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<article xmlns:xlink="http://www.w3.org/1999/xlink" xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:oasis="http://docs.oasis-open.org/ns/oasis-exchange/table" dtd-version="3.0">
  <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>
<abbrev-journal-title abbrev-type="nlm-ta">Atmos. Chem. Phys.</abbrev-journal-title>
</journal-title-group>
<issn pub-type="epub">1680-7324</issn>
<publisher><publisher-name>Copernicus Publications</publisher-name>
<publisher-loc>Göttingen, Germany</publisher-loc>
</publisher>
</journal-meta>

    <article-meta>
      <article-id pub-id-type="doi">10.5194/acp-16-12205-2016</article-id><title-group><article-title>Meteorological constraints on oceanic halocarbons above the Peruvian
upwelling</article-title>
      </title-group><?xmltex \runningtitle{Meteorological constraints on oceanic halocarbons}?><?xmltex \runningauthor{S. Fuhlbr\"{u}gge et al.}?>
      <contrib-group>
        <contrib contrib-type="author" corresp="no" rid="aff1">
          <name><surname>Fuhlbrügge</surname><given-names>Steffen</given-names></name>
          
        </contrib>
        <contrib contrib-type="author" corresp="no" rid="aff1">
          <name><surname>Quack</surname><given-names>Birgit</given-names></name>
          
        </contrib>
        <contrib contrib-type="author" corresp="no" rid="aff2">
          <name><surname>Atlas</surname><given-names>Elliot</given-names></name>
          
        <ext-link>https://orcid.org/0000-0003-3847-5346</ext-link></contrib>
        <contrib contrib-type="author" corresp="no" rid="aff1">
          <name><surname>Fiehn</surname><given-names>Alina</given-names></name>
          
        <ext-link>https://orcid.org/0000-0003-3376-4405</ext-link></contrib>
        <contrib contrib-type="author" corresp="no" rid="aff1">
          <name><surname>Hepach</surname><given-names>Helmke</given-names></name>
          
        <ext-link>https://orcid.org/0000-0002-4939-590X</ext-link></contrib>
        <contrib contrib-type="author" corresp="yes" rid="aff3">
          <name><surname>Krüger</surname><given-names>Kirstin</given-names></name>
          <email>kirstin.krueger@geo.uio.no</email>
        <ext-link>https://orcid.org/0000-0002-0636-9488</ext-link></contrib>
        <aff id="aff1"><label>1</label><institution>GEOMAR Helmholtz Centre for Ocean Research Kiel, Kiel, Germany</institution>
        </aff>
        <aff id="aff2"><label>2</label><institution>Rosenstiel School for Marine and Atmospheric Sciences, Miami, Florida,
USA</institution>
        </aff>
        <aff id="aff3"><label>3</label><institution>Department of Geosciences, University of Oslo, Oslo, Norway</institution>
        </aff>
      </contrib-group>
      <author-notes><corresp id="corr1">Kirstin Krüger (kirstin.krueger@geo.uio.no)</corresp></author-notes><pub-date><day>29</day><month>September</month><year>2016</year></pub-date>
      
      <volume>16</volume>
      <issue>18</issue>
      <fpage>12205</fpage><lpage>12217</lpage>
      <history>
        <date date-type="received"><day>23</day><month>June</month><year>2015</year></date>
           <date date-type="rev-request"><day>31</day><month>July</month><year>2015</year></date>
           <date date-type="rev-recd"><day>29</day><month>August</month><year>2016</year></date>
           <date date-type="accepted"><day>30</day><month>August</month><year>2016</year></date>
      </history>
      <permissions>
<license license-type="open-access">
<license-p>This work is licensed under a Creative Commons Attribution 3.0 Unported License. To view a copy of this license, visit <ext-link ext-link-type="uri" xlink:href="http://creativecommons.org/licenses/by/3.0/">http://creativecommons.org/licenses/by/3.0/</ext-link></license-p>
</license>
</permissions><self-uri xlink:href="https://acp.copernicus.org/articles/.html">This article is available from https://acp.copernicus.org/articles/.html</self-uri>
<self-uri xlink:href="https://acp.copernicus.org/articles/.pdf">The full text article is available as a PDF file from https://acp.copernicus.org/articles/.pdf</self-uri>


      <abstract>
    <p>During a cruise of R/V <italic>METEOR</italic> in December 2012 the oceanic sources and
emissions of various halogenated trace gases and their mixing ratios in the
marine atmospheric boundary layer (MABL) were investigated above the
Peruvian upwelling. This study presents novel observations of the three very
short lived substances (VSLSs) – bromoform, dibromomethane and methyl iodide – together with high-resolution meteorological measurements, Lagrangian
transport and source–loss calculations. Oceanic emissions of bromoform and
dibromomethane were relatively low compared to other upwelling regions,
while those for methyl iodide were very high. Radiosonde launches during the
cruise revealed a low, stable MABL and a distinct trade inversion above
acting as strong barriers for convection and vertical transport of trace
gases in this region. Observed atmospheric VSLS abundances, sea surface
temperature, relative humidity and MABL height correlated well during the
cruise. We used a simple source–loss estimate to quantify the contribution
of oceanic emissions along the cruise track to the observed atmospheric
concentrations. This analysis showed that averaged, instantaneous emissions
could not support the observed atmospheric mixing ratios of VSLSs and that
the marine background abundances below the trade inversion were
significantly influenced by advection of regional sources. Adding to this
background, the observed maximum emissions of halocarbons in the coastal
upwelling could explain the high atmospheric VSLS concentrations in
combination with their accumulation under the distinct MABL and trade
inversions. Stronger emissions along the nearshore coastline likely added
to the elevated abundances under the steady atmospheric conditions. This
study underscores the importance of oceanic upwelling and trade wind systems
on the atmospheric distribution of marine VSLS emissions.</p>
  </abstract>
    </article-meta>
  </front>
<body>
      

<sec id="Ch1.S1" sec-type="intro">
  <title>Introduction</title>
      <p>Oceanic
fluxes of short-lived halocarbons contribute to reactive halogens in the
atmosphere, where they are subsequently involved in ozone chemistry, aerosol
formation, and other chemical cycles that influence the fate of pollutants
and climate (McGivern et al., 2000; Saiz-Lopez and von Glasow, 2012; Simpson
et al., 2015). Recent studies have identified open-ocean upwelling areas in
the Atlantic as large source regions for a number of brominated and iodinated
oceanic trace gases (Quack et al., 2004, 2007; O'Brien et al., 2009; Raimund
et al., 2011; Hepach et al., 2015). Their sources are related to biological
and chemical processes in the productive waters of the upwelling. Although
oceanic upwelling and nearshore regions are small compared to the global
ocean area, they are known to significantly contribute to the oceanic
bromocarbon fluxes (Quack and Wallace, 2003; Butler et al., 2007; Ziska et
al., 2013). In the upwelling regions the compounds are emitted from the ocean
and are horizontally transported and vertically mixed in the marine
atmospheric boundary layer (MABL) (Carpenter et al., 2010). Meteorological
conditions strongly influenced the atmospheric mixing ratio of the marine
compounds bromoform (CHBr<inline-formula><mml:math display="inline"><mml:mrow><mml:msub><mml:mi/><mml:mn mathvariant="normal">3</mml:mn></mml:msub><mml:mo>)</mml:mo></mml:mrow></mml:math></inline-formula>, dibromomethane (CH<inline-formula><mml:math display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>Br<inline-formula><mml:math display="inline"><mml:mrow><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub><mml:mo>)</mml:mo></mml:mrow></mml:math></inline-formula> and also
methyl iodide (CH<inline-formula><mml:math display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:math></inline-formula>I) (e.g. Fuhlbrügge et al., 2013; Hepach et al.,
2014). The combination of a pronounced low MABL above cold upwelling waters
with high concentrations and emissions of the compounds causes elevated
atmospheric mixing ratios. In a negative feedback process, these high
atmospheric mixing ratios reduce the marine emissions through a decrease in
the sea–air concentration gradient (Fuhlbrügge et al., 2013). Similar
relationships would be expected for other oceanic upwelling areas, where not
only the oceanic emissions but also meteorological conditions in the
lowermost atmosphere, i.e. the height, type and structure of the boundary
layer and trade inversion, determine the very short lived substance (VSLS) abundance and atmospheric
distribution. The intense oceanic upwelling in the south-eastern Pacific off the
coast of Peru transports large amounts of subsurface water to the ocean
surface and creates one of the most productive oceanic regions worldwide
(Codispoti et al., 1982). We therefore expect elevated levels of short-lived
halocarbons in the Peruvian upwelling zone as a potential source for the
atmosphere. Indeed, Schönhardt et al. (2008) detected elevated IO columns
during September and November 2005 along the Peruvian coast with the
SCIAMACHY satellite instrument and inferred elevated iodine source gases from
the Peruvian upwelling.</p>
      <p>Although recent studies have investigated halocarbons in the eastern Pacific
(Yokouchi et al., 2008; Mahajan et al., 2012; Saiz-Lopez et al., 2012;
Gómez Martin et al., 2013; Liu et al., 2013), few have concentrated on
the Peruvian upwelling in the south-eastern Pacific. Only measurements of methyl
iodide exist in this region, revealing atmospheric abundances of 7 ppt
(Rasmussen et al., 1982). Observations of bromocarbons above the Peruvian
upwelling are currently lacking.</p>
      <p>In this study we present a novel dataset of meteorological parameters,
oceanic concentrations and atmospheric abundances of VSLSs and calculated
emissions along the Peruvian coast and in the upwelling. The goal of this
study is to assess the influence of oceanic upwelling and meteorological
conditions on the atmospheric VSLS abundances above the Peruvian upwelling,
and to determine the contribution of the local oceanic emissions to MABL and
free-tropospheric VSLS concentrations.</p>
</sec>
<sec id="Ch1.S2">
  <title>Data and methods</title>
      <p>The Cruise M91 on R/V <italic>METEOR</italic> from 1 to 26 December 2012 started and
ended in Lima, Peru (Fig. 1a). The ship reached the northernmost position
during the cruise on 3 December 2012 at 5<inline-formula><mml:math display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula> S. In the following 3
weeks the ship headed southward and reached its southernmost position at
16<inline-formula><mml:math display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula> S on 21 December 2012. During this time the track alternated
between open-ocean sections and sections close to the Peruvian coast (up to
10 km distance) in the cold upwelling waters. A focus on diurnal variations
was accomplished by 24 h sampling at six stations along the cruise track.</p>

      <?xmltex \floatpos{t}?><fig id="Ch1.F1" specific-use="star"><caption><p><bold>(a)</bold> 10 min mean of wind speed observed on R/V
<italic>METEOR</italic> displayed along the cruise track; monthly mean
(December 2012) of 10 m wind speed and direction from ERA-Interim displayed
as arrows. <bold>(b)</bold> Extract from 10-day FLEXPART back-trajectories
coloured according to the time until they reach the specific ship position on
the cruise track of R/V <italic>METEOR</italic> (black). <bold>(c)</bold> Extract from
10-day FLEXPART forward trajectories coloured according to the time since
they were released. <bold>(d)</bold> Same as <bold>(c)</bold> but coloured according to
the height (km) of the trajectories.</p></caption>
        <?xmltex \igopts{width=341.433071pt}?><graphic xlink:href="https://acp.copernicus.org/articles/16/12205/2016/acp-16-12205-2016-f01.png"/>

