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<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">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-12-3527-2012</article-id>
<title-group>
<article-title>Observed and simulated time evolution of HCl,  ClONO&lt;sub&gt;2&lt;/sub&gt;, and HF total column abundances</article-title>
</title-group>
<contrib-group><contrib contrib-type="author" xlink:type="simple"><name name-style="western"><surname>Kohlhepp</surname>
<given-names>R.</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>Ruhnke</surname>
<given-names>R.</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>Chipperfield</surname>
<given-names>M. 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>De Mazière</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>Notholt</surname>
<given-names>J.</given-names>
</name>
<xref ref-type="aff" rid="aff4">
<sup>4</sup>
</xref>
</contrib>
<contrib contrib-type="author" xlink:type="simple"><name name-style="western"><surname>Barthlott</surname>
<given-names>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>Batchelor</surname>
<given-names>R. L.</given-names>
</name>
<xref ref-type="aff" rid="aff5">
<sup>5</sup>
</xref>
<xref ref-type="aff" rid="aff6">
<sup>6</sup>
</xref>
</contrib>
<contrib contrib-type="author" xlink:type="simple"><name name-style="western"><surname>Blatherwick</surname>
<given-names>R. D.</given-names>
</name>
<xref ref-type="aff" rid="aff7">
<sup>7</sup>
</xref>
</contrib>
<contrib contrib-type="author" xlink:type="simple"><name name-style="western"><surname>Blumenstock</surname>
<given-names>Th.</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>Coffey</surname>
<given-names>M. T.</given-names>
</name>
<xref ref-type="aff" rid="aff6">
<sup>6</sup>
</xref>
</contrib>
<contrib contrib-type="author" xlink:type="simple"><name name-style="western"><surname>Demoulin</surname>
<given-names>P.</given-names>
</name>
<xref ref-type="aff" rid="aff8">
<sup>8</sup>
</xref>
</contrib>
<contrib contrib-type="author" xlink:type="simple"><name name-style="western"><surname>Fast</surname>
<given-names>H.</given-names>
</name>
<xref ref-type="aff" rid="aff9">
<sup>9</sup>
</xref>
</contrib>
<contrib contrib-type="author" xlink:type="simple"><name name-style="western"><surname>Feng</surname>
<given-names>W.</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>Goldman</surname>
<given-names>A.</given-names>
</name>
<xref ref-type="aff" rid="aff6">
<sup>6</sup>
</xref>
</contrib>
<contrib contrib-type="author" xlink:type="simple"><name name-style="western"><surname>Griffith</surname>
<given-names>D. W. T.</given-names>
</name>
<xref ref-type="aff" rid="aff10">
<sup>10</sup>
</xref>
</contrib>
<contrib contrib-type="author" xlink:type="simple"><name name-style="western"><surname>Hamann</surname>
<given-names>K.</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>Hannigan</surname>
<given-names>J. W.</given-names>
</name>
<xref ref-type="aff" rid="aff6">
<sup>6</sup>
</xref>
</contrib>
<contrib contrib-type="author" xlink:type="simple"><name name-style="western"><surname>Hase</surname>
<given-names>F.</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>Jones</surname>
<given-names>N. B.</given-names>
</name>
<xref ref-type="aff" rid="aff10">
<sup>10</sup>
</xref>
</contrib>
<contrib contrib-type="author" xlink:type="simple"><name name-style="western"><surname>Kagawa</surname>
<given-names>A.</given-names>
</name>
<xref ref-type="aff" rid="aff11">
<sup>11</sup>
</xref>
<xref ref-type="aff" rid="aff12">
<sup>12</sup>
</xref>
</contrib>
<contrib contrib-type="author" xlink:type="simple"><name name-style="western"><surname>Kaiser</surname>
<given-names>I.</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>Kasai</surname>
<given-names>Y.</given-names>
</name>
<xref ref-type="aff" rid="aff11">
<sup>11</sup>
</xref>
</contrib>
<contrib contrib-type="author" xlink:type="simple"><name name-style="western"><surname>Kirner</surname>
<given-names>O.</given-names>
</name>
<xref ref-type="aff" rid="aff13">
<sup>13</sup>
</xref>
</contrib>
<contrib contrib-type="author" xlink:type="simple"><name name-style="western"><surname>Kouker</surname>
<given-names>W.</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>Lindenmaier</surname>
