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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-13-1203-2013</article-id>
<title-group>
<article-title>Contribution of very short-lived substances to stratospheric bromine loading: uncertainties and constraints</article-title>
</title-group>
<contrib-group><contrib contrib-type="author" xlink:type="simple"><name name-style="western"><surname>Aschmann</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>Sinnhuber</surname>
<given-names>B.-M.</given-names>
</name>
<xref ref-type="aff" rid="aff2">
<sup>2</sup>
</xref>
</contrib>
</contrib-group><aff id="aff1">
<label>1</label>
<addr-line>Institute of Environmental Physics, University of Bremen, Bremen, Germany</addr-line>
</aff>
<aff id="aff2">
<label>2</label>
<addr-line>Institute for Meteorology and Climate Research, Karlsruhe Institute of Technology, Karlsruhe, Germany</addr-line>
</aff>
<pub-date pub-type="epub">
<day>01</day>
<month>02</month>
<year>2013</year>
</pub-date>
<volume>13</volume>
<issue>3</issue>
<fpage>1203</fpage>
<lpage>1219</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/13/1203/2013/acp-13-1203-2013.html">This article is available from http://www.atmos-chem-phys.net/13/1203/2013/acp-13-1203-2013.html</self-uri>
<self-uri xlink:href="http://www.atmos-chem-phys.net/13/1203/2013/acp-13-1203-2013.pdf">The full text article is available as a PDF file from http://www.atmos-chem-phys.net/13/1203/2013/acp-13-1203-2013.pdf</self-uri>
<abstract>
<p>Very short-lived substances (VSLS) still represent a major factor of
uncertainty in the quantification of stratospheric bromine loading. One of
the major obstacles for short-lived source gases in contributing to the
stratosphere is generally thought to be loss of inorganic bromine (Br&lt;sub&gt;y&lt;/sub&gt;) 
in the tropical tropopause layer (TTL) due to dehydration. We use
sensitivity calculations with a three-dimensional chemistry transport model
comprising a consistent parametrization of convective transport and a
comprehensive chemistry scheme to investigate the associated processes. The
model considers the two most important bromine VSLS, bromoform (CHBr&lt;sub&gt;3&lt;/sub&gt;) and
dibromomethane (CH&lt;sub&gt;2&lt;/sub&gt;Br&lt;sub&gt;2&lt;/sub&gt;). The organic bromine source gases as well as
the resulting profile of inorganic bromine in the model are consistent with
available observations. In contrast to its organic precursors, Br&lt;sub&gt;y&lt;/sub&gt;
is assumed to have a significant sorption capacity regarding sedimenting
liquid or frozen particles thus the fraction of intact source gases during
their ascent through the TTL is a critical factor. We find that source gas
injection is the dominant pathway into the stratosphere, about 50% of
CHBr&lt;sub&gt;3&lt;/sub&gt; and 94% of CH&lt;sub&gt;2&lt;/sub&gt;Br&lt;sub&gt;2&lt;/sub&gt; is able to overcome the cold point
tropopause at approximately 17 km altitude, modulated by the interannual
variability of the vertical transport efficiency. In fact, our sensitivity
calculations indicate that the extent of source gas injection of CHBr&lt;sub&gt;3&lt;/sub&gt; is
highly sensitive to the strength of convection and large-scale ascent; in
contrast, modifying the photolysis or the destruction via OH yields a
significantly smaller response. In principle, the same applies as well to
CH&lt;sub&gt;2&lt;/sub&gt;Br&lt;sub&gt;2&lt;/sub&gt;, though it is considerably less responsive due to its longer
lifetime. The next important aspect we identified is that the partitioning of
available Br&lt;sub&gt;y&lt;/sub&gt; from short-lived sources is clearly shifted away
from HBr, according to our current state of knowledge the only member of the
Br&lt;sub&gt;y&lt;/sub&gt; family which is efficiently adsorbed on ice particles. This
effect is caused by very efficient heterogeneous reactions on ice surfaces
which reduce the HBr/Br&lt;sub&gt;y&lt;/sub&gt; fraction below 15% at the tropical
tropopause. Under these circumstances there is no significant loss of
Br&lt;sub&gt;y&lt;/sub&gt; due to dehydration in the model, VSLS contribute fully to
stratospheric bromine. In addition, we conduct several sensitivity
calculations to test the robustness of this result. If heterogeneous
chemistry is ignored, the HBr/Br&lt;sub&gt;y&lt;/sub&gt; fraction exceeds 50% and
about 10% of bromine from VSLS is scavenged. Dehydration plays a minor
role for Br&lt;sub&gt;y&lt;/sub&gt; removal under the assumption that HOBr is
efficiently adsorbed on ice as well since the heterogeneous reactions alter
the partitioning equilibrium of Br&lt;sub&gt;y&lt;/sub&gt; in favor of HOBr. In
this case, up to 12% of bromine from VSLS is removed. Even in the extreme
and unrealistic case that adsorbed species on ice particles are
instantaneously removed the maximum loss of bromine does not exceed 25%.
Assuming 6 parts per trillion by volume (pptv) of bromine short-lived source
gases in convective updrafts, a value that is supported by observational
data, we find a most likely contribution of VSLS to stratospheric bromine in
the range of 4.5–6 pptv.</p>
</abstract>
<counts><page-count count="17"/></counts>
</article-meta>
</front>
<body/>
<back>
<ref-list>
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