      </fig>

<?xmltex \hack{\newpage}?>
<sec id="Ch1.S2.SS1">
  <title>Meteorological observations</title>
      <p>Meteorological observations of surface air temperature (SAT), sea surface
temperature (SST), relative humidity, air pressure, wind speed and direction
were taken every second at about 25 m height above sea level on R/V
<italic>METEOR</italic> and averaged to 10 min intervals for our investigations.
Atmospheric profiles of temperature, wind, and humidity were obtained by 98
radiosonde launches (00:00, 06:00, 12:00, 18:00 UTC) and additionally at 3 h intervals during the diurnal stations along the cruise track,
using Vaisala RS92 radiosondes. Due to permission limitations, radiosondes
could not be launched within 12 nmi of the Peruvian coast. The
collected radiosonde data were integrated in near-real time into the Global
Telecommunication System (GTS) to improve operational weather forecast models
and meteorological reanalysis for this region, which were used as input
parameters for our trajectory calculations.</p>
</sec>
<sec id="Ch1.S2.SS2">
  <title>MABL</title>
      <p>The radiosonde data are used to identify the height of the MABL, which is the
atmospheric surface layer above the ocean in which trace gas emissions are
mixed on a short timescale of an hour or less by convection and turbulence
(Stull, 1988). Two different kinds of MABL can be distinguished that are
characterized by the gradient of the virtual potential temperature
<inline-formula><mml:math display="inline"><mml:mrow><mml:msub><mml:mi mathvariant="italic">θ</mml:mi><mml:mtext>v</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula>. A negative or neutral gradient reveals an
<italic>unstable</italic> <italic>convective layer</italic>, while a positive gradient
reveals a <italic>stable</italic> atmospheric layer. In the case of an increase in the
virtual potential temperature (positive gradient) near the surface, mixing in
the MABL is suppressed. The upper limit of the convective MABL is set by a
stable layer, e.g. a temperature inversion or a significant reduction in air
moisture, and is typically found above open-ocean regions between 100 m and
3 km height (Stull, 1988; Seibert et al., 2000). For determining the height
of this stable layer above the convective MABL, we use the practical approach
described in Seibert et al. (2000) and compute the virtual potential
temperature for which an increase with altitude indicates the base of a
stable layer. In this study, its base is increased by half of its thickness,
which is the definition for the MABL height. Over oceanic upwelling regions
the stable layer can even descend to the ocean surface (e.g. Höflich et
al., 1972; Fuhlbrügge et al., 2013).</p>
      <p>Estimates for atmospheric surface stability and MABL conditions can be also
obtained from variations in the surface humidity. While the absolute humidity
determines the amount of water in a specific volume of air, the relative
humidity is the ratio of the partial pressure of water vapour to the
equilibrium vapour pressure at the observed temperature. Variations in the
SAT directly influence the relative humidity at the surface (Sect. 3.1).
Elevated relative humidity in this oceanic region likely points to stable
layers with suppressed mixing of surface air and to a low and stable MABL
height. Relative humidity is also used to derive the MABL height above the
upwelling areas close to the coast, where radiosonde launches were not
permitted (Sect. 2.1). We applied a multiple linear regression (Eq. 1), using
meteorological parameters along the cruise track that had significant
correlations (see Sect. 3.5) with the observed MABL height (relative humidity
(<inline-formula><mml:math display="inline"><mml:mrow><mml:msub><mml:mi>x</mml:mi><mml:mn mathvariant="normal">1</mml:mn></mml:msub><mml:mo>)</mml:mo></mml:mrow></mml:math></inline-formula>, SAT (<inline-formula><mml:math display="inline"><mml:mrow><mml:msub><mml:mi>x</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msub><mml:mo>)</mml:mo></mml:mrow></mml:math></inline-formula>, SST (<inline-formula><mml:math display="inline"><mml:mrow><mml:msub><mml:mi>x</mml:mi><mml:mn mathvariant="normal">3</mml:mn></mml:msub><mml:mo>)</mml:mo></mml:mrow></mml:math></inline-formula> and wind speed (<inline-formula><mml:math display="inline"><mml:mrow><mml:msub><mml:mi>x</mml:mi><mml:mn mathvariant="normal">4</mml:mn></mml:msub><mml:mo>)</mml:mo><mml:mo>)</mml:mo></mml:mrow></mml:math></inline-formula>:

                <disp-formula id="Ch1.E1" content-type="numbered"><mml:math display="block"><mml:mrow><mml:mtext>MABL height</mml:mtext><mml:mo>=</mml:mo><mml:msub><mml:mi>b</mml:mi><mml:mn mathvariant="normal">1</mml:mn></mml:msub><mml:msub><mml:mi>x</mml:mi><mml:mn mathvariant="normal">1</mml:mn></mml:msub><mml:mo>+</mml:mo><mml:msub><mml:mi>b</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msub><mml:msub><mml:mi>x</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msub><mml:mo>+</mml:mo><mml:msub><mml:mi>b</mml:mi><mml:mn mathvariant="normal">3</mml:mn></mml:msub><mml:msub><mml:mi>x</mml:mi><mml:mn mathvariant="normal">3</mml:mn></mml:msub><mml:mo>+</mml:mo><mml:msub><mml:mi>b</mml:mi><mml:mn mathvariant="normal">4</mml:mn></mml:msub><mml:msub><mml:mi>x</mml:mi><mml:mn mathvariant="normal">4</mml:mn></mml:msub><mml:mo>,</mml:mo></mml:mrow></mml:math></disp-formula>

          with <inline-formula><mml:math display="inline"><mml:mrow><mml:msub><mml:mi>b</mml:mi><mml:mn mathvariant="normal">1</mml:mn></mml:msub><mml:mo>=</mml:mo><mml:mo>-</mml:mo><mml:mn>0.0117</mml:mn></mml:mrow></mml:math></inline-formula>, <inline-formula><mml:math display="inline"><mml:mrow><mml:msub><mml:mi>b</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msub><mml:mo>=</mml:mo><mml:mn>0.0202</mml:mn></mml:mrow></mml:math></inline-formula>, <inline-formula><mml:math display="inline"><mml:mrow><mml:msub><mml:mi>b</mml:mi><mml:mn mathvariant="normal">3</mml:mn></mml:msub><mml:mo>=</mml:mo><mml:mn>0.0467</mml:mn></mml:mrow></mml:math></inline-formula>, and <inline-formula><mml:math display="inline"><mml:mrow><mml:msub><mml:mi>b</mml:mi><mml:mn mathvariant="normal">4</mml:mn></mml:msub><mml:mo>=</mml:mo><mml:mn>0.0089</mml:mn></mml:mrow></mml:math></inline-formula>.</p>
      <p>Missing MABL data close to the coast were then completed with the regressed
MABL height (Eq. 1) at the VSLS sampling location.</p><?xmltex \hack{\newpage}?>
</sec>
<sec id="Ch1.S2.SS3">
  <title>Atmospheric and oceanic VSLS measurements and sea–air fluxes</title>
      <p>A total of 198 air samples was collected at 3-hourly intervals during the
cruise at about 20 m height above sea level on the fifth superstructure deck
of R/V <italic>METEOR</italic> using a portside jib of 5–6 m. The air samples were
pressurized to 2 atm in pre-cleaned stainless steel canisters with a metal
bellows pump and were analysed at the Rosenstiel School for Marine and
Atmospheric Sciences (RSMAS, Miami, Florida) within 6 months after the
cruise. Details about the analysis, the instrumental precision and the
preparation of the samples are described in Schauffler et al. (1999) and
Fuhlbrügge et al. (2013). The VSLS atmospheric mixing ratios were
calculated with a NOAA standard (SX3573) from GEOMAR.</p>
      <p>Starting from 9 December 2012, 102 water samples were taken at 3 h
intervals at a depth of 6.8 m from a continuously working water pump in the
hydrographic shaft, an opening in the base of the hull of R/V
<italic>METEOR</italic>. The samples were then analysed for bromoform, dibromomethane, methyl iodide and other halogenated trace gases by a purge and trap
system attached to a gas chromatograph combined with an ECD (electron capture
detector). The analysis has a precision of 10 % (1<inline-formula><mml:math display="inline"><mml:mi mathvariant="italic">σ</mml:mi></mml:math></inline-formula>) determined
from duplicate samples. The approach is described in detail by Hepach et
al. (2014).</p>
      <p>The sea–air flux (<inline-formula><mml:math display="inline"><mml:mrow><mml:mi>F</mml:mi><mml:mo>)</mml:mo></mml:mrow></mml:math></inline-formula> of bromoform, dibromomethane and methyl iodide is
calculated with <inline-formula><mml:math display="inline"><mml:mrow><mml:msub><mml:mi>k</mml:mi><mml:mi>w</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> as a transfer coefficient and <inline-formula><mml:math display="inline"><mml:mrow><mml:mi mathvariant="normal">Δ</mml:mi><mml:mi>c</mml:mi></mml:mrow></mml:math></inline-formula> as a
concentration gradient between the water and equilibrium water concentration
determined from the atmospheric concentrations (Eq. 2). The transfer
coefficient was determined by the air–sea gas exchange parameterization of
Nightingale et al. (2000) after a Schmidt number (<italic>Sc</italic>) correction for
the three gases (Eq. 3).

                <disp-formula specific-use="align" content-type="numbered"><mml:math display="block"><mml:mtable displaystyle="true"><mml:mlabeledtr id="Ch1.E2"><mml:mtd/><mml:mtd/><mml:mtd><mml:mrow><mml:mi>F</mml:mi><mml:mo>=</mml:mo><mml:msub><mml:mi>k</mml:mi><mml:mi>w</mml:mi></mml:msub><mml:mo>⋅</mml:mo><mml:mi mathvariant="normal">Δ</mml:mi><mml:mi>c</mml:mi></mml:mrow></mml:mtd></mml:mlabeledtr><mml:mlabeledtr id="Ch1.E3"><mml:mtd/><mml:mtd/><mml:mtd><mml:mrow><mml:msub><mml:mi>k</mml:mi><mml:mi>w</mml:mi></mml:msub><mml:mo>=</mml:mo><mml:msub><mml:mi>k</mml:mi><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">CO</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:mrow></mml:msub><mml:mo>⋅</mml:mo><mml:mstyle displaystyle="true"><mml:mfrac style="display"><mml:mrow><mml:msup><mml:mtext mathvariant="italic">Sc</mml:mtext><mml:mrow><mml:mo>-</mml:mo><mml:mfrac><mml:mn mathvariant="normal">1</mml:mn><mml:mn mathvariant="normal">2</mml:mn></mml:mfrac></mml:mrow></mml:msup></mml:mrow><mml:mn>600</mml:mn></mml:mfrac></mml:mstyle></mml:mrow></mml:mtd></mml:mlabeledtr></mml:mtable></mml:math></disp-formula>