<given-names>R.</given-names>
</name>
<xref ref-type="aff" rid="aff5">
<sup>5</sup>
</xref>
</contrib>
<contrib contrib-type="author" xlink:type="simple"><name name-style="western"><surname>Mahieu</surname>
<given-names>E.</given-names>
</name>
<xref ref-type="aff" rid="aff8">
<sup>8</sup>
</xref>
</contrib>
<contrib contrib-type="author" xlink:type="simple"><name name-style="western"><surname>Mittermeier</surname>
<given-names>R. L.</given-names>
</name>
<xref ref-type="aff" rid="aff9">
<sup>9</sup>
</xref>
</contrib>
<contrib contrib-type="author" xlink:type="simple"><name name-style="western"><surname>Monge-Sanz</surname>
<given-names>B.</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>Morino</surname>
<given-names>I.</given-names>
</name>
<xref ref-type="aff" rid="aff14">
<sup>14</sup>
</xref>
</contrib>
<contrib contrib-type="author" xlink:type="simple"><name name-style="western"><surname>Murata</surname>
<given-names>I.</given-names>
</name>
<xref ref-type="aff" rid="aff15">
<sup>15</sup>
</xref>
</contrib>
<contrib contrib-type="author" xlink:type="simple"><name name-style="western"><surname>Nakajima</surname>
<given-names>H.</given-names>
</name>
<xref ref-type="aff" rid="aff16">
<sup>16</sup>
</xref>
</contrib>
<contrib contrib-type="author" xlink:type="simple"><name name-style="western"><surname>Palm</surname>
<given-names>M.</given-names>
</name>
<xref ref-type="aff" rid="aff4">
<sup>4</sup>
</xref>
</contrib>
<contrib contrib-type="author" xlink:type="simple"><name name-style="western"><surname>Paton-Walsh</surname>
<given-names>C.</given-names>
</name>
<xref ref-type="aff" rid="aff10">
<sup>10</sup>
</xref>
</contrib>
<contrib contrib-type="author" xlink:type="simple"><name name-style="western"><surname>Raffalski</surname>
<given-names>U.</given-names>
</name>
<xref ref-type="aff" rid="aff17">
<sup>17</sup>
</xref>
</contrib>
<contrib contrib-type="author" xlink:type="simple"><name name-style="western"><surname>Reddmann</surname>
<given-names>Th.</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>Rettinger</surname>
<given-names>M.</given-names>
</name>
<xref ref-type="aff" rid="aff18">
<sup>18</sup>
</xref>
</contrib>
<contrib contrib-type="author" xlink:type="simple"><name name-style="western"><surname>Rinsland</surname>
<given-names>C. P.</given-names>
</name>
<xref ref-type="aff" rid="aff19">
<sup>19</sup>
</xref>
<xref ref-type="aff" rid="aff24">
<sup>24</sup>
</xref>
</contrib>
<contrib contrib-type="author" xlink:type="simple"><name name-style="western"><surname>Rozanov</surname>
<given-names>E.</given-names>
</name>
<xref ref-type="aff" rid="aff20">
<sup>20</sup>
</xref>
<xref ref-type="aff" rid="aff21">
<sup>21</sup>
</xref>
</contrib>
<contrib contrib-type="author" xlink:type="simple"><name name-style="western"><surname>Schneider</surname>
<given-names>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>Senten</surname>
<given-names>C.</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>Servais</surname>
<given-names>C.</given-names>
</name>
<xref ref-type="aff" rid="aff8">
<sup>8</sup>
</xref>
</contrib>
<contrib contrib-type="author" xlink:type="simple"><name name-style="western"><surname>Sinnhuber</surname>
<given-names>B.-M.</given-names>
</name>
<xref ref-type="aff" rid="aff1">
<sup>1</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>Smale</surname>
<given-names>D.</given-names>
</name>
<xref ref-type="aff" rid="aff22">
<sup>22</sup>
</xref>
</contrib>
<contrib contrib-type="author" xlink:type="simple"><name name-style="western"><surname>Strong</surname>
<given-names>K.</given-names>
</name>
<xref ref-type="aff" rid="aff5">
<sup>5</sup>
</xref>
</contrib>
<contrib contrib-type="author" xlink:type="simple"><name name-style="western"><surname>Sussmann</surname>
<given-names>R.</given-names>
</name>
<xref ref-type="aff" rid="aff18">
<sup>18</sup>
</xref>
</contrib>
<contrib contrib-type="author" xlink:type="simple"><name name-style="western"><surname>Taylor</surname>
<given-names>J. R.</given-names>
</name>
<xref ref-type="aff" rid="aff5">
<sup>5</sup>
</xref>
<xref ref-type="aff" rid="aff23">
<sup>23</sup>
</xref>
</contrib>
<contrib contrib-type="author" xlink:type="simple"><name name-style="western"><surname>Vanhaelewyn</surname>
