. K., Buchmann, B., Reimann, S., and Hueglin, C.: Perennial observations of molecular hydrogen (H&lt;sub&gt;2&lt;/sub&gt;) at a suburban site in Switzerland, Atmos. Environ., 41, 2111â€“2124, 2007. </mixed-citation>
</ref>
<ref id="ref76">
<label>76</label><mixed-citation publication-type="other" xlink:type="simple"> Szegvary, T.: European $^222$Rn flux map for atmospheric tracer applications, Ph.D. Thesis, Institute of Environmental Geosciences, University of Basel, Switzerland, Basel, 2007a. </mixed-citation>
</ref>
<ref id="ref77">
<label>77</label><mixed-citation publication-type="other" xlink:type="simple"> Szegvary, T., Leuenberger, M. C., and Conen, F.: Predicting terrestrial $^222$Rn flux using gamma dose rate as a proxy, Atmos. Chem. Phys., 7, 2789â€“2795, http://dx.doi.org/10.5194/acp-7-2789-2007doi:10.5194/acp-7-2789-2007, 2007b. </mixed-citation>
</ref>
<ref id="ref78">
<label>78</label><mixed-citation publication-type="other" xlink:type="simple"> Talukdar, R. K.: Kinetics of hydroxyl radical reactions with isotopically labeled hydrogen, J. Phys. Chem., 100, 3037â€“3043, 1996. </mixed-citation>
</ref>
<ref id="ref79">
<label>79</label><mixed-citation publication-type="other" xlink:type="simple"> Tromp, T. K., Shia, R. L., Allen, M., Eiler, J. M., and Yung, Y. L.: Potential environmental impact of a hydrogen economy on the stratosphere, Science, 300, p 1740, 2003. </mixed-citation>
</ref>
<ref id="ref80">
<label>80</label><mixed-citation publication-type="other" xlink:type="simple"> Vermeulen, A. T., Eisma, R., Hensen, A., and Slanina, J.: Transport model calculations of NW-European methane emissions, Environ. Sci. Pol., 2, 315â€“324, 1999. </mixed-citation>
</ref>
<ref id="ref81">
<label>81</label><mixed-citation publication-type="other" xlink:type="simple"> Vermeulen, A. T., Pieterse, G., Hensen, A., van den Bulk, W. C. M., and Erisman, J. W.: COMET: a Lagrangian transport model for greenhouse gas emission estimation - forward model technique and performance for methane, Atmos. Chem. Phys. Discuss., 6, 8727â€“8779, http://dx.doi.org/10.5194/acpd-6-8727-2006doi:10.5194/acpd-6-8727-2006, 2006. </mixed-citation>
</ref>
<ref id="ref82">
<label>82</label><mixed-citation publication-type="other" xlink:type="simple"> Vermeulen, A. T., Hensen, A., Popa, M. E., van den Bulk, W. C. M., and Jongejan, P. A. C.: Greenhouse gas observations from Cabauw Tall Tower (1992-2010), Atmos. Meas. Tech. Discuss., 3, 4169â€“4230, http://dx.doi.org/10.5194/amtd-3-4169-2010doi:10.5194/amtd-3-4169-2010, 2010. </mixed-citation>
</ref>
<ref id="ref83">
<label>83</label><mixed-citation publication-type="other" xlink:type="simple"> Vollmer, M. K., Juergens, N., Steinbacher, M., Reimann, S., Weilenmann, M., and Buchmann, B.: Road vehicle emissions of molecular hydrogen (H&lt;sub&gt;2&lt;/sub&gt;) from a tunnel study, Atmos. Environ., 41, 8355â€“8369, 2007. </mixed-citation>
</ref>
<ref id="ref84">
<label>84</label><mixed-citation publication-type="other" xlink:type="simple"> Vollmer, M. K., Walter, S., Bond, S. W., Soltic, P., and RÃ¶ckmann, T.: Molecular hydrogen (H&lt;sub&gt;2&lt;/sub&gt;) emissions and their isotopic signatures (H/D) from a motor vehicle: implications on atmospheric H&lt;sub&gt;2&lt;/sub&gt;, Atmos. Chem. Phys., 10, 5707â€“5718, http://dx.doi.org/10.5194/acp-10-5707-2010doi:10.5194/acp-10-5707-2010, 2010. </mixed-citation>
</ref>
<ref id="ref85">
<label>85</label><mixed-citation publication-type="other" xlink:type="simple"> Warwick, N. J., Bekki, S., Nisbet, E. G., and Pyle, J. A.: Impact of a hydrogen economy on the stratosphere and troposphere studied in a 2-D model, Geophys. Res. Lett, 31, L05107, http://dx.doi.org/10.1029/2003GL019224doi:10.1029/2003GL019224, 2004. </mixed-citation>