            Details on deriving the air–sea concentration gradient and emissions are
further described in Hepach et al. (2014) and references therein.</p>
</sec>
<sec id="Ch1.S2.SS4">
  <title>Trajectory calculations</title>
      <p>The Lagrangian particle dispersion model FLEXPART of the Norwegian Institute
for Air Research in the Department of Atmospheric and Climate Research (Stohl
et al., 2005) was used for trajectory calculations to analyse the air mass
origins and the transport of surface air masses along the cruise track to the
free troposphere (Stohl et al., 1998; Stohl and Trickl, 1999). The model
includes moist convection and turbulence parameterizations in the atmospheric
boundary layer and free troposphere (Stohl and Thomson, 1999; Forster et al.,
2007). We use the ECMWF (European Centre for Medium-Range Weather Forecasts)
reanalysis product ERA-Interim (Dee et al., 2011) with a horizontal resolution of
1<inline-formula><mml:math display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula> <inline-formula><mml:math display="inline"><mml:mo>×</mml:mo></mml:math></inline-formula> 1<inline-formula><mml:math display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula> and 60 vertical model levels as
meteorological input fields, providing air temperature, horizontal and
vertical winds, boundary layer height, specific humidity, and
convective and large-scale precipitation with a 6-hourly temporal
resolution. Trajectories were released every 3 to 6 h coincident
with VSLS measurements along the cruise track on R/V <italic>METEOR</italic>. At each
of these release points 10 000 forward- and 50 back-trajectories with a
total runtime of <inline-formula><mml:math display="inline"><mml:mo>∼</mml:mo></mml:math></inline-formula> 30 days were initiated from the ocean surface within
<inline-formula><mml:math display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula>30 min and <inline-formula><mml:math display="inline"><mml:mo>∼</mml:mo></mml:math></inline-formula> 20 m distance of the measurements. In total 98
release points for the forward- and back-trajectory calculations were
analysed, determined by the spatial resolution of ERA-Interim data along the
Peruvian coast, defining the land–sea mask of our trajectory calculations.</p><?xmltex \hack{\newpage}?>
</sec>
<sec id="Ch1.S2.SS5">
  <title>Oceanic contribution to MABL VSLS abundances</title>
      <p>To estimate the contribution of local oceanic sources to the atmospheric
mixing ratios in the lowermost atmosphere above the Peruvian upwelling, we
apply a mass balance concept to the oceanic emissions, the timescales of air
mass transport and the chemical loss (Fuhlbrügge et al., 2016). First we
define a box above each release event with a size of <inline-formula><mml:math display="inline"><mml:mo>∼</mml:mo></mml:math></inline-formula> 400 m<inline-formula><mml:math display="inline"><mml:msup><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msup></mml:math></inline-formula>
around the measurement location and the height of the MABL and assume
steady state in the box (Fig. 2). During each trajectory release event we
assume the specific sea–air flux to be constant and the emissions to be
homogeneously mixed within the box. Then the contribution of the sea–air flux
is computed as the ratio of the VSLS flux from the ocean into the MABL (in
moles per day) and the total amount of VSLSs in the box (in moles). This ratio is
defined as the oceanic delivery (OD) and is given in percentage per day. In
addition to the delivery of oceanic VSLSs to the box, the loss of VSLSs out of
the box and into the free troposphere is defined as the convective loss (COL) and
this quantity is derived from the mean residence time of the FLEXPART
trajectories in the box during each release event. Note that the COL
indicates the loss of surface air due to all kinds of vertical movement out
of the box. Since this is a loss process, COL is given as a negative quantity
expressed as percentage per day. The chemical degradation of VSLSs by OH and
photolysis in the MABL is calculated from the chemical lifetime of each
compound in the MABL. We use lifetimes of 15 days for bromoform, 94 days for
dibromomethane and 4 days for methyl iodide (Carpenter et al., 2014),
representative of the tropical boundary layer. The chemical loss (CL) is
given as a negative quantity in percentage per day. OD, COL and CL must be
balanced by an advective transport of air masses in and out of the box. The
change of the VSLSs through advective transport is defined as advective
delivery (AD) and is also given in percentage per day.</p>

      <?xmltex \floatpos{t}?><fig id="Ch1.F2"><caption><p>Schematic summary of the components of the applied mass-balance
concept from Fuhlbrügge et al. (2016): oceanic delivery (OD), the
convective loss (COL), the chemical loss (CL), the advective delivery (AD),
the oceanic delivery ratio (ODR), the chemical loss ratio (CLR) and the
advective delivery ratio (ADR). The shaded area reflects an area of
400 m<inline-formula><mml:math display="inline"><mml:msup><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msup></mml:math></inline-formula>.</p></caption>
          <?xmltex \igopts{width=236.157874pt}?><graphic xlink:href="https://acp.copernicus.org/articles/16/12205/2016/acp-16-12205-2016-f02.png"/>

        </fig>

      <p>To estimate the relative importance of ocean emissions (OD) to the halocarbon
loss through vertical mixing (COL) we define an oceanic delivery ratio (ODR)
(Eq. 4) as the ratio between OD and COL:</p>
      <p><disp-formula specific-use="align" content-type="numbered"><mml:math display="block"><mml:mtable displaystyle="true"><mml:mtr><mml:mtd><mml:mrow><mml:mtext>ODR</mml:mtext></mml:mrow></mml:mtd><mml:mtd><mml:mrow><mml:mo>=</mml:mo><mml:mstyle displaystyle="true"><mml:mfrac style="display"><mml:mrow><mml:mtext>OD</mml:mtext><mml:mo>[</mml:mo><mml:mi mathvariant="italic">%</mml:mi><mml:mspace width="0.125em" linebreak="nobreak"/><mml:msup><mml:mtext>d</mml:mtext><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup><mml:mo>]</mml:mo></mml:mrow><mml:mrow><mml:mtext>COL</mml:mtext><mml:mo>[</mml:mo><mml:mi mathvariant="italic">%</mml:mi><mml:mspace width="0.125em" linebreak="nobreak"/><mml:msup><mml:mtext>d</mml:mtext><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup><mml:mo>]</mml:mo></mml:mrow></mml:mfrac></mml:mstyle></mml:mrow></mml:mtd></mml:mtr><mml:mlabeledtr id="Ch1.E4"><mml:mtd/><mml:mtd/><mml:mtd><mml:mrow><mml:mo>=</mml:mo><mml:mstyle displaystyle="true"><mml:mfrac style="display"><mml:mrow><mml:mtext>sea–air flux contribution</mml:mtext><mml:mo>[</mml:mo><mml:mi mathvariant="italic">%</mml:mi><mml:mspace width="0.125em" linebreak="nobreak"/><mml:msup><mml:mtext>d</mml:mtext><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup><mml:mo>]</mml:mo></mml:mrow><mml:mrow><mml:mtext>loss of box air to the FT</mml:mtext><mml:mo>[</mml:mo><mml:mi mathvariant="italic">%</mml:mi><mml:mspace linebreak="nobreak" width="0.125em"/><mml:msup><mml:mtext>d</mml:mtext><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup><mml:mo>]</mml:mo></mml:mrow></mml:mfrac></mml:mstyle><mml:mo>.</mml:mo></mml:mrow></mml:mtd></mml:mlabeledtr></mml:mtable></mml:math></disp-formula></p>
      <p>Similarly, the chemical loss in the box (CL) and the change in VSLSs due to
advection (AD) are related to COL to get the chemical loss ratio (CLR) and
the advective delivery ratio (ADR). From mass balance considerations, ODR –
CLR <inline-formula><mml:math display="inline"><mml:mo>+</mml:mo></mml:math></inline-formula> ADR <inline-formula><mml:math display="inline"><mml:mo>=</mml:mo></mml:math></inline-formula> 1. Since CL, OD and AD are divided by COL, ratios for
source processes are positive and negative for loss processes (Fuhlbrügge
et al., 2016).</p><?xmltex \hack{\newpage}?>
</sec>
</sec>
<sec id="Ch1.S3">
  <?xmltex \opttitle{Observations on R/V \textit{METEOR}}?><title>Observations on R/V <italic>METEOR</italic></title>
<sec id="Ch1.S3.SS1">
  <title>Meteorology</title>
      <p>The Peruvian coast is dominated by the Southern Hemisphere trade wind regime
with predominantly south-easterly winds (Fig. 1). The Andes, which are known
to act as a barrier to zonal wind in this region, affect the horizontal air
mass transport along the coast (Fig. 1b–d). The steeply sloping mountains at
the coast form strong winds parallel to the South American coastline
(Garreaud and Munoz, 2005). The 10-day back-trajectories reveal a mix of
open-ocean and coastal air masses (Fig. 1). The average wind direction observed on
R/V <italic>METEOR</italic> during the cruise is 160<inline-formula><mml:math display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula> <inline-formula><mml:math display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 34<inline-formula><mml:math display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>
(mean <inline-formula><mml:math display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> <inline-formula><mml:math display="inline"><mml:mrow><mml:mi mathvariant="italic">σ</mml:mi><mml:mo>)</mml:mo></mml:mrow></mml:math></inline-formula> with a moderate average wind speed of
6.2 <inline-formula><mml:math display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 2.2 m s<inline-formula><mml:math display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula> (Fig. 3b). ERA-Interim reveals similar winds
along the cruise track with a mean wind speed of 5.6 <inline-formula><mml:math display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 1.8 m s<inline-formula><mml:math display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula>
and a mean wind direction of 168<inline-formula><mml:math display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula> <inline-formula><mml:math display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 21<inline-formula><mml:math display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula> (not shown
here). The divergence of the wind-driven Ekman transport along the Peruvian
coast leads to the observed oceanic upwelling of cold waters. The most
intense upwelling was observed several times near the coast, where both SST
and SAT rapidly drop from 19–22 <inline-formula><mml:math display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>C to less than 18 <inline-formula><mml:math display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>C
(Fig. 3a). The impact of the cold upwelling water on the air masses is also
visible in the observed humidity fields (Fig. 3c). Here, the decreasing SAT
reduces the amount of water vapour that the surface air is able to contain,
leading to an increase in the relative humidity and indicating a stable
atmospheric surface layer with suppressed vertical mixing. The absolute
humidity stays constant or even decreases above the oceanic upwelling due to
condensation of water vapour when surface air cools and becomes saturated,
coinciding with fog observations on the ship. A decrease in the absolute
humidity outside the upwelling points to a change in advected air masses
(e.g. 9, 11, 19 December 2012; Fig. 3c).</p>

      <?xmltex \floatpos{t}?><fig id="Ch1.F3"><caption><p>Observations during 1–25 December 2012 on R/V <italic>METEOR</italic>.
Diurnal stations are indicated by grey background shading.
<bold>(a)</bold> 10 min mean of the SAT (orange) and the SST (blue) in
<inline-formula><mml:math display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>C. According to SST decrease, upwelling regions are marked with
light-blue background shading in <bold>(b–e)</bold>. <bold>(b)</bold> 10 min mean of
wind direction in cardinal directions (ochre) and wind speed in m s<inline-formula><mml:math display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula>
(blue). <bold>(c)</bold> 10 min mean of relative humidity in % (dark blue)
and absolute humidity in gm<inline-formula><mml:math display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">3</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula> (green). <bold>(d)</bold> Oceanic surface
concentrations of bromoform (CHBr<inline-formula><mml:math display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:math></inline-formula>, blue), dibromomethane
(CH<inline-formula><mml:math display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>Br<inline-formula><mml:math display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>, dark grey) and methyl iodide (CH<inline-formula><mml:math display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:math></inline-formula>I, red) in pmol L<inline-formula><mml:math display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula>. <bold>(e)</bold> Atmospheric mixing ratios of bromoform, dibromomethane
and methyl iodide in ppt. <bold>(f)</bold> Concentration ratio of atmospheric dibromomethane
and bromoform. <bold>(g)</bold> Sea–air flux for bromoform, dibromomethane and
methyl iodide in nmol m<inline-formula><mml:math display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">2</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula> h<inline-formula><mml:math display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula>.</p></caption>
          <?xmltex \igopts{width=236.157874pt}?><graphic xlink:href="https://acp.copernicus.org/articles/16/12205/2016/acp-16-12205-2016-f03.pdf"/>