<given-names>G.</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>Warneke</surname>
<given-names>T.</given-names>
</name>
<xref ref-type="aff" rid="aff4">
<sup>4</sup>
</xref>
</contrib>
<contrib contrib-type="author" xlink:type="simple"><name name-style="western"><surname>Whaley</surname>
<given-names>C.</given-names>
</name>
<xref ref-type="aff" rid="aff5">
<sup>5</sup>
</xref>
</contrib>
<contrib contrib-type="author" xlink:type="simple"><name name-style="western"><surname>Wiehle</surname>
<given-names>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>Wood</surname>
<given-names>S. W.</given-names>
</name>
<xref ref-type="aff" rid="aff22">
<sup>22</sup>
</xref>
</contrib>
</contrib-group><aff id="aff1">
<label>1</label>
<addr-line>Karlsruhe Institute of Technology (KIT), Institute for Meteorology and Climate Research (IMK-ASF), Karlsruhe, Germany</addr-line>
</aff>
<aff id="aff2">
<label>2</label>
<addr-line>Institute for Climate and Atmospheric Science, School of Earth and Environment, University of Leeds, Leeds, UK</addr-line>
</aff>
<aff id="aff3">
<label>3</label>
<addr-line>Belgian Institute for Space Aeronomy (BIRA-IASB), Brussels, Belgium</addr-line>
</aff>
<aff id="aff4">
<label>4</label>
<addr-line>Institute of Environmental Physics, University of Bremen, Bremen, Germany</addr-line>
</aff>
<aff id="aff5">
<label>5</label>
<addr-line>Department of Physics, University of Toronto, Toronto, Ontario, Canada</addr-line>
</aff>
<aff id="aff6">
<label>6</label>
<addr-line>National Center for Atmospheric Research (NCAR), Boulder, CO, USA</addr-line>
</aff>
<aff id="aff7">
<label>7</label>
<addr-line>Department of Physics and Astronomy, University of Denver, Denver, CO, USA</addr-line>
</aff>
<aff id="aff8">
<label>8</label>
<addr-line>Institute of Astrophysics and Geophysics, University of Liège, Liège, Belgium</addr-line>
</aff>
<aff id="aff9">
<label>9</label>
<addr-line>Environment Canada, Toronto, Ontario, Canada</addr-line>
</aff>
<aff id="aff10">
<label>10</label>
<addr-line>Centre for Atmospheric Chemistry, University of Wollongong, Wollongong, Australia</addr-line>
</aff>
<aff id="aff11">
<label>11</label>
<addr-line>National Institute of Information and Communications Technology, Tokyo, Japan</addr-line>
</aff>
<aff id="aff12">
<label>12</label>
<addr-line>Fujitsu FIP Corporation, Tokyo, Japan</addr-line>
</aff>
<aff id="aff13">
<label>13</label>
<addr-line>Karlsruhe Institute of Technology (KIT), Steinbuch Centre for Computing, Karlsruhe, Germany</addr-line>
</aff>
<aff id="aff14">
<label>14</label>
<addr-line>Center for Global Environmental Research, National Institute for Environmental Studies (NIES), Japan</addr-line>
</aff>
<aff id="aff15">
<label>15</label>
<addr-line>Department of Environmental Studies, Graduate School of Environmental Studies, Tohoku University, Japan</addr-line>
</aff>
<aff id="aff16">
<label>16</label>
<addr-line>Atmospheric Environment Division, National Institute for Environmental Studies (NIES), Japan</addr-line>
</aff>
<aff id="aff17">
<label>17</label>
<addr-line>Swedish Institute of Space Physics (IRF), Kiruna, Sweden</addr-line>
</aff>
<aff id="aff18">
<label>18</label>
<addr-line>Karlsruhe Institute of Technology (KIT), Institute for Meteorology and Climate Research (IMK-IFU), Garmisch-Partenkirchen, Germany</addr-line>
</aff>
<aff id="aff19">
<label>19</label>
<addr-line>NASA Langley Research Center, Hampton, VA, USA</addr-line>
</aff>
<aff id="aff20">
<label>20</label>
<addr-line>ETH Zürich, Institute for Atmospheric and Climate Science (IACETH), Zürich, Switzerland</addr-line>
</aff>
<aff id="aff21">
<label>21</label>
<addr-line>Physical-Meteorological Observatory, World Radiation Center, Davos, Switzerland</addr-line>
</aff>
<aff id="aff22">
<label>22</label>
<addr-line>National Institute of Water and Atmospheric Research Ltd (NIWA), Lauder, New Zealand</addr-line>
</aff>
<aff id="aff23">
<label>23</label>
<addr-line>National Ecological Observatory Network (NEON), Boulder, CO, USA</addr-line>
</aff>
<aff id="aff24">
<label>24</label>
<addr-line>deceased</addr-line>
</aff>
<pub-date pub-type="epub">
<day>12</day>
<month>04</month>
<year>2012</year>
</pub-date>
<volume>12</volume>