</ref>
<ref id="ref86">
<label>86</label><mixed-citation publication-type="other" xlink:type="simple"> Whittlestone, S. and Zahorowski, W.: Baseline radon detectors for shipboard use: Development and deployment in the First Aerosol Characterization Experiment (ACE 1), J. Geophys. Res., 103, 16743â€“16751, 1998. </mixed-citation>
</ref>
<ref id="ref87">
<label>87</label><mixed-citation publication-type="other" xlink:type="simple"> Wilson, S. R., Dick, A. L., Fraser, P. J., and Whittlestone, S.: Nitrous oxide flux estimates for south-eastern Australia, J. Atmos. Chem., 26, 169â€“188, 1997. </mixed-citation>
</ref>
<ref id="ref88">
<label>88</label><mixed-citation publication-type="other" xlink:type="simple"> Xiao, X., Prinn, R. G., Simmonds, P. G., Steele, L. P., Novelli, P. C., Huang, J., Langenfelds, R. L., O&apos;Doherty, S., Krummel, P. B., Fraser, P. J., Porter, L. W., Weiss, R. F., Salameh, P., and Wang, R. H. J.: Optimal estimation of the soil uptake rate of molecular hydrogen from the Advanced Global Atmospheric Gases Experiment and other measurements, J. Geophys. Res. Atmos., 112, D07303, http://dx.doi.org/10.1029/2006JD007241doi:10.1029/2006JD007241, 2007. </mixed-citation>
</ref>
<ref id="ref89">
<label>89</label><mixed-citation publication-type="other" xlink:type="simple"> Yonemura, S., Kawashima, S., and Tsuruta, H.: Continuous measurements of CO and H&lt;sub&gt;2&lt;/sub&gt; deposition velocities onto an andisol: uptake control by soil moisture, Tellus B, 51, 688â€“700, 1999. </mixed-citation>
</ref>
<ref id="ref90">
<label>90</label><mixed-citation publication-type="other" xlink:type="simple"> Yonemura, S., Kawashima, S., and Tsuruta, H.: Carbon monoxide, hydrogen, and methane uptake by soils in a temperate arable field and a forest, J. Geophys. Res., 105, 14347â€“14362, 2000. </mixed-citation>
</ref>
<ref id="ref91">
<label>91</label><mixed-citation publication-type="other" xlink:type="simple"> Yonemura, S., Yokozawa, M., Kawashima, S., and Tsuruta, H.: Model analysis of the influence of gas diffusivity in soil on CO and H&lt;sub&gt;2&lt;/sub&gt; uptake, Tellus B, 52, 919â€“933, 2000. </mixed-citation>
</ref>
<ref id="ref92">
<label>92</label><mixed-citation publication-type="other" xlink:type="simple"> York, D., Evensen, N. M., Martinez , M. L., and Delgado, J. D. B.: Unified equations for the slope, intercept, and standard errors of the best straight line, Am. J. Phys., 72, 367â€“375, 2004. </mixed-citation>
</ref>
<ref id="ref93">
<label>93</label><mixed-citation publication-type="other" xlink:type="simple"> Yver, C., Schmidt, M., Bousquet, P., Zahorowski, W., and Ramonet, M.: Estimation of the molecular hydrogen soil uptake and traffic emissions at a suburban site near Paris through hydrogen, carbon monoxide, and radon-222 semicontinuous measurements, J. Geophys. Res., 114, D18304, http://dx.doi.org/10.1029/2009JD012122doi:10.1029/2009JD012122, 2009. </mixed-citation>
</ref>
<ref id="ref94">
<label>94</label><mixed-citation publication-type="other" xlink:type="simple"> Yver, C., Pison, I., Fortems-Cheiney, A., Schmidt, M., Bousquet, P., Ramonet, M., Jordan, A., Søvde, A., Engel, A., Fisher, R., Lowry, D., Nisbet, E., Levin, I., Hammer, S., Necki, J., Bartyzel, J., Reimann, S., Vollmer, M. K., Steinbacher, M., Aalto, T., Maione, M., Arduini, I., O&apos;Doherty, S., Grant, A., Sturges, W., Lunder, C. R., Privalov, V., and Paramonova, N.: A new estimation of the recent tropospheric molecular hydrogen budget using atmospheric observations and variational inversion, Atmos. Chem. Phys. Discuss., 10, 28963â€“29005, http://dx.doi.org/10.5194/acpd-10-28963-2010doi:10.5194/acpd-10-28963-2010, 2010. </mixed-citation>
</ref>
</ref-list>
</back>
</article>