        </fig>

<?xmltex \floatpos{t}?><table-wrap id="Ch1.T1" specific-use="star"><caption><p>Oceanic concentrations, atmospheric mixing ratios and sea–air fluxes
of bromoform (CHBr<inline-formula><mml:math display="inline"><mml:mrow><mml:msub><mml:mi/><mml:mn mathvariant="normal">3</mml:mn></mml:msub><mml:mo>)</mml:mo></mml:mrow></mml:math></inline-formula>, dibromomethane (CH<inline-formula><mml:math display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>Br<inline-formula><mml:math display="inline"><mml:mrow><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub><mml:mo>)</mml:mo></mml:mrow></mml:math></inline-formula>, the
concentration ratio of bromoform and dibromomethane and methyl iodide
(CH<inline-formula><mml:math display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:math></inline-formula>I) observed during the cruise. Values are given in mean
<inline-formula><mml:math display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula>1<inline-formula><mml:math display="inline"><mml:mi mathvariant="italic">σ</mml:mi></mml:math></inline-formula>. The range is given in square brackets.</p></caption><oasis:table frame="topbot"><oasis:tgroup cols="5">
     <oasis:colspec colnum="1" colname="col1" align="left"/>
     <oasis:colspec colnum="2" colname="col2" align="right"/>
     <oasis:colspec colnum="3" colname="col3" align="right"/>
     <oasis:colspec colnum="4" colname="col4" align="right"/>
     <oasis:colspec colnum="5" colname="col5" align="right"/>
     <oasis:thead>
       <oasis:row rowsep="1">  
         <oasis:entry colname="col1"/>  
         <oasis:entry colname="col2">CHBr<inline-formula><mml:math display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:math></inline-formula></oasis:entry>  
         <oasis:entry colname="col3">CH<inline-formula><mml:math display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>Br<inline-formula><mml:math display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula></oasis:entry>  
         <oasis:entry colname="col4">CH<inline-formula><mml:math display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>Br<inline-formula><mml:math display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula> <inline-formula><mml:math display="inline"><mml:mo>/</mml:mo></mml:math></inline-formula> CHBr<inline-formula><mml:math display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:math></inline-formula></oasis:entry>  
         <oasis:entry colname="col5">CH<inline-formula><mml:math display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:math></inline-formula>I</oasis:entry>
       </oasis:row>
     </oasis:thead>
     <oasis:tbody>
       <oasis:row>  
         <oasis:entry colname="col1">Oceanic concentration</oasis:entry>  
         <oasis:entry colname="col2">6.6 <inline-formula><mml:math display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 5.5</oasis:entry>  
         <oasis:entry colname="col3">4.3 <inline-formula><mml:math display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 3.4</oasis:entry>  
         <oasis:entry colname="col4">0.9 <inline-formula><mml:math display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.8</oasis:entry>  
         <oasis:entry colname="col5">9.8 <inline-formula><mml:math display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 6.3</oasis:entry>
       </oasis:row>
       <oasis:row rowsep="1">  
         <oasis:entry colname="col1">(pmol L<inline-formula><mml:math display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula>)</oasis:entry>  
         <oasis:entry colname="col2">[0.2–21.5]</oasis:entry>  
         <oasis:entry colname="col3">[0.2–12.7]</oasis:entry>  
         <oasis:entry colname="col4">[0.1–4.2]</oasis:entry>  
         <oasis:entry colname="col5">[1.1–35.4]</oasis:entry>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1">Atmospheric mixing ratio</oasis:entry>  
         <oasis:entry colname="col2">2.9 <inline-formula><mml:math display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.7</oasis:entry>  
         <oasis:entry colname="col3">1.3 <inline-formula><mml:math display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.3</oasis:entry>  
         <oasis:entry colname="col4">0.4 <inline-formula><mml:math display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.1</oasis:entry>  
         <oasis:entry colname="col5">1.5 <inline-formula><mml:math display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.5</oasis:entry>
       </oasis:row>
       <oasis:row rowsep="1">  
         <oasis:entry colname="col1">(ppt)</oasis:entry>  
         <oasis:entry colname="col2">[1.5–5.9]</oasis:entry>  
         <oasis:entry colname="col3">[0.8–2.0]</oasis:entry>  
         <oasis:entry colname="col4">[0.3–0.7]</oasis:entry>  
         <oasis:entry colname="col5">[0.6–3.2]</oasis:entry>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1">Sea–air flux</oasis:entry>  
         <oasis:entry colname="col2">117 <inline-formula><mml:math display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 492</oasis:entry>  
         <oasis:entry colname="col3">245 <inline-formula><mml:math display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 299</oasis:entry>  
         <oasis:entry colname="col4">0.4 <inline-formula><mml:math display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 8.6</oasis:entry>  
         <oasis:entry colname="col5">856 <inline-formula><mml:math display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 623</oasis:entry>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1">(pmol m<inline-formula><mml:math display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">2</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula> h<inline-formula><mml:math display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula>)</oasis:entry>  
         <oasis:entry colname="col2">[<inline-formula><mml:math display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>477–1916]</oasis:entry>  
         <oasis:entry colname="col3">[<inline-formula><mml:math display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>112–1169]</oasis:entry>  
         <oasis:entry colname="col4">[<inline-formula><mml:math display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>24.5–48.9]</oasis:entry>  
         <oasis:entry colname="col5">[18–4179]</oasis:entry>
       </oasis:row>
     </oasis:tbody>
   </oasis:tgroup></oasis:table></table-wrap>

<?xmltex \floatpos{t}?><table-wrap id="Ch1.T2" specific-use="star"><caption><p>Spearman correlation coefficients (<inline-formula><mml:math display="inline"><mml:mi>R</mml:mi></mml:math></inline-formula>) of meteorological
parameters, MABL height and trade inversion height correlated with
atmospheric bromoform (CHBr<inline-formula><mml:math display="inline"><mml:mrow><mml:msub><mml:mi/><mml:mn mathvariant="normal">3</mml:mn></mml:msub><mml:mo>)</mml:mo></mml:mrow></mml:math></inline-formula>, dibromomethane (CH<inline-formula><mml:math display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>Br<inline-formula><mml:math display="inline"><mml:mrow><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub><mml:mo>)</mml:mo></mml:mrow></mml:math></inline-formula> and
methyl iodide (CH<inline-formula><mml:math display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:math></inline-formula>I). MABL height<inline-formula><mml:math display="inline"><mml:msup><mml:mi/><mml:mo>*</mml:mo></mml:msup></mml:math></inline-formula> is the determined MABL height from
the radiosonde launches, complemented by the regressed MABL height
(Sect. 3.3). Bold coefficients are significant with a <inline-formula><mml:math display="inline"><mml:mi>p</mml:mi></mml:math></inline-formula> value of
<inline-formula><mml:math display="inline"><mml:mo>&lt;</mml:mo></mml:math></inline-formula> 0.05.</p></caption><oasis:table frame="topbot"><oasis:tgroup cols="7">
     <oasis:colspec colnum="1" colname="col1" align="left"/>
     <oasis:colspec colnum="2" colname="col2" align="right"/>
     <oasis:colspec colnum="3" colname="col3" align="right"/>
     <oasis:colspec colnum="4" colname="col4" align="right"/>
     <oasis:colspec colnum="5" colname="col5" align="right"/>
     <oasis:colspec colnum="6" colname="col6" align="right"/>
     <oasis:colspec colnum="7" colname="col7" align="right"/>
     <oasis:thead>
       <oasis:row rowsep="1">  
         <oasis:entry colname="col1"/>  
         <oasis:entry colname="col2">MABL height</oasis:entry>  
         <oasis:entry colname="col3">MABL height<inline-formula><mml:math display="inline"><mml:msup><mml:mi/><mml:mo>*</mml:mo></mml:msup></mml:math></inline-formula></oasis:entry>  
         <oasis:entry colname="col4">Trade inversion</oasis:entry>  
         <oasis:entry colname="col5">CHBr<inline-formula><mml:math display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:math></inline-formula></oasis:entry>  
         <oasis:entry colname="col6">CH<inline-formula><mml:math display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>Br<inline-formula><mml:math display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula></oasis:entry>  
         <oasis:entry colname="col7">CH<inline-formula><mml:math display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:math></inline-formula>I</oasis:entry>
       </oasis:row>
     </oasis:thead>
     <oasis:tbody>
       <oasis:row>  
         <oasis:entry colname="col1">Wind speed</oasis:entry>  
         <oasis:entry colname="col2"><bold>0.35</bold></oasis:entry>  
         <oasis:entry colname="col3"><bold>0.44</bold></oasis:entry>  
         <oasis:entry colname="col4"><inline-formula><mml:math display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>0.06</oasis:entry>  
         <oasis:entry colname="col5"><inline-formula><mml:math display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula><bold>0.38</bold></oasis:entry>  
         <oasis:entry colname="col6"><inline-formula><mml:math display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula><bold>0.53</bold></oasis:entry>  
         <oasis:entry colname="col7"><inline-formula><mml:math display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula><bold>0.33</bold></oasis:entry>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1">SAT</oasis:entry>  
         <oasis:entry colname="col2"><bold>0.65</bold></oasis:entry>  
         <oasis:entry colname="col3"><bold>0.79</bold></oasis:entry>  
         <oasis:entry colname="col4"><bold>0.24</bold></oasis:entry>  
         <oasis:entry colname="col5"><inline-formula><mml:math display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula><bold>0.50</bold></oasis:entry>  
         <oasis:entry colname="col6"><inline-formula><mml:math display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula><bold>0.78</bold></oasis:entry>  
         <oasis:entry colname="col7"><inline-formula><mml:math display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula><bold>0.37</bold></oasis:entry>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1">SST</oasis:entry>  
         <oasis:entry colname="col2"><bold>0.66</bold></oasis:entry>  
         <oasis:entry colname="col3"><bold>0.80</bold></oasis:entry>  
         <oasis:entry colname="col4"><bold>0.23</bold></oasis:entry>  
         <oasis:entry colname="col5"><inline-formula><mml:math display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula><bold>0.57</bold></oasis:entry>  
         <oasis:entry colname="col6"><inline-formula><mml:math display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula><bold>0.81</bold></oasis:entry>  
         <oasis:entry colname="col7"><inline-formula><mml:math display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula><bold>0.42</bold></oasis:entry>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1">SAT–SST</oasis:entry>  
         <oasis:entry colname="col2"><inline-formula><mml:math display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula><bold>0.39</bold></oasis:entry>  
         <oasis:entry colname="col3"><inline-formula><mml:math display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula><bold>0.47</bold></oasis:entry>  
         <oasis:entry colname="col4"><inline-formula><mml:math display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>0.11</oasis:entry>  
         <oasis:entry colname="col5"><bold>0.38</bold></oasis:entry>  
         <oasis:entry colname="col6"><bold>0.48</bold></oasis:entry>  
         <oasis:entry colname="col7"><bold>0.30</bold></oasis:entry>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1">Rel. humidity</oasis:entry>  
         <oasis:entry colname="col2"><inline-formula><mml:math display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula><bold>0.77</bold></oasis:entry>  
         <oasis:entry colname="col3"><inline-formula><mml:math display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula><bold>0.81</bold></oasis:entry>  
         <oasis:entry colname="col4"><inline-formula><mml:math display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>0.06</oasis:entry>  
         <oasis:entry colname="col5"><bold>0.74</bold></oasis:entry>  
         <oasis:entry colname="col6"><bold>0.77</bold></oasis:entry>  
         <oasis:entry colname="col7"><bold>0.67</bold></oasis:entry>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1">MABL height<inline-formula><mml:math display="inline"><mml:msup><mml:mi/><mml:mo>*</mml:mo></mml:msup></mml:math></inline-formula></oasis:entry>  
         <oasis:entry colname="col2">–</oasis:entry>  
         <oasis:entry colname="col3">–</oasis:entry>  
         <oasis:entry colname="col4">0.08</oasis:entry>  
         <oasis:entry colname="col5"><inline-formula><mml:math display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula><bold>0.55</bold></oasis:entry>  
         <oasis:entry colname="col6"><inline-formula><mml:math display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula><bold>0.61</bold></oasis:entry>  
         <oasis:entry colname="col7"><inline-formula><mml:math display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula><bold>0.45</bold></oasis:entry>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1">CHBr<inline-formula><mml:math display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:math></inline-formula></oasis:entry>  
         <oasis:entry colname="col2"><inline-formula><mml:math display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula><bold>0.55</bold></oasis:entry>  
         <oasis:entry colname="col3"><inline-formula><mml:math display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula><bold>0.60</bold></oasis:entry>  
         <oasis:entry colname="col4"><inline-formula><mml:math display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>0.03</oasis:entry>  
         <oasis:entry colname="col5">–</oasis:entry>  
         <oasis:entry colname="col6"><bold>0.79</bold></oasis:entry>  
         <oasis:entry colname="col7"><bold>0.79</bold></oasis:entry>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1">CH<inline-formula><mml:math display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>Br<inline-formula><mml:math display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula></oasis:entry>  
         <oasis:entry colname="col2"><inline-formula><mml:math display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula><bold>0.61</bold></oasis:entry>  
         <oasis:entry colname="col3"><inline-formula><mml:math display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula><bold>0.72</bold></oasis:entry>  
         <oasis:entry colname="col4"><inline-formula><mml:math display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>0.02</oasis:entry>  
         <oasis:entry colname="col5"><bold>0.79</bold></oasis:entry>  
         <oasis:entry colname="col6">–</oasis:entry>  
         <oasis:entry colname="col7"><bold>0.66</bold></oasis:entry>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1">CH<inline-formula><mml:math display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:math></inline-formula>I</oasis:entry>  
         <oasis:entry colname="col2"><inline-formula><mml:math display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula><bold>0.45</bold></oasis:entry>  
         <oasis:entry colname="col3"><inline-formula><mml:math display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula><bold>0.50</bold></oasis:entry>  
         <oasis:entry colname="col4"><bold>0.30</bold></oasis:entry>  
         <oasis:entry colname="col5"><bold>0.79</bold></oasis:entry>  
         <oasis:entry colname="col6"><bold>0.66</bold></oasis:entry>  
         <oasis:entry colname="col7">–</oasis:entry>
       </oasis:row>
     </oasis:tbody>
   </oasis:tgroup></oasis:table></table-wrap>