<issue>7</issue>
<fpage>3527</fpage>
<lpage>3556</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/12/3527/2012/acp-12-3527-2012.html">This article is available from http://www.atmos-chem-phys.net/12/3527/2012/acp-12-3527-2012.html</self-uri>
<self-uri xlink:href="http://www.atmos-chem-phys.net/12/3527/2012/acp-12-3527-2012.pdf">The full text article is available as a PDF file from http://www.atmos-chem-phys.net/12/3527/2012/acp-12-3527-2012.pdf</self-uri>
<abstract>
<p>Time series of total column abundances of hydrogen chloride (HCl), chlorine
nitrate (ClONO&lt;sub&gt;2&lt;/sub&gt;), and hydrogen fluoride (HF) were determined from
ground-based Fourier transform infrared (FTIR) spectra recorded at 17 sites
belonging to the Network for the Detection of Atmospheric Composition Change
(NDACC) and located between 80.05° N and 77.82° S. By
providing such a near-global overview on ground-based measurements of the two
major stratospheric chlorine reservoir species, HCl and ClONO&lt;sub&gt;2&lt;/sub&gt;, the
present study is able to confirm the decrease of the atmospheric inorganic
chlorine abundance during the last few years. This decrease is expected
following the 1987 Montreal Protocol and its amendments and adjustments,
where restrictions and a subsequent phase-out of the prominent anthropogenic
chlorine source gases (solvents, chlorofluorocarbons) were agreed upon to
enable a stabilisation and recovery of the stratospheric ozone layer. The
atmospheric fluorine content is expected to be influenced by the Montreal
Protocol, too, because most of the banned anthropogenic gases also represent
important fluorine sources. But many of the substitutes to the banned gases
also contain fluorine so that the HF total column abundance is expected to
have continued to increase during the last few years.
&lt;br&gt;&lt;br&gt;
The measurements are compared with calculations from five different models:
the two-dimensional Bremen model, the two chemistry-transport models KASIMA
and SLIMCAT, and the two chemistry-climate models EMAC and SOCOL. Thereby,
the ability of the models to reproduce the absolute total column amounts, the
seasonal cycles, and the temporal evolution found in the FTIR measurements is
investigated and inter-compared. This is especially interesting because the
models have different architectures. The overall agreement between the
measurements and models for the total column abundances and the seasonal
cycles is good.
&lt;br&gt;&lt;br&gt;
Linear trends of HCl, ClONO&lt;sub&gt;2&lt;/sub&gt;, and HF are calculated from both measurement
and model time series data, with a focus on the time range 2000–2009. This
period is chosen because from most of the measurement sites taking part in
this study, data are available during these years. The precision of the
trends is estimated with the bootstrap resampling method. The sensitivity of
the trend results with respect to the fitting function, the time of year
chosen and time series length is investigated, as well as a bias due to the
irregular sampling of the measurements.
&lt;br&gt;&lt;br&gt;
The measurements and model results investigated here agree qualitatively on a
decrease of the chlorine species by around 1% yr&lt;sup&gt;−1&lt;/sup&gt;. The models simulate an
increase of HF of around 1% yr&lt;sup&gt;−1&lt;/sup&gt;. This also agrees well with most of the
measurements, but some of the FTIR series in the Northern Hemisphere show a
stabilisation or even a decrease in the last few years. In general, for all
three gases, the measured trends vary more strongly with latitude and
hemisphere than the modelled trends. Relative to the FTIR measurements, the
models tend to underestimate the decreasing chlorine trends and to
overestimate the fluorine increase in the Northern Hemisphere.
&lt;br&gt;&lt;br&gt;
At most sites, the models simulate a stronger decrease of ClONO&lt;sub&gt;2&lt;/sub&gt; than of
HCl. In the FTIR measurements, this difference between the trends of HCl and
ClONO&lt;sub&gt;2&lt;/sub&gt; depends strongly on latitude, especially in the Northern
Hemisphere.</p>
</abstract>
<counts><page-count count="30"/></counts>
</article-meta>
</front>
<body/>
<back>
<ref-list>
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