      <?xmltex \floatpos{t}?><fig id="Ch1.F4"><caption><p><bold>(a–c)</bold> Radiosonde observations of the lower 6 km of the
atmosphere between 2 and 24 December 2012 on R/V <italic>METEOR</italic>. Shown are
<bold>(a)</bold> the relative humidity in %, <bold>(b)</bold> the meridional wind
in m s<inline-formula><mml:math display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula> and <bold>(c)</bold> the gradient of the virtual potential
temperature in 10<inline-formula><mml:math display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">2</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula> K m<inline-formula><mml:math display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula> in combination with the determined MABL
height (black) and the associated MABL height above the oceanic upwelling
from the multiple linear regressions (blue). <bold>(d)</bold> Distribution of
10-day FLEXPART forward trajectories. The black contour lines give the amount
of trajectories in percentage reaching an altitude of 0–6 km height within
the 10 days. The elapsed time in days until these trajectories reach this
height is reflected by the colour shading. The white line shows the
ERA-Interim MABL height at the ship's position. Trajectory analyses gaps close
to the coast are whitened (Sect. 2.4). The <inline-formula><mml:math display="inline"><mml:mi>y</mml:mi></mml:math></inline-formula> axes are non-linear.</p></caption>
          <?xmltex \igopts{width=236.157874pt}?><graphic xlink:href="https://acp.copernicus.org/articles/16/12205/2016/acp-16-12205-2016-f04.jpg"/>

        </fig>

</sec>
<sec id="Ch1.S3.SS2">
  <title>VSLS abundances and oceanic emissions</title>
      <p>Surface water samples of the coastal upwelling areas show elevated VSLS
concentrations compared to the open ocean for all compounds, especially for
methyl iodide (Hepach et al., 2016). Atmospheric mixing ratios of bromoform
were on average 2.91 <inline-formula><mml:math display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.68 ppt (Table 1). Dibromomethane mixing
ratios (average 1.25 <inline-formula><mml:math display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.26 ppt) show a similar pattern and good
correlation with bromoform (Table 2). Elevated mixing ratios for all three
compounds are generally found above the intense cold oceanic upwelling
regions close to the Peruvian coast (Fig. 3e). While the bromocarbons double
above the upwelling, methyl iodide mixing ratios increase up to 5-fold,
demonstrating its stronger accumulation in the low and stable boundary layer.</p>
      <p>The concentration ratio of atmospheric dibromomethane to bromoform can be
used as an indicator of bromocarbon sources along coastal areas. Low ratios
of about 0.1 have been observed in coastal source regions and have been
interpreted as the emission ratios of macro algae (Yokouchi et al., 2005;
Carpenter et al., 2003). The shorter chemical lifetime of bromoform (15 days)
in contrast to dibromomethane (94 days) in the boundary layer leads to an
increase in the ratio during transport as long as the air mass is not newly
enriched with bromoform (Carpenter et al., 2014). This concentration ratio
generally decreased from the north to the south (Fig. 3f), implying an
intensification of fresh bromoform sources towards the southern part of the
cruise track, which is also reflected by increasing water concentrations.
Atmospheric methyl iodide measurements along the cruise track reveal a mean
mixing ratio of 1.54 <inline-formula><mml:math display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.49 ppt, which, similar to the two
bromocarbons, maximizes over the coastal upwelling regions (Fig. 3e).</p>
      <p>Oceanic emissions during the cruise were calculated from the approximately
synchronous measurements of sea water concentrations and atmospheric mixing
ratios, sea surface temperatures and wind speeds, measured on R/V
<italic>METEOR</italic>. Oceanic concentrations and atmospheric mixing ratios of each
compound were weakly or not at all correlated (<inline-formula><mml:math display="inline"><mml:mrow><mml:msub><mml:mi>R</mml:mi><mml:mtext>bromoform</mml:mtext></mml:msub><mml:mo>=</mml:mo><mml:mn>0.00</mml:mn></mml:mrow></mml:math></inline-formula>,
<inline-formula><mml:math display="inline"><mml:mrow><mml:msub><mml:mi>R</mml:mi><mml:mtext>dibromomethane</mml:mtext></mml:msub><mml:mo>=</mml:mo><mml:mn>0.29</mml:mn></mml:mrow></mml:math></inline-formula> and <inline-formula><mml:math display="inline"><mml:mrow><mml:msub><mml:mi>R</mml:mi><mml:mtext>methyl iodide</mml:mtext></mml:msub><mml:mo>=</mml:mo><mml:mn>0.34</mml:mn></mml:mrow></mml:math></inline-formula>). Mean
sea–air fluxes of the bromocarbons during the cruise are low, at <inline-formula><mml:math display="inline"><mml:mrow><mml:mn>117</mml:mn><mml:mo>±</mml:mo><mml:mn>492</mml:mn></mml:mrow></mml:math></inline-formula> pmol m<inline-formula><mml:math display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">2</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula> h<inline-formula><mml:math display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula> for bromoform and <inline-formula><mml:math display="inline"><mml:mrow><mml:mn>245</mml:mn><mml:mo>±</mml:mo><mml:mn>299</mml:mn></mml:mrow></mml:math></inline-formula> pmol m<inline-formula><mml:math display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">2</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula> h<inline-formula><mml:math display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula> for dibromomethane compared to other oceanic
regions (e.g. Fuhlbrügge et al., 2013; Hepach et al., 2015), but for
methyl iodide the fluxes were elevated at <inline-formula><mml:math display="inline"><mml:mrow><mml:mn>856</mml:mn><mml:mo>±</mml:mo><mml:mn>623</mml:mn></mml:mrow></mml:math></inline-formula> pmol m<inline-formula><mml:math display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">2</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula> h<inline-formula><mml:math display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula> (Fig. 3g, Table 1). Further investigations of
the distributions and sources of iodinated compounds during this cruise are
carried out by Hepach et al. (2016).</p>
</sec>
<sec id="Ch1.S3.SS3">
  <title>Lower atmosphere conditions</title>
      <p>A strong positive vertical gradient of relative humidity at <inline-formula><mml:math display="inline"><mml:mo>∼</mml:mo></mml:math></inline-formula> 1 km
height (Fig. 4a) indicates an increase in the atmospheric stability. This
convective barrier, known as the trade inversion (Riehl, 1954, 1979;
Höflich, 1972), is also reflected in the meridional wind (Fig. 4b). Below
<inline-formula><mml:math display="inline"><mml:mo>∼</mml:mo></mml:math></inline-formula> 1 km altitude the south-easterly trade winds create a strong
positive meridional wind component, also visible in the forward trajectories
(Fig. 1c–d). The flow of air masses in the Hadley cell back to the
subtropics causes a predominantly northerly wind above <inline-formula><mml:math display="inline"><mml:mo>∼</mml:mo></mml:math></inline-formula> 1 km height.
The intense increase in <inline-formula><mml:math display="inline"><mml:mrow><mml:msub><mml:mi mathvariant="italic">θ</mml:mi><mml:mi>v</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> in combination with the relative
humidity decrease and the wind shear at <inline-formula><mml:math display="inline"><mml:mo>∼</mml:mo></mml:math></inline-formula> 1 km height identifies this
level as a strong vertical transport barrier (Fig. 4c). Above the cold
upwelling water, temperature inversions create additional stable layers above
the surface, leading to very low MABL heights of <inline-formula><mml:math display="inline"><mml:mo>&lt;</mml:mo></mml:math></inline-formula> 100 m (e.g. on 3, 8
or 17 December 2012) and a reduced vertical transport of surface air. The
mean MABL height from the radiosonde observations is <inline-formula><mml:math display="inline"><mml:mrow><mml:mn>370</mml:mn><mml:mo>±</mml:mo><mml:mn>170</mml:mn></mml:mrow></mml:math></inline-formula> m
(ERA-Interim <inline-formula><mml:math display="inline"><mml:mrow><mml:mn>376</mml:mn><mml:mo>±</mml:mo><mml:mn>169</mml:mn></mml:mrow></mml:math></inline-formula> m). The relative humidity, SAT, SST and wind
speed show significant correlations with the observed MABL height (Table 2).
The regressed MABL heights (Sect. 2.2) show a distinct decrease above the
cold upwelling regions close to the coast with <inline-formula><mml:math display="inline"><mml:mrow><mml:mn>158</mml:mn><mml:mo>±</mml:mo><mml:mn>79</mml:mn></mml:mrow></mml:math></inline-formula> m on average.
Taking the regressed MABL height into account, the mean MABL height during
the cruise decreases to <inline-formula><mml:math display="inline"><mml:mrow><mml:mn>307</mml:mn><mml:mo>±</mml:mo><mml:mn>177</mml:mn></mml:mrow></mml:math></inline-formula> m. The stable atmospheric conditions
from the surface to the trade inversion lead to strong transport barriers
also visible in the accumulation of below 2-day-old air masses within the
first kilometre of the atmosphere (Fig. 4d).</p>
</sec>
<sec id="Ch1.S3.SS4">
  <title>Contribution of oceanic emissions to VSLS abundances in the MABL</title>
      <p>We estimate the contribution of oceanic emissions to mixing ratios within the
MABL and below the trade inversion with a VSLS source–loss estimate
(Table 3). The mean loss of VSLSs out of the MABL box is 351.0 % d<inline-formula><mml:math display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula>
and equal for all compounds, since it is computed from the loss of
trajectories out of the box. The loss is based on a mean residence time of
the FLEXPART trajectories of 7 h in the observed in situ MABL height during
the cruise. The ratio of the individual OD of each compound and the COL at
this location results in the particular ODR for each compound. The ODR
reveals that on average only 3 % of the observed atmospheric bromoform in
the MABL originates from local oceanic emissions and 99 % are advected
including a chemical loss of 2 %. The numbers show that the observed mean
atmospheric concentrations cannot be explained by the mean local oceanic
emissions. While the surface air masses can leave the MABL within hours, they
are restricted from entering the free troposphere through the trade
inversion. FLEXPART trajectories indicate an average residence time of air
48 h below the average trade inversion height of 1.1 km. During the 48 h
and the prevailing southerly mean wind speed of 6.2 m s<inline-formula><mml:math display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula> oceanic VSLS
emissions can accumulate over a fetch of 10<inline-formula><mml:math display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula> latitude. The impact of
these conditions on VSLS emissions is discussed in Sect. 4.</p>

<?xmltex \floatpos{t}?><table-wrap id="Ch1.T3" specific-use="star"><caption><p>VSLS source–loss calculations: mean <inline-formula><mml:math display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula>1<inline-formula><mml:math display="inline"><mml:mi mathvariant="italic">σ</mml:mi></mml:math></inline-formula> of oceanic
delivery (OD), advective delivery (AD), chemical loss (CL), convective loss
(COL), oceanic delivery ratio (ODR), advective delivery ratio (ADR) and
chemical loss ratio (CLR) of bromoform (CHBr<inline-formula><mml:math display="inline"><mml:mrow><mml:msub><mml:mi/><mml:mn mathvariant="normal">3</mml:mn></mml:msub><mml:mo>)</mml:mo></mml:mrow></mml:math></inline-formula>, dibromomethane
(CH<inline-formula><mml:math display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>Br<inline-formula><mml:math display="inline"><mml:mrow><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub><mml:mo>)</mml:mo></mml:mrow></mml:math></inline-formula> and methyl iodide (CH<inline-formula><mml:math display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:math></inline-formula>I). Parameters have been
computed for a box with the vertical extension of the in situ MABL height
(MABLH) and a mean trade inversion height (TIH) of 1.1 km.</p></caption><oasis:table frame="topbot"><oasis:tgroup cols="9">
     <oasis:colspec colnum="1" colname="col1" align="left"/>
     <oasis:colspec colnum="2" colname="col2" align="left"/>
     <oasis:colspec colnum="3" colname="col3" align="right"/>
     <oasis:colspec colnum="4" colname="col4" align="right"/>
     <oasis:colspec colnum="5" colname="col5" align="right"/>
     <oasis:colspec colnum="6" colname="col6" align="right"/>
     <oasis:colspec colnum="7" colname="col7" align="right"/>
     <oasis:colspec colnum="8" colname="col8" align="right"/>
     <oasis:colspec colnum="9" colname="col9" align="right"/>
     <oasis:thead>
       <oasis:row>  
         <oasis:entry colname="col1"/>  
         <oasis:entry colname="col2"/>  
         <oasis:entry colname="col3">OD</oasis:entry>  
         <oasis:entry colname="col4">AD</oasis:entry>  
         <oasis:entry colname="col5">CL</oasis:entry>  
         <oasis:entry colname="col6">COL</oasis:entry>  
         <oasis:entry colname="col7">ODR</oasis:entry>  
         <oasis:entry colname="col8">ADR</oasis:entry>  
         <oasis:entry colname="col9">CLR</oasis:entry>
       </oasis:row>
       <oasis:row rowsep="1">  
         <oasis:entry colname="col1"/>  
         <oasis:entry colname="col2"/>  
         <oasis:entry colname="col3">[% d<inline-formula><mml:math display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula>]</oasis:entry>  
         <oasis:entry colname="col4">[% d<inline-formula><mml:math display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula>]</oasis:entry>  
         <oasis:entry colname="col5">[% d<inline-formula><mml:math display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula>]</oasis:entry>  
         <oasis:entry colname="col6">[% d<inline-formula><mml:math display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula>]</oasis:entry>  
         <oasis:entry colname="col7"/>  
         <oasis:entry colname="col8"/>  
         <oasis:entry colname="col9"/>
       </oasis:row>
     </oasis:thead>
     <oasis:tbody>
       <oasis:row>  
         <oasis:entry colname="col1">CHBr<inline-formula><mml:math display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:math></inline-formula></oasis:entry>  
         <oasis:entry rowsep="1" colname="col2">MABLH</oasis:entry>  
         <oasis:entry rowsep="1" colname="col3">9.1 <inline-formula><mml:math display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 28.0</oasis:entry>  
         <oasis:entry rowsep="1" colname="col4">349.0 <inline-formula><mml:math display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 113.4</oasis:entry>  
         <oasis:entry rowsep="1" colname="col5">7.1</oasis:entry>  
         <oasis:entry rowsep="1" colname="col6">351.0 <inline-formula><mml:math display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 109.4</oasis:entry>  
         <oasis:entry rowsep="1" colname="col7">0.03 <inline-formula><mml:math display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.08</oasis:entry>  
         <oasis:entry rowsep="1" colname="col8">0.99 <inline-formula><mml:math display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.08</oasis:entry>  
         <oasis:entry rowsep="1" colname="col9">0.02 <inline-formula><mml:math display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.01</oasis:entry>
       </oasis:row>
       <oasis:row rowsep="1">  
         <oasis:entry colname="col1"/>  
         <oasis:entry colname="col2">TIH</oasis:entry>  
         <oasis:entry colname="col3">3.9 <inline-formula><mml:math display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 12.0</oasis:entry>  
         <oasis:entry colname="col4">53.2 <inline-formula><mml:math display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 23.2</oasis:entry>  
         <oasis:entry colname="col5">7.1</oasis:entry>  
         <oasis:entry colname="col6">50.0 <inline-formula><mml:math display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 18.4</oasis:entry>  
         <oasis:entry colname="col7">0.11 <inline-formula><mml:math display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.4</oasis:entry>  
         <oasis:entry colname="col8">1.06 <inline-formula><mml:math display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.39</oasis:entry>  
         <oasis:entry colname="col9">0.17 <inline-formula><mml:math display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.07</oasis:entry>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1">CH<inline-formula><mml:math display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>Br<inline-formula><mml:math display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula></oasis:entry>  
         <oasis:entry rowsep="1" colname="col2">MABLH</oasis:entry>  
         <oasis:entry rowsep="1" colname="col3">32.1 <inline-formula><mml:math display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 38.7</oasis:entry>  
         <oasis:entry rowsep="1" colname="col4">320.1 <inline-formula><mml:math display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 115.6</oasis:entry>  
         <oasis:entry rowsep="1" colname="col5">1.2</oasis:entry>  
         <oasis:entry rowsep="1" colname="col6">351.0 <inline-formula><mml:math display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 109.4</oasis:entry>  
         <oasis:entry rowsep="1" colname="col7">0.10 <inline-formula><mml:math display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.11</oasis:entry>  
         <oasis:entry rowsep="1" colname="col8">0.90 <inline-formula><mml:math display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.11</oasis:entry>  
         <oasis:entry rowsep="1" colname="col9">0.00 <inline-formula><mml:math display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.00</oasis:entry>
       </oasis:row>
       <oasis:row rowsep="1">  
         <oasis:entry colname="col1"/>  
         <oasis:entry colname="col2">TIH</oasis:entry>  
         <oasis:entry colname="col3">13.8 <inline-formula><mml:math display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 16.5</oasis:entry>  
         <oasis:entry colname="col4">37.4 <inline-formula><mml:math display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 25.9</oasis:entry>  
         <oasis:entry colname="col5">1.2</oasis:entry>  
         <oasis:entry colname="col6">50.0 <inline-formula><mml:math display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 18.4</oasis:entry>  
         <oasis:entry colname="col7">0.33 <inline-formula><mml:math display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.54</oasis:entry>  
         <oasis:entry colname="col8">0. 7 <inline-formula><mml:math display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.54</oasis:entry>  
         <oasis:entry colname="col9">0.03 <inline-formula><mml:math display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.01</oasis:entry>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1">CH<inline-formula><mml:math display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:math></inline-formula>I</oasis:entry>  
         <oasis:entry rowsep="1" colname="col2">MABLH</oasis:entry>  
         <oasis:entry rowsep="1" colname="col3">88.9 <inline-formula><mml:math display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 48.1</oasis:entry>  
         <oasis:entry rowsep="1" colname="col4">286.1 <inline-formula><mml:math display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 119.7</oasis:entry>  
         <oasis:entry rowsep="1" colname="col5">24.0</oasis:entry>  
         <oasis:entry rowsep="1" colname="col6">351.0 <inline-formula><mml:math display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 109.4</oasis:entry>  
         <oasis:entry rowsep="1" colname="col7">0.28 <inline-formula><mml:math display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.17</oasis:entry>  
         <oasis:entry rowsep="1" colname="col8">0.80 <inline-formula><mml:math display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.16</oasis:entry>  
         <oasis:entry rowsep="1" colname="col9">0.08 <inline-formula><mml:math display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.03</oasis:entry>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1"/>  
         <oasis:entry colname="col2">TIH</oasis:entry>  
         <oasis:entry colname="col3">36.8 <inline-formula><mml:math display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 20.5</oasis:entry>  
         <oasis:entry colname="col4">37.2 <inline-formula><mml:math display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 32.1</oasis:entry>  
         <oasis:entry colname="col5">24.0</oasis:entry>  
         <oasis:entry colname="col6">50.0 <inline-formula><mml:math display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 18.4</oasis:entry>  
         <oasis:entry colname="col7">0.92 <inline-formula><mml:math display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.69</oasis:entry>  
         <oasis:entry colname="col8">0.64 <inline-formula><mml:math display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.55</oasis:entry>  
         <oasis:entry colname="col9">0.56 <inline-formula><mml:math display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.24</oasis:entry>
       </oasis:row>
     </oasis:tbody>
   </oasis:tgroup></oasis:table></table-wrap>

<?xmltex \hack{\newpage}?>
</sec>
<sec id="Ch1.S3.SS5">
  <title>Meteorological constraints on atmospheric VSLSs in the MABL</title>
      <p>We find significantly high correlations between meteorological parameters and
the abundances of bromoform, dibromomethane and methyl iodide (Table 2) along
the Peruvian coast. The predominantly moderate winds during the cruise are
negatively correlated with the atmospheric VSLSs and positively correlated
with the MABL height. This shows that VSLS abundances tend to be elevated
during periods of lower wind speeds, which lead to reduced mixing of surface
air and therefore to lower MABL heights, in particular above the coastal
upwelling events on 11, 15–17 and 24 December 2012. No significant
correlation is found between the oceanic emissions and the atmospheric VSLSs
(not shown), revealing a stronger influence of the wind speed on the
atmospheric accumulation of the VSLSs rather than the oceanic emissions. SAT
and SST are both negatively correlated with atmospheric VSLSs, since elevated
atmospheric VSLS mixing ratios are generally found close to the oceanic
upwelling regions with low SATs and SSTs. In these regions the decrease in
the SATs leads to an increase in the relative humidity (Sect. 3.1), which
results in a significantly high correlation with the VSLSs. Since SAT and SST
impact the MABL, which affects the relative humidity, these correlation
coefficients are co-correlated. Correlation coefficients between the MABL
height and the VSLSs are slightly lower (Table 2). A principal component
analysis of the parameters in Table 2 also confirmed the strong connection
between SAT, SST, MABL height, relative humidity and atmospheric mixing
ratios of bromoform and dibromomethane (not shown here).</p>
</sec>
<sec id="Ch1.S3.SS6">
  <title>Comparison to other oceanic regions</title>
      <p>Surface water concentrations of bromoform in the Peruvian upwelling during
the cruise were generally lower compared to observations in other coastal
upwelling regions, e.g. the Mauritanian upwelling (Carpenter et al., 2010;
Fuhlbrügge et al., 2013; Hepach et al., 2014). While dibromomethane
concentrations are comparable, methyl iodide concentrations are almost 8
times higher than in the Mauritanian upwelling (Fig. 3d, Table 1; Hepach et
al., 2014). Atmospheric mixing ratios of bromoform and dibromomethane are
significantly lower above the Peruvian upwelling compared to observations
above the Mauritanian upwelling, while methyl iodide mixing ratios are
comparable (Fuhlbrügge et al., 2013).</p>
      <p>MABL properties (height and stability) reveal a stronger influence on the
VSLS abundances at the marine surface during the DRIVE cruise covering the
Mauritanian upwelling compared to this study (M91) covering the Peruvian
upwelling (Fig. 5). Observed local oceanic bromocarbon emissions can only
partly explain the atmospheric VSLS concentrations above the Peruvian
upwelling, while above the Mauritanian upwelling the generally higher
emissions could occasionally explain up to 100 % of the atmospheric
abundances of VSLSs in very low and stable MABL conditions (Fuhlbrügge et
al., 2013; Hepach et al., 2014). The predominantly southerly winds along the
western coastline of Peru allowed only minor continental influence on the
offshore coastal atmosphere, while the Mauritanian upwelling showed a larger
variation in maritime and continental air masses. Although our investigations
revealed low MABL heights close to the Peruvian coast, the maritime air mass
origin led to less developed surface inversions compared to those observed
above the Mauritanian upwelling, where the higher emissions led to a stronger
and more variable enrichment in the MABL. This can lead to the observed
higher correlation coefficients between the MABL height and the VSLS
abundances in the Mauritanian upwelling (Fig. 5).</p>

      <?xmltex \floatpos{t}?><fig id="Ch1.F5"><caption><p>Scatter plots of near-surface atmospheric mixing ratios of
bromoform, dibromomethane, methyl iodide and relative humidity vs. MABL
height. Black circles reflect observations from the DRIVE campaign covering
the Mauritanian upwelling (Fuhlbrügge et al., 2013) and red circles from
this study (M91) covering the Peruvian upwelling. <inline-formula><mml:math display="inline"><mml:mrow><mml:msub><mml:mi>R</mml:mi><mml:mtext>total</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula> gives the
Spearman correlation coefficients for both datasets together.</p></caption>
          <?xmltex \igopts{width=236.157874pt}?><graphic xlink:href="https://acp.copernicus.org/articles/16/12205/2016/acp-16-12205-2016-f05.pdf"/>

        </fig>

      <p>Compared to the two eastern boundary upwelling systems, observed VSLS sources
at the coasts of the South China and Sulu seas were significantly higher
(Fuhlbrügge et al., 2016). Despite the elevated emissions there, the
atmospheric VSLS abundances in the West Pacific were lower, due to the
presence of a convective active, well-ventilated MABL. The comparison between
the different regions demonstrates that the atmospheric abundances of VSLSs
over the ocean are significantly controlled by prevailing meteorological
conditions next to their oceanic sources and emissions.</p>
</sec>
</sec>
<sec id="Ch1.S4">
  <title>Discussion</title>
      <p>Compounds emitted from the Peruvian upwelling are first homogeneously
distributed within the MABL in only a few hours according to the observations
during the M91 cruise. Afterwards the emitted compounds are distributed
within and transported below the trade inversion. For air masses above or
close to oceanic upwelling regions, the MABL height is the first transport
barrier on short timescales, while the trade inversion acts as a second,
more pronounced barrier for vertical transport on longer timescales. The
residence time of air masses below the trade inversion of 48 h leads to a
stronger enrichment of VSLSs from the oceanic emissions, reflected in the OD
(Table 3), compared to the enrichment in the MABL. For the mean wind speed of
6.2 m s<inline-formula><mml:math display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula> and wind direction of 160<inline-formula><mml:math display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula> observed during the
cruise, air masses accumulate oceanic emissions from approximately 1.5<inline-formula><mml:math display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>
latitude distance during the residence time of 7 h in the MABL and below the
trade wind inversion from approximately 10<inline-formula><mml:math display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula> latitude during 48 h, which
covers the southern Peruvian as well as part of the Chilean coast.</p><?xmltex \hack{\newpage}?>
<sec id="Ch1.S4.SS1">
  <title>Accumulation of background concentrations</title>
      <p>The observed near-surface atmospheric mixing ratios suggest background
concentrations of the compounds which were around 2 ppt for CHBr<inline-formula><mml:math display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:math></inline-formula>,
0.8 ppt of CH<inline-formula><mml:math display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>Br<inline-formula><mml:math display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula> and 1 ppt for CH<inline-formula><mml:math display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:math></inline-formula>I (Figs. 3e and 5). The
back-trajectories revealed air masses originating from the southern Peruvian
and Chilean coast, which were transported along the coast for about 5 days.
In combination with a stable MABL and a distinct trade inversion acting as
strong barriers to the vertical mixing of trace gases, these air masses
travelled close to the surface where they could be enriched during 48 h with
regional emissions before they enter the free troposphere. Mean emissions of
around 2000 pmol m<inline-formula><mml:math display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">2</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula> h<inline-formula><mml:math display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula> for CHBr<inline-formula><mml:math display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:math></inline-formula> and for CH<inline-formula><mml:math display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:math></inline-formula>I and
800 pmol m<inline-formula><mml:math display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">2</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula> h<inline-formula><mml:math display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula> for CH<inline-formula><mml:math display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>Br<inline-formula><mml:math display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula> would have been needed
during the residence time of 48 h of air below the trade wind inversion to
reach the elevated background concentrations observed on board the ship.
These emissions are close to the maximum observed during the cruise and are
frequently observed in other coastal oceanic regions (Quack and Wallace,
2003; Carpenter and Liss, 2000; Carpenter et al., 2014; Ziska et al., 2013). Thus, although our measurements
along the cruise track did not reflect conditions that produced an average
ocean emission rate sufficient to support high background VSLS abundances, we
propose that higher emissions may be present at other times and locations
along the coast, which were passed by the air mass trajectories (Fig. 1) and
added additional VSLSs to the MABL. We suspect that waters very close to the
coast, where generally elevated concentrations of the bromocarbons are found
(Carpenter et al., 2005; Leedham et al., 2013; Ziska et al., 2013), might
even be stronger source regions although these areas were not crossed by the
cruise track.</p>
</sec>
<sec id="Ch1.S4.SS2">
  <title>Maximum mixing ratios in the coastal upwelling</title>
      <p>In addition to the background concentrations, Fig. 5 shows the good
correlation of MABL height and the three atmospheric VSLSs. The slopes reveal
approximately 0.5 ppt per 100 m MABL height for CHBr<inline-formula><mml:math display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:math></inline-formula>, 0.2 ppt for
CH<inline-formula><mml:math display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>Br<inline-formula><mml:math display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula> and 0.3 ppt for CH<inline-formula><mml:math display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:math></inline-formula>I, yielding mean maximum mixing
ratios of around 4.5 ppt for CHBr<inline-formula><mml:math display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:math></inline-formula>, 1.8 ppt for CH<inline-formula><mml:math display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>Br<inline-formula><mml:math display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula> and
2.4 ppt for CH<inline-formula><mml:math display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:math></inline-formula>I in the lowest observed MABL heights. The difference of
2.5 ppt for CHBr<inline-formula><mml:math display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:math></inline-formula>, 1.0 ppt for CH<inline-formula><mml:math display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>Br<inline-formula><mml:math display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula> and 1.4 ppt for CH<inline-formula><mml:math display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:math></inline-formula>I
to the accumulated background concentration requires mean source fluxes of
2500 pmol m<inline-formula><mml:math display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">2</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula> h<inline-formula><mml:math display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula> for CHBr<inline-formula><mml:math display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:math></inline-formula>, 1000 pmol m<inline-formula><mml:math display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">2</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula> h<inline-formula><mml:math display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula> for CH<inline-formula><mml:math display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>Br<inline-formula><mml:math display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula> and
1400 pmol m<inline-formula><mml:math display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">2</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula> h<inline-formula><mml:math display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula> for CH<inline-formula><mml:math display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:math></inline-formula>I into a stable MABL height of 100 m during 4 h
accumulation. Although the mean fluxes during the cruise were lower, higher
fluxes of 2000 pmol m<inline-formula><mml:math display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">2</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula> h<inline-formula><mml:math display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula> for CHBr<inline-formula><mml:math display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:math></inline-formula>, 1000 pmol m<inline-formula><mml:math display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">2</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula> h<inline-formula><mml:math display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula> for
CH<inline-formula><mml:math display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>Br<inline-formula><mml:math display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula> and 4000 pmol m<inline-formula><mml:math display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">2</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula> h<inline-formula><mml:math display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula> for CH<inline-formula><mml:math display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:math></inline-formula>I were occasionally observed, especially
near the coastline (Fig. 3, Table 1), which plays an important role as a
source region for the trace gases. As an example, the same coastal upwelling
region was crossed two times during the cruise (17 and 25 December 2012).
While other conditions where similar, the wind direction on the second
occasion was from the coast and the air showed elevated atmospheric mixing
ratios compared to the first occasion. Thus, we strongly believe that major
source regions for the accumulation of the VSLSs below the stable MABL and the
distinct trade wind inversion above the coastal upwelling are associated with
the coastal upwelling waters and regions even closer to the coastlines,
which are also under the influence of steady and stable meteorological
conditions due to topography and the upwelling of cold waters along the
Peruvian and Chilean coast. Overall, we suggest that the observed high
atmospheric mixing ratios above the Peruvian upwelling resulted from the
close interaction between steady meteorological conditions, advection of
elevated background air, increased atmospheric stability above the cold
oceanic upwelling region, and VSLS sources in the coastal upwelling itself
and even closer to the shore line, which we were not able to examine during
our cruise.</p>
</sec>
<sec id="Ch1.S4.SS3">
  <title>Transport from the upwelling</title>
      <p>After the air masses were observed on R/V <italic>METEOR</italic>, the 10-day forward
trajectories revealed a near-surface transport towards the Equator (Fig. 1).
These trajectories predominantly stayed below 1 km altitude due to the
horizontal extent of the trade inversion. A contribution of oceanic emissions
from the Peruvian upwelling to the free troposphere is only achieved in the
inner tropics after a transport time of 5–8 days, where the VSLS abundances
were transported into higher altitudes. Since the lifetime of methyl iodide
is only 4 days in the MABL, a significant contribution of methyl iodide
from the Peruvian upwelling to observations made by Yokouchi et al. (2008) at
San Cristóbal, Galápagos, cannot be expected. However, it can partly explain
the elevated IO observed above the Peruvian upwelling (Schönhardt et al.,
2008), which is further investigated by the companion study of Hepach et
al. (2016). The low contribution of oceanic emissions and boundary layer air
to the free troposphere in this region is representative for the prevalent
neutral El Niño–Southern Oscillation (ENSO) conditions as were observed
during December 2012 (ENSO Diagnostic Discussion, NCEP/CPC issue,
November 2012). Different ENSO conditions can be expected to influence VSLS
air–sea interactions above the Peruvian upwelling and should be investigated
in future studies.</p>
</sec>
<sec id="Ch1.S4.SS4">
  <title>Uncertainties</title>
      <p>Uncertainties in our study may result from the applied method, which takes
in situ observations during the cruise and close to the ship's position into
account. Although the cruise track covered a significant area of the
Peruvian upwelling between 5 and 16<inline-formula><mml:math display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula> S, elevated sea surface
concentrations and emissions, especially closer to coastlines, may have
contributed to the observed VSLS abundances, which were not sampled during
the cruise. In regions with low MABL heights very close to the coast, where
the source–loss estimate could not be applied due to trajectory analysis gaps
(Sect. 2.4), potentially high emissions in combination with the stable
atmospheric stratification could significantly increase the oceanic
contribution to the MABL. Different parameterizations for the wind-based
transfer coefficient <inline-formula><mml:math display="inline"><mml:mrow><mml:msub><mml:mi>k</mml:mi><mml:mi>w</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula>, as discussed in Lennartz et al. (2015) and
Fuhlbrügge et al. (2016), lead only to an overall difference of 34 %
in the calculated oceanic emissions during M91, due to the relatively low
prevailing winds. Additional uncertainties in our source–loss estimate may
arise from deficiencies in the meteorological input fields from ERA-Interim
reanalysis as well as from the air mass transport simulated by FLEXPART, but
these uncertainties are difficult to quantify. Both could lead to either a
shorter or longer residence time of the surface air masses within the MABL or
below the trade inversion. However, Fuhlbrügge et al. (2016) showed that
differences in the MABL height of ERA-Interim and radiosonde observations
affect the computed ODR only marginally. Further uncertainties may arise from
spatial variations in the VSLS lifetimes and thus the chemical degradation of
the compounds we used in this study. These effects are expected to be small
for bromoform and dibromomethane since the overall impact of photochemical
loss rates is only a few percent of the total budget. The uncertainty in
chemical loss rates for methyl iodide is larger, and more detailed photolysis
rate calculations and actinic flux measurements would be useful to better
constrain this process for compounds whose main loss is through photolysis.
Finally, future studies need to investigate in particular the near-coastal
processes and sources to estimate their contribution to the air–sea gas
exchange and lower atmospheric VSLS abundances above the Peruvian upwelling.</p>
</sec>
</sec>
<sec id="Ch1.S5" sec-type="conclusions">
  <title>Summary</title>
      <p>This study investigated the contribution of oceanic emissions to VSLS
abundances in the lowermost atmosphere above coastal upwelling and open-ocean
regions along the Peruvian coast during December 2012. Meteorological data
were obtained on R/V <italic>METEOR</italic> and by radiosondes up to the
stratosphere. Oceanic VSLS emissions along the cruise track were determined
from air and surface water measurements. The transport of air masses was
calculated with FLEXPART trajectories using ERA-Interim reanalysis. All data were
synthesized in a source–loss model, investigating the influences of VSLS
emissions and atmospheric transport on the observed VSLS abundances.</p>
      <p>Oceanic upwelling was observed close to the Peruvian coast, which strongly
impacted meteorological conditions in this region. On average a low, stable
MABL height of 307 <inline-formula><mml:math display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 177 m was encountered during the cruise,
decreasing to about 100 m above the upwelling. A distinct trade inversion at
1.1 <inline-formula><mml:math display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.3 km height was identified as the dominant transport barrier
for MABL air into the free troposphere during the cruise. The halogenated
VSLSs bromoform and dibromomethane showed low average oceanic emissions of
117 <inline-formula><mml:math display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 492 pmol m<inline-formula><mml:math display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">2</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula> h<inline-formula><mml:math display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula> for bromoform and
245 <inline-formula><mml:math display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 299 pmol m<inline-formula><mml:math display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">2</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula> h<inline-formula><mml:math display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula> for dibromomethane, while methyl
iodide emissions were elevated at 856 <inline-formula><mml:math display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 623 pmol m<inline-formula><mml:math display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">2</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula> h<inline-formula><mml:math display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula>. In contrast, the atmospheric
mixing ratios of the compounds were elevated compared to average open-ocean
regions with 2.9 <inline-formula><mml:math display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.7 ppt (bromoform), 1.3 <inline-formula><mml:math display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.3 ppt
(dibromomethane) and 1.5 <inline-formula><mml:math display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.5 ppt (methyl iodide). The mean oceanic
emissions along the cruise track explained on average 3 % (<inline-formula><mml:math display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>8 to
33 %) of bromoform, 10 % (<inline-formula><mml:math display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>5 to 45 %) of dibromomethane, and
28 % (3 to 80 %) of methyl iodide abundances in the MABL. Thus, the
significant contribution of local oceanic VSLS emissions to the overlying
atmosphere that we expected was not captured during the time and location of
our sample collection, showing the need for a separation of transported
and local signals. The elevated atmospheric VSLS background concentrations in
the region appear largely advected and enriched below the trade wind
inversion during 2 days of transport from further south. The pronounced
stable and steady atmospheric conditions close to the Peruvian and Chilean
coast led, during a few hours, to an additional accumulation and increase in
the atmospheric VSLS mixing ratios above the coastal upwelling, where
stronger source regions are likely to exist close to the coastline, which
were not sampled during the cruise.</p>
      <p>Our study demonstrates the close linkage between VSLS abundances and
stability of the MABL. Additionally, a pronounced trade inversion can lead
to a near-surface accumulation of the VSLSs and thus also impacts oceanic
emissions. Further studies are necessary to investigate the coastal and nearshore source regions of the elevated atmospheric VSLSs in the Peruvian
upwelling during different seasons and ENSO conditions.</p>
</sec>
<sec id="Ch1.S6">
  <title>Data availability</title>
      <p>The underlying data are available at the open-access library Pangaea (<uri>http://www.pangaea.de</uri>).
Model outputs can be acquired from the corresponding author.</p>
</sec>

      
      </body>
    <back><ack><title>Acknowledgements</title><p>This study was supported by BMBF grant SOPRAN II FKZ 03F0611A. We
acknowledge the authorities of Peru for the permissions to work in their
territorial waters. We thank the European Centre for Medium-Range Weather
Forecasts (ECMWF) for the provision of ERA-Interim reanalysis data and the
Lagrangian particle dispersion model FLEXPART used in this publication. We
would also like to thank the captain and crew of R/V <italic>METEOR</italic>, and the
Deutscher Wetterdienst (DWD) for the support. E. Atlas acknowledges financial
support of his work through the Upper Atmosphere Research Program of the US
NASA. Additional thanks go to the editor, H. Bange, for leading the review process,
as well as to the two anonymous reviewers for their helpful comments to improve the manuscript.<?xmltex \hack{\newline}?><?xmltex \hack{\newline}?> Edited by: H. Bange<?xmltex \hack{\newline}?>
Reviewed by: two anonymous referees</p></ack><ref-list>
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    <!--<article-title-html>Meteorological constraints on oceanic halocarbons above the Peruvian
upwelling</article-title-html>
<abstract-html><p class="p">During a cruise of R/V <i>METEOR</i> in December 2012 the oceanic sources and
emissions of various halogenated trace gases and their mixing ratios in the
marine atmospheric boundary layer (MABL) were investigated above the
Peruvian upwelling. This study presents novel observations of the three very
short lived substances (VSLSs) – bromoform, dibromomethane and methyl iodide – together with high-resolution meteorological measurements, Lagrangian
transport and source–loss calculations. Oceanic emissions of bromoform and
dibromomethane were relatively low compared to other upwelling regions,
while those for methyl iodide were very high. Radiosonde launches during the
cruise revealed a low, stable MABL and a distinct trade inversion above
acting as strong barriers for convection and vertical transport of trace
gases in this region. Observed atmospheric VSLS abundances, sea surface
temperature, relative humidity and MABL height correlated well during the
cruise. We used a simple source–loss estimate to quantify the contribution
of oceanic emissions along the cruise track to the observed atmospheric
concentrations. This analysis showed that averaged, instantaneous emissions
could not support the observed atmospheric mixing ratios of VSLSs and that
the marine background abundances below the trade inversion were
significantly influenced by advection of regional sources. Adding to this
background, the observed maximum emissions of halocarbons in the coastal
upwelling could explain the high atmospheric VSLS concentrations in
combination with their accumulation under the distinct MABL and trade
inversions. Stronger emissions along the nearshore coastline likely added
to the elevated abundances under the steady atmospheric conditions. This
study underscores the importance of oceanic upwelling and trade wind systems
on the atmospheric distribution of marine VSLS emissions.</p></abstract-html>
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